Organic Semiconductor Compounds

Abstract

The present invention relates to novel organic semiconductor compounds containing polycyclic units, processes for their preparation and educts or intermediates used therein, compositions, polymer blends and formulations containing them, the use of the compounds, compositions and polymer blends as organic semiconductors in or for the preparation of organic electronic (OE) devices, in particular organic photovoltaic (OPV) devices, perovskite-based solar cell (PSC) devices, organic photodetectors (OPDs), organic field effect transistors (OFETs) and organic light-emitting diodes (OLEDs), and OE, OPV, PSC, OPD, OFET and OLED devices comprising these compounds, compositions or polymer blends.

Description

[Technical Field]

[0001] The present invention relates to novel organic semiconductor compounds containing polycyclic units, processes for their preparation and educts or intermediates used therein, compositions, polymer blends and formulations containing them, the use of the compounds, compositions and polymer blends as organic semiconductors in or for the preparation of organic electronic (OE) devices, in particular organic photovoltaic (OPV) devices, perovskite-based solar cell (PSC) devices, organic photodetectors (OPDs), organic field effect transistors (OFETs) and organic light emitting diodes (OLEDs), and OE, OPV, PSC, OPD, OFET and OLED devices comprising these compounds, compositions or polymer blends. [Background technology]

[0002] In recent years, there has been the development of organic semiconducting (OSC) materials to produce more versatile, lower-cost electronic devices. Such materials are utilized in a wide range of devices or apparatuses, including organic field effect transistors (OFETs), organic light-emitting diodes (OLEDs), organic photodetectors (OPDs), organic photovoltaic (OPV) cells, perovskite-based solar cell (PSC) devices, sensors, memory elements, and logic circuits, to name just a few. Organic semiconductor materials are typically present in electronic devices in the form of thin layers, e.g., 50-300 nm thick.

[0003] One specific area of ​​importance is organic photovoltaic devices (OPVs). Conjugated polymers are used in OPVs because they allow the devices to be fabricated by solution processing techniques such as spin-casting, dip-coating, or inkjet printing. Solution processing can be performed more cheaply and on a larger scale than the vapor deposition techniques used to make inorganic thin-film devices. Currently, polymer-based photovoltaic devices achieve efficiencies of over 10%.

[0004] Another specific area of ​​importance is OFETs. The performance of OFET devices is primarily based on the charge carrier mobility and current on / off ratio of the semiconductor material, so an ideal semiconductor would have high charge carrier mobility (>1×10 -3 cm 2 V -1 s -1 ), along with low conductivity in the off-state. Furthermore, it is important that the semiconducting material be stable to oxidation, i.e., have a high ionization potential, since oxidation leads to degradation of device performance. Further requirements for the semiconducting material are good processability, especially for large-scale production of thin layers and desired patterns, as well as high stability, film uniformity, and integrity of the organic semiconductor layer.

[0005] Organic photodetectors (OPDs) are an important further specific area where conjugated light-absorbing polymers offer the hope that efficient devices can be fabricated by solution processing techniques such as spin-casting, dip-coating or inkjet printing, to name just a few.

[0006] The photosensitive layer in an OPV or OPD device is usually composed of at least two materials: a p-type semiconductor (typically a conjugated polymer, oligomer, or defined molecular unit), and an n-type semiconductor (typically a fullerene or substituted fullerene, graphene, metal oxide, or quantum dot).

[0007] However, OSC materials disclosed in the prior art for use in OE devices have several drawbacks. They are often difficult to synthesize or purify (fullerenes) and / or do not absorb light strongly in the near-IR spectrum above 700 nm. Furthermore, other OSC materials often do not form the preferred morphology and / or donor phase compatibility for use in organic photovoltaic devices or organic photodetectors.

[0008] Therefore, there remains a need for OSC materials for use in OE devices such as OPVs, PSCs, OPDs, and OFETs that have advantageous properties, particularly good processability, high solubility in organic solvents, and good structural organization and film-forming properties. Furthermore, OSC materials should be easy to synthesize, particularly by methods suitable for mass production. For use in OPV cells and OPD devices, OSC materials should have low bandgaps, which can enable improved light harvesting by the photoactive layer and lead to higher cell efficiency, high stability, and long lifetimes. For use in OFETs, OSC materials should have high charge carrier mobility, high on / off ratios in transistor devices, high oxidative stability, and long lifetimes.

[0009] The object of the present invention was to provide novel OSC compounds, in particular n-type OSCs, which are able to overcome the drawbacks of OSCs from the prior art and which provide one or more of the above-mentioned advantageous properties, in particular easy synthesis by methods suitable for mass production, good processability, high stability, long lifetime in OE devices, good solubility in organic solvents, high charge carrier mobility, and low band gap. Another object of the present invention was to expand the pool of OSC materials and n-type OSCs available to the expert. Other objects of the present invention will be immediately apparent to the expert from the detailed description below.

[0010] The present inventors have discovered that one or more of the above objects may be achieved by providing the compounds disclosed and claimed below, which contain an indaceno-type polycyclic central unit as shown in Formula I.

[0011] It has been found that compounds comprising such a central polycyclic unit and further comprising two terminal electron-withdrawing groups can be used as n-type OSCs that exhibit the advantageous properties described above. Conjugated polymers based on linearly fused polycyclic aromatic units, such as indacenodithiophene (IDT), disclosed for example in U.S. Patent Nos. 5,629,999 and 5,729,999, or indacenodithienothiophene (IDTT), disclosed for example in U.S. Patent No. 5,729,999, have been disclosed in the prior art for use as p-type OSCs.

[0012] OSC small molecules with an IDT core have been proposed for use as chromophores in OLEDs by [1]. More recently, OSC small molecules containing an IDT or IDTT core end-capped with 2-(3-oxo-2,3-dihydroinden-1-ylidene)malononitrile have been reported for use as non-fullerene n-type OSCs in OPV devices, for example, by J. S. et al., J. Chem. Soc. 1999, 10, 1111-1112, and ... in U.S. Patent No. 5,613,711 and U.S. Patent No. 5,613,711. [Prior art documents] [Patent documents]

[0013] [Patent Document 1] International Publication No. 2010 / 020329 A1 Brochure [Patent Document 2] European Patent Application Publication No. 2075274 A1 [Patent Document 3] International Publication No. 2015 / 154845 A1 Brochure [Patent Document 4] Chinese Patent Application No. 104557968A [Patent Document 5] Chinese Patent Application No. 105315298 A [Non-patent literature]

[0014] [Non-Patent Document 1] KT. Wong, TC. Chao, LC. Chi, YY. Chu, A. Balaiah, SF. Chiu, YH. Liu, and Y. Wang, Organic Letters, 2006, 8, 5033 [Non-patent document 2] Y. Lin, J. Wang, Z.-G. Zhang, H. Bai, Y. Li, D. Zhu, and X. Zhan, Adv. Mater., 2015, 27, 1170 [Non-patent document 3] H. Lin, S. Chen, Z. Li, J. Y. Lai, G. Yang, T. McAfee, K. Jiang, Y. Li, Y. Liu, H. Hu, J. Zhao, W. Ma, H. Ade, and H. Yan, Zhan, Adv. Mater., 2015, 27, 7299 Summary of the Invention [Problem to be solved by the invention]

[0015] However, the compounds disclosed and claimed below have not previously been disclosed in the prior art. [Means for solving the problem]

[0016] The present invention relates to compounds of formula I

[0017] [ka]

[0018] wherein the individual radicals, independently of one another, on each occurrence, identically or differently, have the following meanings: Ar 2,3 arylene or heteroarylene having 5 to 20 ring atoms, which is monocyclic or polycyclic, optionally containing fused rings, and which is unsubstituted or substituted with one or more identical or different groups L; Ar 4,5 It has 5 to 20 ring atoms, is monocyclic or polycyclic, optionally contains fused rings, is unsubstituted or contains one or more identical or different groups L, or CY 1 =CY 2 or an arylene or heteroarylene substituted with -C≡C-; Y 1 , Y 2 H, F, Cl or CN, W 1,2 S, O or Se, U 1 CR 1 R 2 , SiR 1 R 2 , GeR 1 R 2 , N.R. 1 or C=O, U 2 CR 3 R 4 , SiR 3 R 4 , GeR 3 R 4 , N.R. 3 or C=O, R 1~4H, F, Cl or linear, branched or cyclic alkyl having 1 to 30, preferably 1 to 20, C atoms (wherein one or more CH groups are selected from -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 - or -C≡C-, one or more H atoms are optionally replaced by F, Cl, Br, I or CN, and one or more CH2 or CH3 groups are optionally replaced by cationic or anionic groups), or aryl, heteroaryl, arylalkyl, heteroarylalkyl, aryloxy or heteroaryloxy, wherein each of the above cyclic groups has 5 to 20 ring atoms, is monocyclic or polycyclic, optionally contains fused rings and is unsubstituted or substituted with one or more identical or different groups L; R 1 and R 2 Pairs of and / or R 3 and R 4 may also form, together with the C, Si or Ge atom to which they are attached, a spiro group having 5 to 20 ring atoms, which is monocyclic or polycyclic, optionally containing fused rings, and which is unsubstituted or substituted with one or more identical or different groups L, R T1 , R T2 a carbyl or hydrocarbyl group having 1 to 30 C atoms, optionally substituted with one or more groups L and optionally containing one or more heteroatoms, where R T1 and R T2 at least one of is an electron-withdrawing group, LF, Cl, -NO2, -CN, -NC, -NCO, -NCS, -OCN, -SCN, R 0 , OR 0 , S.R. 0 , -C(=O)X0 , -C(=O)R 0 , -C(=O)-OR 0 , -OC(=O)-R 0 , -NH2, -NHR 0 , -NR 0 R 00 , -C(=O)NHR 0 , -C(=O)NR 0 R 00 , -SO3R 0 , -SO2R 0 , -OH, -NO2, -CF3, -SF5, or optionally substituted silyl, or carbyl or hydrocarbyl having 1 to 30, preferably 1 to 20, C atoms, which are optionally substituted and optionally contain one or more heteroatoms, preferably F, -CN, R 0 , -OR 0 , -SR 0 , -C(=O)-R 0 , -C(=O)-OR 0 , -OC(=O)-R 0 , -OC(=O)-OR 0 , -C(=O)-NHR 0 , or -C(=O)-NR 0 R 00 , R 0 , R 00 H or optionally fluorinated linear or branched alkyl having 1 to 20, preferably 1 to 12, C atoms, X 0 halogen, preferably F or Cl, a, b 0, 1, 2 or 3, m 1, 2 or 3 It has.

[0019] The present invention further relates to novel synthetic methods for preparing compounds of formula I and novel intermediates used therein. The present invention further relates to the use of compounds of formula I as semiconductors, preferably as electron acceptors or n-type semiconductors, preferably in semiconductor materials, electronic or optoelectronic devices or components of electronic or optoelectronic devices.

[0020] The present invention further relates to the use of compounds of formula I as dyes or pigments. The present invention further relates to compositions comprising one or more compounds of Formula I and further comprising one or more compounds having one or more semiconducting, hole or electron transporting, hole or electron blocking, insulating, bonding, conductive, photoconductive, photoactive, or luminescent properties.

[0021] The present invention further relates to compositions comprising one or more compounds of Formula I and further comprising a binder, preferably an electrically inactive binder, and most preferably an electrically inactive polymeric binder.

[0022] The present invention further relates to compositions comprising a compound of formula I, further comprising one or more electron donors or p-type semiconductors, preferably selected from conjugated polymers. The present invention further relates to compositions comprising one or more n-type semiconductors, at least one of which is a compound of Formula I, and further comprising one or more p-type semiconductors.

[0023] The present invention further relates to compositions comprising one or more n-type semiconductors, at least one of which is a compound of Formula I and at least one of which is a fullerene or fullerene derivative, and further comprising one or more p-type semiconductors, preferably selected from conjugated polymers.

[0024] The present invention further relates to a bulk heterojunction (BHJ) formed from a composition comprising a compound of Formula I as an electron acceptor or n-type semiconductor, and one or more compounds that are electron donors or p-type semiconductors, preferably selected from conjugated polymers.

[0025] The present invention further relates to the use of compounds or compositions of Formula I as described above and below as semiconducting, charge transporting, conductive, photoconductive, photoactive or light emitting materials. The present invention further relates to the use of a compound or composition of formula I as described above and below in an electronic or optoelectronic device, or a component of such a device or an assembly comprising such a device.

[0026] The present invention further relates to semiconducting, charge transporting, electrically conductive, photoconducting, photoactive or light emitting materials comprising compounds or compositions of Formula I described above and below. The present invention further relates to electronic or optoelectronic devices comprising compounds or compositions of formula I described above and below, or components thereof, or assemblies comprising same.

[0027] The present invention further relates to electronic or optoelectronic devices comprising, or components thereof, or assemblies comprising, the semiconducting, charge transporting, electrically conductive, photoconducting or light emitting materials described above and below.

[0028] The present invention further relates to formulations comprising one or more compounds of formula I as described above and below, or comprising compositions or semiconducting materials, preferably further comprising one or more solvents selected from organic solvents.

[0029] The present invention further relates to the use of the formulations described above and below for the fabrication of electronic or optoelectronic devices or components thereof. The present invention further relates to electronic or optoelectronic devices or components thereof obtained by use of the formulations described above and below.

[0030] Electronic or optoelectronic devices include, but are not limited to, organic field effect transistors (OFETs), organic thin film transistors (OTFTs), organic light emitting diodes (OLEDs), organic light emitting transistors (OLETs), organic light emitting electrochemical cells (OLECs), organic photovoltaic devices (OPVs), organic photodetectors (OPDs), organic solar cells, dye-sensitized solar cells (DSSCs), organic photoelectrochemical cells (OPECs), perovskite-based solar cells (PSCs), laser diodes, Schottky diodes, photoconductors, photodetectors, and thermoelectric devices.

[0031] Preferred devices are OFETs, OTFTs, OPVs, PSCs, OPDs and OLEDs, in particular OPDs and BHJ OPVs or inverted BHJ OPVs. Components of electronic or optoelectronic devices include, but are not limited to, charge injection layers, charge transport layers, intermediate layers, planarization layers, antistatic films, polymer electrolyte membranes (PEMs), conductive substrates, and conductive patterns.

[0032] Assemblies containing electronic or optoelectronic devices include, but are not limited to, integrated circuits (ICs), radio frequency identification (RFID) tags, security marks, security devices, flat panel displays, backlights for flat panel displays, electrophotographic devices, electrophotographic recording devices, organic memory devices, sensor devices, biosensors, and biochips.

[0033] Additionally, the compounds of formula I and compositions described above and below can be used as electrode materials in batteries or in components or devices for detecting and identifying DNA sequences. Terms and Definitions As used herein, the term "polymer" is understood to mean a molecule of high relative molecular weight, the structure of which essentially comprises a plurality of repeating units derived, actually or conceptually, from a molecule of low relative molecular weight (Pure Appl. Chem., 1996, 68, 2291). The term "oligomer" is understood to mean a molecule of intermediate relative molecular weight, the structure of which essentially comprises a plurality of smaller units derived, actually or conceptually, from a molecule of lower relative molecular weight (Pure Appl. Chem., 1996, 68, 2291). In the preferred sense as used herein, polymer is understood to mean a compound having more than one repeating unit, i.e., at least two, preferably five or more, and very preferably ten or more, repeating units, and oligomer is understood to mean a compound having more than one and fewer than ten, preferably fewer than five, repeating units.

[0034] Furthermore, as used herein, the term "polymer" is understood to mean a molecule that includes a backbone (also called a "main chain") of one or more different types of repeating units (the smallest building blocks of a molecule), and includes commonly known terms such as "oligomer," "copolymer," "homopolymer," "random polymer," and the like. Furthermore, the term polymer is understood to include, in addition to the polymer itself, residues from initiators, catalysts, and other elements involved in the synthesis of such polymers, where such residues are understood to be not covalently incorporated into the polymer. Furthermore, while such residues and other elements are usually removed during post-polymerization purification processes, they are typically mixed or intermixed with the polymer so as to remain with the polymer when it is transferred between containers or solvents or dispersion media.

[0035] As used herein, in formulas representing polymers or repeat units, such as units of formula I or polymers of formula III or IV or subformulas thereof, an asterisk ( * ) will be understood to mean a chemical bond to an adjacent unit or end group in the polymer backbone. For example, in a ring such as a benzene or thiophene ring, an asterisk ( * ) will be understood to mean a C atom fused to an adjacent ring.

[0036] As used herein, the terms "repeat unit," "repeating unit," and "monomeric unit" will be used interchangeably and will be understood to mean a constitutional repeating unit (CRU), the repetition of which is the smallest building block that makes up a regular polymer, regular oligomeric molecule, regular block, or regular chain (Pure Appl. Chem., 1996, 68, 2291). As used further herein, the term "unit" will be understood to mean a structural unit that may be a repeating unit by itself or that may form a constitutional repeating unit together with other units.

[0037] As used herein, "end group" will be understood to mean a group that terminates the polymer backbone. The expression "at a terminal position of the backbone" will be understood to mean a divalent unit or repeat unit that is connected at one side to such an end group and at the other side to another repeat unit. Such an end group can be, for example, an R group, as defined below. 31 or R 32 or reactive groups attached to monomers forming the polymer backbone that do not participate in the polymerization reaction.

[0038] As used herein, the term "end-capping group" will be understood to mean a group attached to or substituting the terminal group of a polymer backbone. An end-capping group can be introduced into a polymer by an end-capping process. End-capping can be carried out, for example, by reacting the terminal group of the polymer backbone with a monofunctional compound ("end-capper") (such as, for example, an alkyl or aryl halide, an alkyl or aryl stannane, or an alkyl or aryl boronate). The end-capper can be added, for example, after the polymerization reaction. Alternatively, the end-capper can be added in situ to the reaction mixture before or during the polymerization reaction. In situ addition of an end-capper can also be used to terminate the polymerization reaction, thereby controlling the molecular weight of the polymer being formed. Typical end-capping groups are, for example, H, phenyl, and lower alkyl.

[0039] As used herein, the term "small molecule" will be understood to mean a monomeric compound that typically does not contain reactive groups that can be reacted to form a polymer and is shown to be used in monomeric form. In contrast, the term "monomer," unless otherwise specified, will be understood to mean a monomeric compound that possesses one or more reactive functional groups that can be reacted to form a polymer.

[0040] As used herein, the terms "donor" or "donating" and "acceptor" or "accepting" will be understood to mean an electron donor or electron acceptor, respectively. An "electron donor" will be understood to mean a chemical substance that donates electrons to another compound or another group of atoms in a compound. An "electron acceptor" will be understood to mean a chemical substance that accepts electrons transferred to it from another compound or another group of atoms in a compound. See also International Union of Pure and Applied Chemistry, Compendium of Chemical Technology, Gold Book, Edition 2.3.2, August 19, 2012, pp. 477 and 480.

[0041] As used herein, the terms "n-type" or "n-type semiconductor" will be understood to mean an extrinsic semiconductor in which the conduction electron density exceeds the mobile hole density, and the terms "p-type" or "p-type semiconductor" will be understood to mean an extrinsic semiconductor in which the mobile hole density exceeds the conduction electron density (see also J. Thewlis, Concise Dictionary of Physics, Pergamon Press, Oxford, 1973).

[0042] As used herein, the term "leaving group" will be understood to mean an atom or group (which may be charged or uncharged) that is cleaved from an atom that is considered to be the residue or major part of a molecule involved in a particular reaction (see also Pure Appl. Chem., 1994, 66, 1134).

[0043] As used herein, the term "conjugated" refers primarily to sp 2It is understood to mean compounds (e.g. polymers) containing C atoms with hybridization (or optionally also sp hybridization), and these C atoms can also be replaced by heteroatoms. In the simplest case, this is, for example, a compound with alternating C-C single and double (or triple) bonds, but also includes compounds with aromatic units such as 1,4-phenylene. The term "predominantly" in this context will be understood to mean that compounds with naturally occurring (spontaneously) occurring defects or defects included by design that can lead to interruptions in conjugation are still considered conjugated compounds.

[0044] As used herein, unless otherwise specified, molecular weight refers to the number average molecular weight M n or weight average molecular weight M W The degree of polymerization, n, also referred to as the total number of repeating units, is given as n = M, as determined by gel permeation chromatography (GPC) against polystyrene standards in an eluent solvent such as tetrahydrofuran, trichloromethane (TCM, chloroform), chlorobenzene, or 1,2,4-trichlorobenzene. Unless otherwise noted, chlorobenzene is used as the solvent. n / M U (In the formula, M n is the number average molecular weight, and M U where m is the molecular weight of a single repeating unit (see J. M. G. Cowie, Polymers: Chemistry & Physics of Modern Materials, Blackie, Glasgow, 1991).

[0045] As used herein, the term "carbyl group" will be understood to mean any monovalent or polyvalent organic moiety containing at least one carbon atom without any non-carbon atoms (e.g., as in -C≡C-) or optionally in combination with at least one non-carbon atom such as B, N, O, S, P, Si, Se, As, Te, or Ge (e.g., as in carbonyl).

[0046] As used herein, the term "hydrocarbyl group" will be understood to mean a carbyl group further containing one or more H atoms and optionally containing one or more heteroatoms such as, for example, B, N, O, S, P, Si, Se, As, Te or Ge.

[0047] As used herein, the term "heteroatom" will be understood to mean an atom in an organic compound that is not an H atom or a C atom, and will preferably be understood to mean B, N, O, S, P, Si, Se, Sn, As, Te or Ge.

[0048] Carbyl or hydrocarbyl groups comprising a chain of three or more C atoms may be linear, branched and / or cyclic and may contain spiro-linked and / or fused rings. Preferred carbyl and hydrocarbyl groups include alkyl, alkoxy, thioalkyl, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy and alkoxycarbonyloxy, each of which is optionally substituted and has 1 to 40, preferably 1 to 25 and very preferably 1 to 18 C atoms, further optionally substituted aryl or aryloxy having 6 to 40, preferably 6 to 25 atoms, further alkylaryloxy, arylcarbonyl, aryloxycarbonyl, arylcarbonyloxy and aryloxycarbonyloxy, each of which is optionally substituted and has 6 to 40, preferably 7 to 40 C atoms, where all these groups optionally contain one or more heteroatoms, preferably selected from B, N, O, S, P, Si, Se, As, Te and Ge.

[0049] Further preferred carbyl and hydrocarbyl groups include, for example: C1-C 40 Alkyl groups, C1-C 40 Fluoroalkyl groups, C1-C 40 Alkoxy or oxaalkyl groups, C2-C 40 Alkenyl groups, C2-C 40 Alkynyl groups, C3-C 40 Allyl group, C4-C 40 Alkyldienyl group, C4-C 40 Polyenyl group, C2-C 40 Ketone group, C2-C 40 Ester group, C6-C 18 Aryl groups, C6-C 40 Alkylaryl group, C6-C 40 Aryl alkyl groups, C4-C 40 Cycloalkyl groups, C4-C 40 Among the above groups, preferred are C1 to C cycloalkenyl groups. 20 Alkyl groups, C1-C 20 Fluoroalkyl groups, C2-C 20 Alkenyl groups, C2-C 20 Alkynyl groups, C3-C 20Allyl group, C4-C 20 Alkyldienyl group, C2-C 20 Ketone group, C2-C 20 Ester group, C6-C 12 Aryl groups, and C4-C 20 It is a polyenyl group.

[0050] Also included are combinations of groups having carbon atoms and groups having hetero atoms, such as, for example, an alkynyl group, preferably ethynyl, substituted with a silyl group, preferably a trialkylsilyl group.

[0051] The carbyl or hydrocarbyl group can be an acyclic or cyclic group. If the carbyl or hydrocarbyl group is an acyclic group, it can be linear or branched. If the carbyl or hydrocarbyl group is a cyclic group, it can be a non-aromatic carbocyclic or heterocyclic group, or an aryl or heteroaryl group.

[0052] The non-aromatic carbocyclic groups mentioned above and below are saturated or unsaturated and preferably have 4 to 30 ring C atoms. The non-aromatic heterocyclic groups mentioned above and below preferably have 4 to 30 ring C atoms, wherein one or more of the C ring atoms are optionally substituted with a heteroatom, preferably selected from N, O, P, S, Si and Se, or with a -S(O)- or -S(O)2- group. The non-aromatic carbocyclic and heterocyclic groups are monocyclic or polycyclic and may also contain fused rings, preferably 1, 2, 3 or 4 fused or non-fused rings, optionally substituted with one or more groups L, wherein L is F, Cl, -CN, -NC, -NCO, -NCS, -OCN, -SCN, -R 0 , -OR 0 , -SR 0 , -C(=O)X 0 , -C(=O)R 0 , -C(=O)-OR 0 , -OC(=O)-R 0 , -NH2, -NHR 0 , -NR 0 R00 , -C(=O)NHR 0 , -C(=O)NR 0 R 00 , -SO3R 0 , -SO2R 0 , -OH, -NO2, -CF3, -SF5, or optionally substituted silyl, or carbyl or hydrocarbyl having 1 to 30, preferably 1 to 20, C atoms, which are optionally substituted and optionally contain one or more heteroatoms, where X 0 is halogen, preferably F or Cl, and R 0 , R 00 represents H or optionally fluorinated straight or branched alkyl having 1 to 20, preferably 1 to 12 atoms.

[0053] Preferably, L is F, —CN, R 0 , -OR 0 , -SR 0 , -C(=O)-R 0 , -C(=O)-OR 0 , -OC(=O)-R 0 , -OC(=O)-OR 0 , -C(=O)-NHR 0 and -C(=O)-NR 0 R 00 is selected from.

[0054] More preferably, L is selected from F or alkyl, alkoxy, oxaalkyl, thioalkyl, fluoroalkyl, fluoroalkoxy, alkylcarbonyl, alkoxycarbonyl having 1 to 12 C atoms, or alkenyl or alkynyl having 2 to 12 C atoms.

[0055] Preferred non-aromatic carbocyclic or heterocyclic groups are tetrahydrofuran, indane, pyran, pyrrolidine, piperidine, cyclopentane, cyclohexane, cycloheptane, cyclopentanone, cyclohexanone, dihydro-furan-2-one, tetrahydro-pyran-2-one and oxepan-2-one.

[0056] The aryl groups mentioned above and below preferably have 4 to 30 ring C atoms and are monocyclic or polycyclic, may also contain fused rings, preferably 1, 2, 3 or 4 fused or non-fused rings, and are optionally substituted by one or more groups L as defined above.

[0057] The heteroaryl groups mentioned above and below preferably have 4 to 30 ring C atoms, in which one or more of the C ring atoms are preferably substituted by a heteroatom selected from N, O, S, Si and Se, and are monocyclic or polycyclic and may also contain fused rings, preferably 1, 2, 3 or 4 fused or non-fused rings, and are optionally substituted by one or more groups L as defined above.

[0058] The arylalkyl or heteroarylalkyl groups mentioned above and below are preferably —(CH) a -aryl or -(CH2) a -heteroaryl, where a is an integer from 1 to 6, preferably 1, and "aryl" and "heteroaryl" have the meanings given above and below. A preferred arylalkyl group is benzyl optionally substituted with L.

[0059] As used herein, "arylene" is understood to mean a divalent aryl group, and "heteroarylene" is understood to mean a divalent heteroaryl group, including all the preferred meanings of aryl and heteroaryl given above and below.

[0060] Preferred aryl and heteroaryl groups are phenyl (in which further one or more CH groups may be substituted with N), naphthalene, thiophene, selenophene, thienothiophene, dithienothiophene, fluorene and oxazole, all of which may be unsubstituted or mono- or polysubstituted with L as defined above. Highly preferred aryl and heteroaryl groups are pyrrole, preferably N-pyrrole, furan, pyridine, preferably 2- or 3-pyridine, pyrimidine, pyridazine, pyrazine, triazole, tetrazole, pyrazole, imidazole, isothiazole, thiazole, thiadiazole, isoxazole, oxazole, oxadiazole, thiophene, preferably 2-thiophene, selenophene, preferably 2-selenophene, 2,5-dithiophene-2',5'-diyl, thieno[3,2-b]thiophene, thieno[2,3-b]thiophene, furo[3,2-b]furan, furo[2,3-b]furan, seleno[3,2-b]selenophene, seleno[2,3-b]selenophene, thieno[3,2-b]seleno phene, thieno[3,2-b]furan, indole, isoindole, benzo[b]furan, benzo[b]thiophene, benzo[1,2-b;4,5-b']dithiophene, benzo[2,1-b;3,4-b']dithiophene, quinol, 2-methylquinol, isoquinol, quinoxaline, quinazoline, benzotriazole, benzimidazole, benzothiazole, benzisothiazole, benzisoxazole, benzoxadiazole, benzoxazole, benzothiadiazole, 4H-cyclopenta[2,1-b;3,4-b']dithiophene, 7H-3,4-dithia-7-sila-cyclopenta[a]pentalene, all of which may be unsubstituted or mono- or polysubstituted by L as defined above. Further examples of aryl and heteroaryl groups are those selected from the groups shown below.

[0061] Alkyl or alkoxy groups (i.e., the terminal CH group is replaced by -O-) can be linear or branched. Particularly preferred linear groups have 2, 3, 4, 5, 6, 7, 8, 12 or 16 carbon atoms, and thus preferably represent, for example, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, dodecyl or hexadecyl, ethoxy, propoxy, butoxy, pentoxy, hexoxy, heptoxy, octoxy, dodecoxy or hexadecoxy, and also methyl, nonyl, decyl, undecyl, tridecyl, tetradecyl, pentadecyl, nonoxy, decoxy, undecoxy, tridecoxy or tetradecoxy.

[0062] Alkenyl groups (ie, one or more CH2 groups are replaced with -CH=CH-) can be straight-chained or branched. It is preferably linear and has 2 to 10 C atoms and is therefore preferably vinyl, prop-1- or prop-2-enyl, but-1-, 2- or but-3-enyl, pent-1-, 2-, 3- or pent-4-enyl, hex-1-, 2-, 3-, 4- or hex-5-enyl, hept-1-, 2-, 3-, 4-, 5- or hept-6-enyl, oct-1-, 2-, 3-, 4-, 5-, 6- or oct-7-enyl, non-1-, 2-, 3-, 4-, 5-, 6-, 7- or non-8-enyl, dec-1-, 2-, 3-, 4-, 5-, 6-, 7-, 8- or dec-9-enyl.

[0063] Particularly preferred alkenyl groups are C2-C7-1E-alkenyl, C4-C7-3E-alkenyl, C5-C7-4-alkenyl, C6-C7-5-alkenyl and C7-6-alkenyl, in particular C2-C7-1E-alkenyl, C4-C7-3E-alkenyl and C5-C7-4-alkenyl. Examples of particularly preferred alkenyl groups are vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E-hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl, etc. Groups having up to 5 C atoms are generally preferred.

[0064] Oxaalkyl groups (i.e., one CH group is replaced by -O-) may be linear. Particularly preferred linear groups are, for example, 2-oxapropyl (= methoxymethyl), 2-(= ethoxymethyl) or 3-oxabutyl (= 2-methoxyethyl), 2-, 3- or 4-oxapentyl, 2-, 3-, 4- or 5-oxahexyl, 2-, 3-, 4-, 5- or 6-oxaheptyl, 2-, 3-, 4-, 5-, 6- or 7-oxaoctyl, 2-, 3-, 4-, 5-, 6-, 7- or 8-oxanonyl or 2-, 3-, 4-, 5-, 6-, 7-, 8- or 9-oxadecyl.

[0065] In alkyl groups in which one CH group is replaced by -O- and one CH group is replaced by -C(O)-, these radicals are preferably adjacent. Thus, together they form a carbonyloxy group -C(O)-O- or an oxycarbonyl group -OC(O)-. Preferably, this group is linear and has 2 to 6 C atoms. It is therefore preferably acetyloxy, propionyloxy, butyryloxy, pentanoyloxy, hexanoyloxy, acetyloxymethyl, propionyloxymethyl, butyryloxymethyl, pentanoyloxymethyl, 2-acetyloxyethyl, 2-propionyloxyethyl, 2-butyryloxyethyl, 3-acetyloxypropyl, 3-propionyloxypropyl, 4-acetyloxybutyl, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl, pentoxycarbonyl, methoxycarbonylmethyl, ethoxycarbonylmethyl, propoxycarbonylmethyl, butoxycarbonylmethyl, 2-(methoxycarbonyl)ethyl, 2-(ethoxycarbonyl)ethyl, 2-(propoxycarbonyl)ethyl, 3-(methoxycarbonyl)propyl, 3-(ethoxycarbonyl)propyl, 4-(methoxycarbonyl)-butyl.

[0066] The alkyl group in which two or more CH2 groups are replaced by -O- and / or -C(O)O- can be linear or branched. It is preferably linear and has 3 to 12 C atoms. Thus, it is preferably bis-carboxy-methyl, 2,2-bis-carboxy-ethyl, 3,3-bis-carboxy-propyl, 4,4-bis-carboxy-butyl, 5,5-bis-carboxy-pentyl, 6,6-bis-carboxy-hexyl, 7,7-bis-carboxy-heptyl, 8,8-bis-carboxy-octyl, 9,9-bis-carboxy-nonyl, 10,10-bis-carboxy-decyl, bis-(methoxycarbonyl)-methyl, 2,2-bis-(methoxycarbonyl)-ethyl, 3,3-bis-(methoxycarbonyl)- bis-(ethoxycarbonyl)-propyl, 4,4-bis-(methoxycarbonyl)-butyl, 5,5-bis-(methoxycarbonyl)-pentyl, 6,6-bis-(methoxycarbonyl)-hexyl, 7,7-bis-(methoxycarbonyl)-heptyl, 8,8-bis-(methoxycarbonyl)-octyl, bis-(ethoxycarbonyl)-methyl, 2,2-bis-(ethoxycarbonyl)-ethyl, 3,3-bis-(ethoxycarbonyl)-propyl, 4,4-bis-(ethoxycarbonyl)-butyl, 5,5-bis-(ethoxycarbonyl)-hexyl.

[0067] Thioalkyl groups, i.e., one CH group is replaced by -S-, are preferably linear thiomethyl (-SCH), 1-thioethyl (-SCHCH), 1-thiopropyl (=-SCHCHCH), 1-(thiobutyl), 1-(thiopentyl), 1-(thiohexyl), 1-(thioheptyl), 1-(thiooctyl), 1-(thiononyl), 1-(thiodecyl), 1-(thioundecyl) or 1-(thiododecyl), where preferably sp 2 The CH2 group adjacent to the hybridized vinyl carbon atom is substituted.

[0068] The fluoroalkyl group is perfluoroalkyl C i F 2i+1 (wherein i is an integer from 1 to 15), in particular CF3, C2F5, C3F7, C4F9, C5F11 , C6F 13 , C7F 15 or C8F 17 , very preferably CF 13 or preferably a partially fluorinated alkyl having 1 to 15 C atoms, in particular a 1,1-difluoroalkyl, all of which are linear or branched.

[0069] Preferably, "fluoroalkyl" refers to a partially fluorinated (ie, non-perfluorinated) alkyl group. The alkyl, alkoxy, alkenyl, oxaalkyl, thioalkyl, carbonyl and carbonyloxy groups can be achiral or chiral groups. Particularly preferred chiral groups are, for example, 2-butyl (=1-methylpropyl), 2-methylbutyl, 2-methylpentyl, 3-methylpentyl, 2-ethylhexyl, 2-butyloctyl, 2-hexyldecyl, 2-octyldodecyl, 3,7-dimethyloctyl, 3,7,11-trimethyldodecyl, 2-propylpentyl, in particular 2-methylbutyl, 2-methylbutoxy, 2-methylpentoxy, 3-methylpentyl. 1-pentoxy, 2-ethylhexoxy, 2-butyloctoxy, 2-hexyldecoxy, 2-octyldodecoxy, 3,7-dimethyloctoxy, 3,7,11-trimethyldodecoxy, 1-methylhexoxy, 2-octyloxy, 2-oxa-3-methylbutyl, 3-oxa-4-methylpentyl, 4-methylhexyl, 2-hexyl, 2-octyl, 2-nonyl, 2-decyl, 2-dodecyl, 6 1-methoxy-octoxy, 6-methyloctoxy, 6-methyloctanoyloxy, 5-methylheptyloxy-carbonyl, 2-methylbutyryloxy, 3-methylvaleroyloxy, 4-methylhexanoyloxy, 2-chloro-propionyloxy, 2-chloro-3-methylbutyryloxy, 2-chloro-4-methyl-valeryloxy, 2-chloro-3-methylvaleryloxy, 2-methyl-3-oxapentyl, 2-methyl-3-oxa-hexyl, 1-methoxypropyl-2-oxy, 1-ethoxypropyl-2-oxy, 1-propoxypropyl-2-oxy, 1-butoxypropyl-2-oxy, 2-fluorooctyloxy, 2-fluorodecyloxy, 1,1,1-trifluoro-2-octyloxy, 1,1,1-trifluoro-2-octyl, 2-fluoromethyloctyloxy. Highly preferred are 2-methylbutyl, 2-ethylhexyl, 2-butyloctyl, 2-hexyldecyl, 2-octyldodecyl, 3,7-dimethyloctyl, 3,7,11-trimethyldodecyl, 2-hexyl, 2-octyl, 2-octyloxy, 1,1,1-trifluoro-2-hexyl, 1,1,1-trifluoro-2-octyl and 1,1,1-trifluoro-2-octyloxy.

[0070] Preferred achiral branched groups are isopropyl, isobutyl (=methylpropyl), isopentyl (=3-methylbutyl), tert.butyl, isopropoxy, 2-methyl-propoxy and 3-methylbutoxy.

[0071] In a preferred embodiment, the substituents on the aryl or heteroaryl ring are independently selected from primary, secondary or tertiary alkyl, alkoxy, oxaalkyl, thioalkyl, alkylcarbonyl or alkoxycarbonyl having 1 to 30 C atoms, in which one or more H atoms are optionally substituted with F, or aryl, aryloxy, heteroaryl or heteroaryloxy, which are optionally alkylated, alkoxylated, alkylthiolated or esterified and have 4 to 30 ring atoms. Further preferred substituents are those of the formula

[0072] [ka]

[0073] wherein RSub is selected from the group consisting of 1~3 denotes L as defined above and below, and 1~3 are preferably all alkyl, alkoxy, oxaalkyl, thioalkyl, alkylcarbonyl or alkoxycarbonyl (which may optionally be fluorinated) having 1 to 24 C atoms, preferably 1 to 20 C atoms, and the dashed line indicates the bond to the ring to which these groups are attached. Among these substituents, very preferred are all RSub 1~3 The subgroups are identical.

[0074] As used herein, when an aryl(oxy) or heteroaryl(oxy) group is "alkylated or alkoxylated", this means that it is substituted with one or more alkyl or alkoxy groups having 1 to 24 C atoms and being linear or branched, wherein one or more H atoms are optionally replaced with F atoms.

[0075] In the above and below, Y 1 and Y 2 are, independently of each other, H, F, Cl or CN. As used herein, -CO-, -C(=O)-, and -C(O)- refer to carbonyl groups, i.e., the structure

[0076] [ka]

[0077] It will be understood that the term "a" refers to a group having the formula: As used herein, C=CR 1 R 2 is the structure

[0078] [ka]

[0079] It will be understood that the term "a" refers to a group having the formula: As used herein, "halogen" includes F, Cl, Br or I, preferably F, Cl or Br. A halogen atom representing a substituent on a ring or chain is preferably F or Cl, very preferably F. A halogen atom representing a reactive group in a monomer or intermediate is preferably Br or I.

[0080] Above and below, the term "mirror image" means a part that is obtained from another part by vertically or horizontally inverting the part across an external plane of symmetry or a plane of symmetry extending through the part. For example, a part

[0081] [ka]

[0082] is a mirror image

[0083] [ka]

[0084] Also includes. DETAILED DESCRIPTION OF THE INVENTION

[0085] The compounds of the present invention are easy to synthesize and exhibit advantageous properties: they exhibit good processability for device fabrication processes, high solubility in organic solvents, and are particularly suitable for mass production using solution processing methods.

[0086] The compounds of formula I are particularly suitable as (electron) acceptors or n-type semiconductors and for making blends of n-type and p-type semiconductors suitable for use in OPD or BHJ OPV devices.

[0087] The compounds of Formula I are also suitable to replace fullerene compounds previously used as n-type semiconductors in OPV or OPD devices. In addition, the compounds of formula I exhibit the following advantageous properties: i) position R 1~4 and / or Ar 2~5 The substitution at allows for higher photostability of the bulk heterojunction.

[0088] ii) position R 1~4 and / or Ar2~5 The substitution at allows for higher stability of the bulk heterojunction against photoirradiation by mediating the crystallization and / or phase separation kinetics, thus stabilizing the initial equilibrium thermodynamics at the BHJ.

[0089] iii) position R 1~4 and / or Ar 2~5 The substitution at allows for higher thermal stability of the bulk heterojunction by mediating the crystallization and / or phase separation kinetics, thus stabilizing the initial equilibrium thermodynamics at the BHJ.

[0090] iv) Compared to previously disclosed n-type OSCs for OPV / OPD applications, compounds of formula I offer the advantage that they allow further optimization of the HOMO and LUMO levels of the polycyclic units by substitution, and Ar 2~5 Careful selection of the units results in improved light absorption.

[0091] v)Ar 2~5 Further optimization of the HOMO and LUMO levels of the polycyclic units in Formula I by substitution and / or careful selection of units can improve the open circuit potential (V oc ) can be increased.

[0092] vi) When the compound is used as an n-type OSC in a composition together with a p-type OSC in the photoactive layer of an OPV or OPD, e.g., Ar 2~5 Further fine tuning of the HOMO and LUMO levels of the polycyclic units in Formula I through unit substitution and / or careful selection can reduce the energy loss in the electron transfer process between the n-type acceptor and p-type donor materials in the photoactive layer.

[0093] vii) Position R 1~4 and / or Ar 2~5 Substitution at may allow for greater solubility in non-halogenated solvents due to the increased number of solubilizing groups. The synthesis of compounds of formula I can be carried out based on literature methods known to those skilled in the art, as further shown herein.

[0094] Preferred compounds of formula I are 1 and W 2 denotes S or Se, very preferably S. Further preferred compounds of formula I are W 1 and W 2 have the same meaning and preferably both denote S or Se, very preferably S.

[0095] Further preferred compounds of formula I are W 1 and W 2 have different meanings, and preferably one represents S and the other represents Se. In the compounds of formula I, Ar 4 and Ar 5 is preferably arylene or heteroarylene as defined above.

[0096] Preferred groups Ar in formula I 2~5 are the following expressions and their mirror images:

[0097] [ka]

[0098] in which the individual radicals, independently of one another, have the following meanings on each occurrence, identically or differently: W 1,2 S, O or Se, W 3 NR 0 , S, O or Se, V 1 CR 5 or N, V 2 CR 6 or N, R 5~10H, F, Cl, CN or a straight-chain, branched or cyclic alkyl having 1 to 30, preferably 1 to 20, C atoms (wherein one or more CH groups are selected from -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -OC(=O)-, -NR 0 -, -SiR 0 R 00 -, -CF2-, -CR 0 =CR 00 -, -CY 1 =CY 2 - or -C≡C-, one or more H atoms are optionally replaced by F, Cl, Br, I or CN, and one or more CH2 or CH3 groups are optionally replaced by a cationic or anionic group), or aryl, heteroaryl, arylalkyl, heteroarylalkyl, aryloxy or heteroaryloxy, wherein each of the above cyclic groups has 5 to 20 ring atoms, is monocyclic or polycyclic, optionally contains fused rings and is unsubstituted or substituted with one or more identical or different groups L as defined above and below.

[0099] Highly preferred groups Ar in formula I 2 and Ar 3 are the following expressions and their mirror images:

[0100] [ka]

[0101] Selected from R 5~10 has the meaning given above and below. Highly preferred groups Ar in formula I 4 and Ar 5 are the following expressions and their mirror images:

[0102] [ka]

[0103] wherein X is selected from 1 , X 2 , X 3 and X 4 However, the above and following R 1 and preferably H, F, Cl, —CN, R 0 , OR 0 or C(=O)OR 0 Shows.

[0104] Preferred formulae AR1, AR2, AR5, AR6, AR7, AR8, AR9, AR10 and AR11 contain at least one, preferably one, two or four substituents X selected from F and Cl, very preferably F. 1~4 It contains:

[0105] Preferably, the group R in formula I T1 and R T2 are H, F, Cl, Br, -NO2, -CN, -CF3, R * , -CF2-R * , -OR * , -SR * , -SO2-R * , -SO3-R * , -C(=O)-H, -C(=O)-R * , -C(=S)-R * , -C(=O)-CF2-R * , -C(=O)-OR * , -C(=S)-OR * , -OC(=O)-R * , -OC(=S)-R * , -C(=O)-SR * , -SC(=O)-R * , -C(=O)NR * R ** , -NR * -C(=O)-R * , -NHR * , -NR * R ** , -CR * =CR * R ** , -C≡CR * , -C≡C-SiR* R ** R *** , -SiR * R ** R *** , -CH=CH(CN), -CH=C(CN)2, -C(CN)=C(CN)2, -CH=C(CN)(R a ), CH=C(CN)-C(=O)-OR * , -CH=C(CO-OR * )2, -CH=C(CO-NR * R ** )2 and the following equation

[0106] [ka]

[0107] [ka]

[0108] [ka]

[0109] [ka]

[0110] in which the individual radicals, independently of one another, have the same or different meanings on each occurrence: R a , R b aryl or heteroaryl, each having 4 to 30 ring atoms and optionally containing fused rings, which are unsubstituted or substituted with one or more groups L, or one of the meanings given for L; R * , R ** , R ***Alkyl having 1 to 20 C atoms, which is linear, branched or cyclic, unsubstituted or substituted with one or more F or Cl atoms or CN groups, or perfluorinated, where one or more C atoms are selected from the group consisting of -O-, -S-, -C(=O)-, -C(=S)-, -SiR, in such a way that O- and / or S atoms are not directly bonded to each other; 0 R 00 -, -NR 0 R 00 -, -CHR 0 =CR 00 - or -C≡C-), LF, Cl, -NO2, -CN, -NC, -NCO, -NCS, -OCN, -SCN, R 0 , OR 0 , S.R. 0 , -C(=O)X 0 , -C(=O)R 0 , -C(=O)-OR 0 , -OC(=O)-R 0 , -NH2, -NHR 0 , -NR 0 R 00 , -C(=O)NHR 0 , -C(=O)NR 0 R 00 , -SO3R 0 , -SO2R 0 , -OH, -NO2, -CF3, -SF5, or optionally substituted silyl, or carbyl or hydrocarbyl having 1 to 30, preferably 1 to 20, C atoms, which are optionally substituted and optionally contain one or more heteroatoms, preferably F, -CN, R 0 , -OR 0 , -SR 0 , -C(=O)-R 0 , -C(=O)-OR 0 , -OC(=O)-R 0 , -OC(=O)-OR 0 , -C(=O)-NHR 0 , -C(=O)-NR 0 R 00 , L' One of the meanings of H or L, R 0 , R00 H or optionally fluorinated linear or branched alkyl having 1 to 20, preferably 1 to 12, C atoms, Y 1 , Y 2 H, F, Cl or CN, X 0 halogen, preferably F or Cl, r 0, 1, 2, 3 or 4, s 0, 1, 2, 3, 4 or 5, t 0, 1, 2 or 3, u 0, 1 or 2, where R T1 and R T2 At least one of the groups represents an electron-withdrawing group.

[0111] Preferred compounds of formula I are those in which R T1 and R T2 Both of these represent electron-withdrawing groups. Preferred electron-withdrawing group R T1 and R T2 -CN, -C(=O)-OR * , -C(=S)-OR * , -CH=CH(CN), -CH=C(CN)2, -C(CN)=C(CN)2, -CH=C(CN)(R a ), CH=C(CN)-C(=O)-OR * , -CH=C(CO-OR * )2, and formulae T1-T53.

[0112] Highly preferred group R T1 and R T2 is expressed as follows:

[0113] [ka]

[0114] wherein L, L', R a, r and s have the meanings given above and below, and L' is H or has one of the meanings given for L. Preferably, in these formulas, L' is H. Even more preferably, in these formulas, r is 0.

[0115] The above formulae T1 to T53 are each a group having an adjacent group Ar 4 or Ar 5 and thus also includes their respective E- or Z-stereoisomers relative to the C=C bond at the alpha position relative to the group

[0116] [ka]

[0117] teeth,

[0118] [ka]

[0119] It can also be shown. Preferred compounds of formula I are of formula Ia

[0120] [ka]

[0121] wherein U is selected from a But, CR 1 R 2 , SiR 1 R 2 or GeR 1 R 2 , preferably CR 1 R 2 or SiR 1 R 2 , very preferably CR 1 R 2 indicates U b But, CR 3 R 4 , SiR 3 R 4 or GeR3 R 4 , preferably CR 3 R 4 or SiR 3 R 4 , very preferably CR 3 R 4 indicates R 1~4 , Ar 1~5 , R T1,T2 , a, b and m have the meanings or preferred meanings given above and below.

[0122] In the compounds of formula I and Ia, preferably R 1~4 However, it is different from H. In a preferred embodiment of the present invention, R in Formula I and Ia 1~4 is selected from F, Cl, or straight-chain or branched alkyl, alkoxy, sulfanylalkyl, sulfonylalkyl, alkylcarbonyl, alkoxycarbonyl and alkylcarbonyloxy, each having 1 to 20 C atoms and being unsubstituted or substituted with one or more F atoms.

[0123] In another preferred embodiment of the present invention, R in Formula I and Ia 1~4 is selected from monocyclic or polycyclic aryl or heteroaryl, each of which is optionally substituted with one or more groups L as defined in formula I and has 4 to 30 ring atoms, where two or more rings can be fused together or linked together by a covalent bond.

[0124] In a preferred embodiment of the present invention, R in Formula I and Ia 5~10 is H. In another preferred embodiment of the present invention, R in Formula I and Ia 5~10 At least one of is different from H.

[0125] In a preferred embodiment of the present invention, R in Formula I and Ia 5~10is different from H and is selected from F, Cl, or straight-chain or branched alkyl, alkoxy, sulfanylalkyl, sulfonylalkyl, alkylcarbonyl, alkoxycarbonyl and alkylcarbonyloxy, each having 1 to 20 C atoms and being unsubstituted or substituted with one or more F atoms and not perfluorinated.

[0126] In another preferred embodiment of the present invention, R in Formula I and Ia 5~10 when different from H, is selected from aryl or heteroaryl, each of which is optionally substituted with one or more groups L as defined in formula I and has 4 to 30 ring atoms.

[0127] Preferred aryl and heteroaryl groups R 1~10 is expressed as follows:

[0128] [ka]

[0129] [ka]

[0130] wherein R 11~17 independently of one another, identically or differently on each occurrence, denote H or have one of the meanings given for L in formula I or one of the preferred meanings thereof given above and below.

[0131] Highly preferred aryl and heteroaryl groups R 1~10 is expressed as follows:

[0132] [ka]

[0133] wherein R 11~15are as defined above. The most preferred aryl groups R1 to R 10 is selected from formulae SUB7 to SUB14 defined above. In another preferred embodiment, R 1~10 denotes a linear, branched or cyclic alkyl group having 1 to 50, preferably 2 to 50, very preferably 2 to 30, more preferably 2 to 24 and most preferably 2 to 16 C atoms, in which one or more CH2 or CH3 groups are substituted by a cationic or anionic group.

[0134] The cationic group is preferably selected from the group consisting of phosphonium, sulfonium, ammonium, uronium, thiouronium, guanidium or heterocyclic cations, such as imidazolium, pyridinium, pyrrolidinium, triazolium, morpholinium or piperidinium cations.

[0135] Preferred cationic groups are selected from the group consisting of tetraalkylammonium, tetraalkylphosphonium, N-alkylpyridinium, N,N-dialkylpyrrolidinium, 1,3-dialkylimidazolium, where "alkyl" preferably denotes a linear or branched alkyl group having 1 to 12 C atoms, very preferably selected from the formulae SUB1 to SUB6.

[0136] Further preferred cationic groups are of the formula:

[0137] [ka]

[0138] [ka]

[0139] wherein R 1 ', R 2 ', R 3 ' and R4 ' denote, independently of one another, H, a straight-chain or branched alkyl group having 1 to 12 C atoms or a non-aromatic carbocyclic or heterocyclic group or an aryl or heteroaryl group, each of which has 3 to 20, preferably 5 to 15, ring atoms and is monocyclic or polycyclic and optionally substituted by one or more identical or different substituents L as defined above, or each group R 1~10 The bond to

[0140] In the above cationic group of the above formula, the group R 1 ', R 2 ', R 3 ' and R 4 ' (if they replace a CH3 group) may be replaced by any one of the groups R 1~10 or two adjacent groups R 1 ', R 2 ', R 3 ' or R 4 ' (if they substitute a CH2 group) are the respective groups R 1 The bond to can be shown.

[0141] The anionic group is preferably selected from the group consisting of borate, imide, phosphate, sulfonate, sulfate, succinate, naphthenate or carboxylate, very preferably phosphate, sulfonate or carboxylate.

[0142] In a preferred embodiment of the present invention, the group R in formula I T1 and R T2 is an alkyl having 1 to 16 C atoms (wherein one or more C atoms are selected from the group consisting of -O-, -S-, -C(O)-, -C(S)-, -SiR), which is linear, branched or cyclic and is unsubstituted or substituted with one or more F or Cl atoms or CN groups or is perfluorinated, so that the O- and / or S atoms are not directly bonded to each other; 0 R 00 -, -NR 0 R 00 -, -CHR 0=CR 00 - or -C≡C-).

[0143] Further preferred compounds of formula I are selected from the following preferred embodiments or any combination thereof: -W 1 and W 2 is S or Se, preferably S; -U 1 But, CR 1 R 2 or SiR 1 R 2 and U 2 But, CR 3 R 4 or SiR 3 R 4 and -U 1 is CR 1 R 2 and U 2 is CR 3 R 4 and -V 1 is CR 5 and V 2 is CR 6 and -V 1 is CR 5 and V 2 is N, -V 1 and V 2 is N, -m=1, - a=b=1 or 2, preferably 1; -a=b=0, -Ar 2 and Ar 3 In one or both of the groups, all the substituents R 5~7 is H, -Ar 2 and Ar 3 In one or both of the 5~7 at least one, preferably one or two, of these are different from H and very preferably denote F, -Ar 4and Ar 5 In one or both of the groups, all the substituents R 5~8 is H, -Ar 4 and Ar 5 In one or both of the 5~8 at least one, preferably one or two, of the following is different from H; -Ar 4 and Ar 5 represents thiophene, thiazole, thieno[3,2-b]thiophene, thiazolo[5,4-d]thiazole, benzene, 2,1,3-benzothiadiazole, 1,2,3-benzothiadiazole, thieno[3,4-b]thiophene, benzotriazole or thiadiazole[3,4-c]pyridine, which are represented by X as defined above. 1 , X 2 , X 3 and X 4 is replaced by -Ar 4 and Ar 5 represents thiophene, thiazole, thieno[3,2-b]thiophene, thiazolo[5,4-d]thiazole, benzene, 2,1,3-benzothiadiazole, 1,2,3-benzothiadiazole, thieno[3,4-b]thiophene, benzotriazole, or thiadiazole[3,4-c]pyridine, where X 1 , X 2 , X 3 and X 4 is H, -Ar 4 and Ar 5 represents thiophene, thiazole, thieno[3,2-b]thiophene, thiazolothiazole, benzene, 2,1,3-benzothiadiazole, 1,2,3-benzothiadiazole, thieno[3,4-b]thiophene, benzotriazole, or thiadiazole[3,4-c]pyridine, where X 1 , X 2 , X 3 and X 4 One or more of are different from H, -R 1 , R 2 , R 3 and R4 However, unlike H, -R 1 , R 2 , R 3 and R 4 is selected from H, F, Cl, or straight-chain or branched alkyl, alkoxy, sulfanylalkyl, sulfonylalkyl, alkylcarbonyl, alkoxycarbonyl and alkylcarbonyloxy, each having 1 to 20 C atoms and being unsubstituted or substituted with one or more F atoms and not perfluorinated, or optionally fluorinated alkyl or alkoxy having 1 to 12 C atoms, -R 1 , R 2 , R 3 and R 4is selected from aryl or heteroaryl, each of which is optionally substituted with one or more groups L as defined in formula I and has 4 to 30 ring atoms, preferably phenyl optionally substituted in the 4- or 3,5-position with alkyl or alkoxy having 1 to 20 C atoms, preferably 1 to 16 C atoms, very preferably 4-alkylphenyl, where alkyl is C1-16 alkyl, most preferably 4-methylphenyl, 4-hexylphenyl, 4-octylphenyl or 4-dodecylphenyl, or 4-alkoxyphenyl, where alkoxy is C1-16 alkoxy, most preferably 4-hexyloxyphenyl, 4-octyloxyphenyl or 4-dodecyloxyphenyl or 3,5-dialkylphenyl (wherein alkyl is C1-16 alkyl), most preferably 3,5-dihexylphenyl or 3,5-dioctylphenyl or 3,5-dialkoxyphenyl (wherein alkoxy is C1-16 alkoxy), most preferably 3,5-dihexyloxyphenyl or 3,5-dioctyloxyphenyl, or 4-thioalkylphenyl (wherein thioalkyl is C1-16 thioalkyl), most preferably 4-thiohexylphenyl, 4-thiooctylphenyl or 4-thiododecylphenyl or 3,5-dithioalkylphenyl (wherein thioalkyl is C1-16 thioalkyl), most preferably 3,5-dithiohexylphenyl or 3,5-dithiooctylphenyl; -L' is H, L, L' represent F, Cl, CN, NO2 or optionally fluorinated alkyl or alkoxy having 1 to 16 C atoms, - r is 2 and L is F, Cl, CN, NO2 or optionally fluorinated alkyl or alkoxy having 1 to 16 C atoms, -r is 1 and L is F, Cl, CN, NO2 or optionally fluorinated alkyl or alkoxy having 1 to 16 C atoms, - r is 4 and L is F, Cl, CN, NO2 or optionally fluorinated alkyl or alkoxy having 1 to 16 C atoms, -R 5~10 is different from H, it is selected from F, Cl, or straight-chain or branched alkyl, alkoxy, sulfanylalkyl, sulfonylalkyl, alkylcarbonyl, alkoxycarbonyl and alkylcarbonyloxy, each having 1 to 20 C atoms and being unsubstituted or substituted with one or more F atoms and not perfluorinated, preferably from F or optionally fluorinated alkyl or alkoxy having 1 to 16 C atoms.

[0144] Preferred compounds of formula I have the following subformula:

[0145] [ka]

[0146] [ka]

[0147] [ka]

[0148] [ka]

[0149] wherein R 1 , R 2 , R 3 , R 4 , R T1 , R T2 , Ar 4 , Ar 5 , a and b have the meanings given above. Highly preferred compounds of formula I are selected from the following group: 1a) the group consisting of compounds of formula I1, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from equation T10.

[0150] 1b) the group consisting of compounds of formula I1, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from equation T36.

[0151] 1c) the group consisting of compounds of formula I1, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T37.

[0152] 1d) the group consisting of compounds of formula I1, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T38.

[0153] 1e) the group consisting of compounds of formula I1, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T39.

[0154] 1f) the group consisting of compounds of formula I1, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T47.

[0155] 2a) the group consisting of compounds of formula I2, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from equation T10.

[0156] 2b) the group consisting of compounds of formula I2, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T36.

[0157] 2c) the group consisting of compounds of formula I2, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T37.

[0158] 2d) the group consisting of compounds of formula I2, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T38.

[0159] 2e) the group consisting of compounds of formula I2, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T39.

[0160] 2f) the group consisting of compounds of formula I2, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1and R T2 is selected from formula T47.

[0161] 3a) the group consisting of compounds of formula I3, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from equation T10.

[0162] 3b) the group consisting of compounds of formula I3, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T36.

[0163] 3c) the group consisting of compounds of formula I3, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T37.

[0164] 3d) the group consisting of compounds of formula I3, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T38.

[0165] 3e) the group consisting of compounds of formula I3, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T39.

[0166] 3f) the group consisting of compounds of formula I3, wherein Ar 4 and Ar 5is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T47.

[0167] 4a) the group consisting of compounds of formula I4, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from equation T10.

[0168] 4b) the group consisting of compounds of formula I4, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T36.

[0169] 4c) the group consisting of compounds of formula I4, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T37.

[0170] 4d) the group consisting of compounds of formula I4, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T38.

[0171] 4e) the group consisting of compounds of formula I4, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T39.

[0172] 4f) the group consisting of compounds of formula I4, wherein Ar4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T47.

[0173] 5a) the group consisting of compounds of formula I5, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from equation T10.

[0174] 5b) the group consisting of compounds of formula I5, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from equation T36.

[0175] 5c) the group consisting of compounds of formula I5, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T37.

[0176] 5d) the group consisting of compounds of formula I5, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T38.

[0177] 5e) the group consisting of compounds of formula I5, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T39.

[0178] 5f) the group consisting of compounds of formula I5, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T47.

[0179] 6a) the group consisting of compounds of formula I6, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from equation T10.

[0180] 6b) the group consisting of compounds of formula I6, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from equation T36.

[0181] 6c) the group consisting of compounds of formula I6, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T37.

[0182] 6d) the group consisting of compounds of formula I6, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T38.

[0183] 6e) the group consisting of compounds of formula I6, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2is selected from formula T39.

[0184] 6f) the group consisting of compounds of formula I6, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T47.

[0185] 7a) the group consisting of compounds of formula I7, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from equation T10.

[0186] 7b) the group consisting of compounds of formula I7, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from equation T36.

[0187] 7c) the group consisting of compounds of formula I7, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T37.

[0188] 7d) the group consisting of compounds of formula I7, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T38.

[0189] 7e) the group consisting of compounds of formula I7, wherein Ar 4 and Ar 5is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T39.

[0190] 7f) the group consisting of compounds of formula I7, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T47.

[0191] 8a) the group consisting of compounds of formula I8, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from equation T10.

[0192] 8b) the group consisting of compounds of formula I8, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T36.

[0193] 8c) the group consisting of compounds of formula I8, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T37.

[0194] 8d) the group consisting of compounds of formula I8, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T38.

[0195] 8e) the group consisting of compounds of formula I8, wherein Ar4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T39.

[0196] 8f) the group consisting of compounds of formula I8, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T47.

[0197] 9a) the group consisting of compounds of formula I9, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from equation T10.

[0198] 9b) the group consisting of compounds of formula I9, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T36.

[0199] 9c) the group consisting of compounds of formula I9, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T37.

[0200] 9d) the group consisting of compounds of formula I9, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T38.

[0201] 9e) the group consisting of compounds of formula I9, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T39.

[0202] 9f) the group consisting of compounds of formula I9, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T47.

[0203] 10a) the group consisting of compounds of formula I10, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from equation T10.

[0204] 10b) the group consisting of compounds of formula I10, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T36.

[0205] 10c) the group consisting of compounds of formula I10, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T37.

[0206] 10d) the group consisting of compounds of formula I10, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2is selected from formula T38. 10e) the group consisting of compounds of formula I10, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T39.

[0207] 10f) the group consisting of compounds of formula I10, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T47.

[0208] 11a) the group consisting of compounds of formula I11, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from the formula T11.

[0209] 11b) the group consisting of compounds of formula I11, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T36.

[0210] 11c) the group consisting of compounds of formula I11, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T37.

[0211] 11d) the group consisting of compounds of formula I11, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1and R T2 is selected from formula T38.

[0212] 11e) the group consisting of compounds of formula I11, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T39.

[0213] 11f) the group consisting of compounds of formula I11, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T47.

[0214] 12a) the group consisting of compounds of formula I12, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T12.

[0215] 12b) the group consisting of compounds of formula I12, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T36.

[0216] 12c) the group consisting of compounds of formula I12, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T37.

[0217] 12d) the group consisting of compounds of formula I12, wherein Ar 4 and Ar 5is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T38.

[0218] 12e) the group consisting of compounds of formula I12, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T39.

[0219] 12f) the group consisting of compounds of formula I12, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T47.

[0220] 13a) the group consisting of compounds of formula I13, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T13.

[0221] 13b) the group consisting of compounds of formula I13, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from equation T36.

[0222] 13c) the group consisting of compounds of formula I13, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T37.

[0223] 13d) the group consisting of compounds of formula I13, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T38.

[0224] 13e) the group consisting of compounds of formula I13, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T39.

[0225] 13f) the group consisting of compounds of formula I13, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T47.

[0226] 14a) the group consisting of compounds of formula I14, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T14.

[0227] 14b) the group consisting of compounds of formula I14, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T36.

[0228] 14c) the group consisting of compounds of formula I14, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2is selected from formula T37.

[0229] 14d) the group consisting of compounds of formula I14, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T38.

[0230] 14e) the group consisting of compounds of formula I14, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T39.

[0231] 14f) the group consisting of compounds of formula I14, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T47.

[0232] 15a) the group consisting of compounds of formula I15, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T14.

[0233] 15b) the group consisting of compounds of formula I15, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from equation T36.

[0234] 15c) the group consisting of compounds of formula I15, wherein Ar 4 and Ar 5is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T37.

[0235] 15d) the group consisting of compounds of formula I15, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T38.

[0236] 15e) the group consisting of compounds of formula I15, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T39.

[0237] 15f) the group consisting of compounds of formula I15, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T47.

[0238] 16a) the group consisting of compounds of formula I16, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T14.

[0239] 16b) the group consisting of compounds of formula I16, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T36.

[0240] 16c) the group consisting of compounds of formula I16, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T37.

[0241] 16d) the group consisting of compounds of formula I16, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T38.

[0242] 16e) the group consisting of compounds of formula I16, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T39.

[0243] 16f) the group consisting of compounds of formula I16, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T47.

[0244] 17a) the group consisting of compounds of formula I17, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T14.

[0245] 17b) the group consisting of compounds of formula I17, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2is selected from equation T36.

[0246] 17c) the group consisting of compounds of formula I17, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T37.

[0247] 17d) the group consisting of compounds of formula I17, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T38.

[0248] 17e) the group consisting of compounds of formula I17, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T39.

[0249] 17f) the group consisting of compounds of formula I17, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T47.

[0250] 18a) the group consisting of compounds of formula I18, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T14.

[0251] 18b) the group consisting of compounds of formula I18, wherein Ar 4 and Ar 5is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T36.

[0252] 18c) the group consisting of compounds of formula I18, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T37.

[0253] 18d) the group consisting of compounds of formula I18, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T38.

[0254] 18e) the group consisting of compounds of formula I18, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T39.

[0255] 18f) the group consisting of compounds of formula I18, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T47.

[0256] 19a) the group consisting of compounds of formula I19, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T14.

[0257] 19b) the group consisting of compounds of formula I19, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T36.

[0258] 19c) the group consisting of compounds of formula I19, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T37.

[0259] 19d) the group consisting of compounds of formula I19, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T38.

[0260] 19e) the group consisting of compounds of formula I19, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T39.

[0261] 19f) the group consisting of compounds of formula I19, wherein Ar 4 and Ar 5 is selected from the formulas AR1 to AR11, a and b are 0, 1 or 2, and R T1 and R T2 is selected from formula T47.

[0262] Further preferred embodiments of the present invention relate to the following: a compound selected from groups 1a to 1f above, a compound selected from groups 2a to 2f above, a compound selected from groups 3a to 3f above, a compound selected from groups 4a to 4f above, a compound selected from groups 5a to 5f above, a compound selected from groups 6a to 6f above, a compound selected from groups 7a to 7f above, a compound selected from groups 8a to 8f above, a compound selected from groups 9a to 9f above, a compound selected from groups 10a to 10f above, a compound selected from groups 11a to 11f above, a compound selected from groups 12a to 12f above, a compound selected from groups 13a to 13f above, a compound selected from groups 14a to 14f above, a compound selected from groups 15a to 15f above, a compound selected from groups 16a to 16f above, a compound selected from groups 17a to 17f above, a compound selected from groups 18a to 18f above, - a compound selected from groups 19a to 19f above.

[0263] Further preferred embodiments of the present invention relate to compounds selected from each of the individual groups 1a to 19f defined above. In the above groups 1a to 19f, R 1~4 is preferably selected from optionally fluorinated alkyl or alkoxy having 1 to 16 C atoms, or aryl or heteroaryl which are monocyclic or polycyclic, optionally containing fused rings, have 4 to 30 ring atoms and are optionally substituted with one or more groups L as defined in formula I, preferably denotes phenyl which is substituted with one or more optionally fluorinated alkyl or alkoxy groups having 1 to 16 C atoms.

[0264] Highly preferred compounds of formula I have the following sub-formula:

[0265]

change

[0266]

change

[0267]

change

[0268]

change

[0269]

change

[0270]

change

[0271]

change

[0272]

change

[0273]

change

[0274]

change

[0275]

change

[0276]

change

[0277]

change

[0278]

change

[0279]

change

[0280]

change

[0281]

change

[0282]

change

[0283]

change

[0284]

change

[0285]

change

[0286]

change

[0287]

change

[0288]

change

[0289]

change

[0290]

change

[0291]

change

[0292]

change

[0293]

change

[0294]

change

[0295]

change

[0296]

change

[0297]

change

[0298]

change

[0299]

change

[0300]

change

[0301]

change

[0302]

change

[0303]

change

[0304]

change

[0305]

change

[0306]

change

[0307]

change

[0308] [ka]

[0309] [ka]

[0310] [ka]

[0311] [ka]

[0312] [ka]

[0313] wherein R 1 , R 2 , R 3 , R 4 , X 1 , X 2 , R a , R b , L, L' and r have the meanings given above, and a and b are 1 or 2. The above formulae I1a to I19m are defined as adjacent groups Ar 1~5 and the E- or Z-stereoisomers thereof relative to the C=C double bond of the terminal group, for example,

[0314] [ka]

[0315] may occur identically or differently in each occurrence,

[0316] [ka]

[0317] It can also be shown. Preferably, in the formulae I1a to I19m, L' is H. More preferably, in the formulae I1a to I19m, r is 0.

[0318] Preferably, in formulae I1a to I19m, R 1 , R 2 , R 3 and R 4 is selected from alkyl or alkoxy having 1 to 16 C atoms, optionally fluorinated. More preferably, in the formulae I1a to I19m, R 1 , R 2 , R 3 and R 4 is selected from alkyl, alkoxy or thioalkyl having 1 to 16 C atoms, preferably phenyl optionally substituted in the 4-position or the 3,5-position.

[0319] Another embodiment of the present invention relates to a composition comprising a compound of Formula I, further comprising one or more electron donors or p-type semiconductors, preferably selected from conjugated polymers. Preferably, the conjugated polymer used in the composition comprises at least one electron donating unit ("donor unit") and at least one electron accepting unit ("acceptor unit"), and optionally at least one spacer unit separating the donor unit from the acceptor unit, wherein each donor and acceptor unit is directly bonded to another donor or acceptor unit or spacer unit, and all of the donor, acceptor, and spacer units are selected from arylene or heteroarylene having 5 to 20 ring atoms, monocyclic or polycyclic, optionally containing fused rings, and unsubstituted or substituted with one or more identical or different groups L, as defined above.

[0320] Preferably, the spacer unit, if present, is located between the donor and acceptor units so that the donor and acceptor units are not directly bonded to each other. Preferred conjugated polymers comprise one or more units selected from formulae U1, U2 and U3, and / or one or more units selected from formulae U3 and U4 -(D-Sp)- U1 -(A-Sp)- U2 -(AD)- U3 -(D)- U4 -(Sp-A-Sp)- U5 wherein D represents a donor unit, A represents an acceptor unit and Sp represents a spacer unit, all of which are selected from arylene or heteroarylene having 5 to 20 ring atoms, being monocyclic or polycyclic, optionally containing fused rings, and which are unsubstituted or substituted with one or more identical or different groups L as defined above.

[0321] Highly preferred are polymers of formula Pi and Pii -[(D-Sp) x -(A-Sp) y ] n -Pi -[(AD) x -(A-Sp) y ] n - Pii -[(D) x -(Sp-A-Sp) y ] n -Piii where A, D, and Sp are as defined in formulas U1-U5, x and y represent the mole fraction of the corresponding units, and x and y are each, independently of one another, greater than 0 and less than 1, where x+y=1, and n is an integer greater than 1.

[0322] A preferred donor unit or unit D is of the formula:

[0323] [ka]

[0324] [ka]

[0325] [ka]

[0326] wherein R 11 , R 12 , R 13 , R 14 denote, independently of one another, H or have one of the meanings of L defined above. A preferred acceptor unit or unit A is of the formula

[0327] [ka]

[0328] wherein R 11 , R 12 , R 13 , R 14 denote, independently of one another, H or have one of the meanings of L defined above. A preferred spacer unit or unit Sp is of the formula

[0329] [ka]

[0330] [ka]

[0331] [ka]

[0332] [ka]

[0333] wherein R 11 , R 12 , R 13 , R 14 denote, independently of one another, H or have one of the meanings of L defined above. In the formulae Sp1 to Sp17, preferably, R 11 and R 12 is H. In formula Sp18, preferably, R 11~14 is H or F.

[0334] Preferably, the conjugated polymer is a) one or more donor units selected from the group consisting of formulae D1, D7, D10, D11, D19, D22, D29, D30, D35, D36, D37, D44, D55, D84, D87, D88, D89, D93, D106, D111, D119, D140, D141, D146, and D147; and / or b) one or more acceptor units selected from the group consisting of formulae A1, A5, A7, A15, A16, A20, A74, A88, A92, A94 and A98, A99, A100 and c) optionally one or more spacer units selected from the group consisting of formulae Sp1 to Sp18, very preferably formulae Sp1, Sp6, Sp11 and Sp14 wherein the spacer unit, if present, is preferably located between the donor and acceptor units such that the donor and acceptor units are not directly bonded to each other.

[0335] In a second preferred embodiment, the compound of formula I is one or more, preferably one, two, three or four different repeat units D, and one or more, preferably one, two or three different repeat units A and preferably a conjugated polymer consisting of these.

[0336] Preferably, the conjugated polymer according to this second preferred embodiment contains 1 to 6, very preferably 1, 2, 3 or 4 different units D and 1 to 6, very preferably 1, 2, 3 or 4 different units A, where d1, d2, d3, d4, d5 and d6 represent the molar ratio of each different unit D and a1, a2, a3, a4, a5 and a6 represent the molar ratio of each different unit A, each of d1, d2, d3, d4, d5, and d6 is 0 to 0.6, and d1+d2+d3+d4+d5+d6 is 0.2 to 0.8, preferably 0.3 to 0.7; each of a1, a2, a3, a4, a5, and a6 is 0 to 0.6, and a1+a2+a3+a4+a5+d6 is 0.2 to 0.8, preferably 0.3 to 0.7; d1+d2+d3+d4+d5+d6+a1+a2+a3+a4+a5+a6 is 0.8 to 1, preferably 1.

[0337] Preferably, the conjugated polymer according to this second preferred embodiment comprises: a) one or more donor units selected from the group consisting of formula D1, D7, D10, D11, D19, D22, D29, D30, D35, D36, D37, D44, D55, D84, D87, D88, D89, D93, D106, D111, D119, D140, D141, D146 and D147, and / or b) one or more acceptor units selected from the group consisting of formulae A1, A5, A7, A15, A16, A20, A74, A88, A92, A94, A98, A99 and A100 It contains, and preferably consists of,

[0338] In the above conjugated polymers, such as those of formula P and subformulas thereof, the total number of repeat units, n, is preferably from 2 to 10,000. The total number of repeat units, n, is preferably 5 or more, very preferably 10 or more, most preferably 50 or more, and preferably 500 or less, very preferably 1,000 or less, and most preferably 2,000 or less, including any combination of the above lower and upper limits for n.

[0339] The conjugated polymer is preferably a statistical or random copolymer. Highly preferred conjugated polymers have the formula:

[0340] [ka]

[0341] [ka]

[0342] [ka]

[0343] [ka]

[0344] [ka]

[0345] [ka]

[0346] [ka]

[0347] [ka]

[0348] [ka]

[0349] [ka]

[0350] [ka]

[0351] [ka]

[0352] [ka]

[0353] wherein R 11~17 , x, y and n are as defined above, w and z have one of the meanings given for y, x+y+w+z=1, and R 18 and R 19 But R 11 has one of the meanings given for X 1 , X 2 , X 3 and X 4 represents H, F or Cl.

[0354] Further preferred are polymers comprising one of the formulae P1 to P53 as one or more repeat units. Two building blocks [ ] x and [ ] yIn the polymers of formula Pi, Pii, Piii and P1 to P53 consisting of: x and y are preferably 0.1 to 0.9, very preferably 0.25 to 0.75, most preferably 0.4 to 0.6.

[0355] Three building blocks [ ] x , [ ] y , and [ ] z In the polymers of formula Pi, Pii, Piii and P1 to P53 consisting of: x, y and z are preferably 0.1 to 0.8, very preferably 0.2 to 0.6, most preferably 0.25 to 0.4.

[0356] In the formulae P1 to P53, preferably, X 1 , X 2 , X 3 and X 4 One or more of X represents F, very preferably 1 , X 2 , X 3 and X 4 All of the above show F or X 1 and X 2 indicates H, and X 3 and X 4 indicates F.

[0357] In the formulae P1 to P53, preferably, R 11 and R 12 is H. More preferably, R 11 and R 12 If different from H, denotes optionally fluorinated straight-chain or branched alkyl having 1 to 30, preferably 1 to 20, C atoms.

[0358] In the formulae P1 to P53, preferably, R 15 and R 16 is H and R 13 and R 14 However, it is different from H. In the formulae P1 to P53, preferably, R 13 , R 14 , R 15 and R 16If is different from H, then the following group: the group consisting of optionally fluorinated linear or branched alkyl, alkoxy or sulfanylalkyl having 1 to 30, preferably 1 to 20, C atoms, the group consisting of linear or branched alkylcarbonyl or alkylcarbonyloxy, optionally fluorinated, having 2 to 30, preferably 2 to 20, C atoms; is selected from.

[0359] In the formulae P1 to P53, preferably, R 17 and R 18 If is different from H, then the following group: the group consisting of optionally fluorinated linear or branched alkyl, alkoxy or sulfanylalkyl having 1 to 30, preferably 1 to 20, C atoms, the group consisting of optionally fluorinated linear or branched alkylcarbonyl or alkylcarbonyloxy having 2 to 30, preferably 2 to 20, C atoms, -The group consisting of F and Cl is selected from.

[0360] Further preferred is a compound of the formula PT R 31 -Chain-R 32 PT wherein "chain" represents a polymer chain selected from formulas Pi, Pii, or P1 to P53; and R 31 and R 32 are, independently of each other, R as defined above 11or independently of one another, represent H, F, Br, Cl, I, -CH2Cl, -CHO, -CR'=CR"2, -SiR'R"R"', -SiR'X'X", -SiR'R"X', -SnR'R"R"', -BR'R", -B(OR')(OR"), -B(OH)2, -O-SO2-R', -C≡CH, -C≡C-SiR'3, -ZnX' or an end-capping group, where X' and X" represent halogen, and R', R" and R'" independently of one another represent the R groups shown in Formula 1. 0 and preferably denotes alkyl having 1 to 12 C atoms, and two of R', R" and R'" together with the respective heteroatom to which they are attached can also form a cyclosilyl, cyclostannyl, cycloborane or cycloboronate group having 2 to 20 C atoms.

[0361] Preferred End-Capping Groups R 31 and R 32 is H, C 1~20 alkyl, or optionally substituted C 6~12 Aryl or C 2~10 Heteroaryl, very preferably H, phenyl or thiophene.

[0362] The compounds of formula I and the conjugated polymers of formula Pi, Pii, Pii, P1-P53 and PT can be synthesized according to or in analogy with methods known to those skilled in the art and described in the literature. Other preparation methods can be found in the examples.

[0363] For example, the compounds of the present invention can be conveniently prepared by aryl-aryl coupling reactions such as Yamamoto coupling, Suzuki coupling, Stille coupling, Sonogashira coupling, Heck coupling or Buchwald coupling. The educts can be prepared according to methods known to those skilled in the art.

[0364] Preferred aryl-aryl coupling methods used in the synthetic methods described above and below are Yamamoto coupling, Kumada coupling, Negishi coupling, Suzuki coupling, Stille coupling, Sonogashira coupling, Heck coupling, C-H activation coupling, Ullmann coupling, or Buchwald coupling. Particularly preferred are Suzuki coupling, Negishi coupling, Stille coupling, and Yamamoto coupling. Suzuki coupling is described, for example, in International Publication No. 00 / 53656 A1. Negishi coupling is described, for example, in J. Chem. Soc., Chem. Commun., 1977, 683-684. Yamamoto coupling is described, for example, in T. Yamamoto et al., Prog. Polym. Sci., 1993, 17, 1153-1205, or in International Publication No. 2004 / 022626 A1. Stille coupling is described, for example, in Z. Bao et al., J. Am. Chem. Soc., 1995, 117, 12426-12435, and C-H activation is described, for example, in M. Leclerc et al., Angew. Chem. Int. Ed., 2012, 51, 2068-2071. For example, when using Yamamoto coupling, educts bearing two reactive halide groups are preferably used. When using Suzuki coupling, educts bearing two reactive boronic acid or boronic ester groups or two reactive halide groups are preferably used. When using Stille coupling, educts bearing two reactive stannane groups or two reactive halide groups are preferably used. When using Negishi coupling, educts bearing two reactive organozinc groups or two reactive halide groups are preferably used.

[0365] In particular, preferred catalysts for Suzuki, Negishi, or Stille couplings are selected from Pd(0) complexes or Pd(II) salts. Preferred Pd(0) complexes have at least one phosphine ligand, such as Pd(Ph3P). Another preferred phosphine ligand is tris(ortho-tolyl)phosphine, i.e., Pd(o-Tol3P). Preferred Pd(II) salts include palladium acetate, i.e., Pd(OAc). Alternatively, Pd(0) complexes can be prepared by mixing a Pd(0) dibenzylideneacetone complex, such as tris(dibenzylideneacetone)dipalladium(0), bis(dibenzylideneacetone)palladium(0), or a Pd(II) salt, such as palladium acetate, with a phosphine ligand, such as triphenylphosphine, tris(ortho-tolyl)phosphine, or tri(tert-butyl)phosphine. The Suzuki coupling is carried out in the presence of a base such as sodium carbonate, potassium carbonate, cesium carbonate, lithium hydroxide, potassium phosphate, or an organic base such as tetraethylammonium carbonate or tetraethylammonium hydroxide. The Yamamoto coupling uses a Ni(0) complex such as bis(1,5-cyclooctadienyl)nickel(0).

[0366] As an alternative to the halogens mentioned above, there are compounds of the formula -O-SOZ 0 can be used, where Z 0 is an alkyl or aryl group, preferably C 1~10 Alkyl or C 6~12 aryl. Particular examples of such leaving groups are tosylate, mesylate and triflate.

[0367] Particularly suitable and preferred methods of synthesis of compounds of formula I and subformulas thereof are illustrated in the synthetic schemes shown below. The synthesis of the cyclic units is illustratively shown in Schemes 1-4.

[0368] Scheme 1a

[0369] [ka]

[0370] [ka]

[0371] Scheme 1b

[0372] [ka]

[0373] [ka]

[0374] Scheme 2

[0375] [ka]

[0376] Scheme 3

[0377] [ka]

[0378] Scheme 4

[0379] [ka]

[0380] The novel processes for preparing compounds of formula I described above and below are another aspect of the present invention. The compounds of formula I may also be used in compositions, for example, together with monomeric or polymeric compounds having charge transporting, semiconducting, conductive, photoconductive and / or light emitting semiconducting properties, or together with compounds having hole blocking or electron blocking properties, for use, for example, as interlayers or charge blocking layers in PSCs or OLEDs.

[0381] Accordingly, another aspect of the present invention relates to compositions comprising one or more compounds of Formula I and one or more small molecule compounds and / or polymers having one or more of charge transporting, semiconducting, electrically conductive, photoconducting, hole blocking, and electron blocking properties.

[0382] These composition blends can be prepared by conventional methods known to those skilled in the art and described in the prior art. Typically, the compounds and / or polymers are mixed with each other or dissolved in suitable solvents and the solutions are combined.

[0383] Another aspect of the invention relates to formulations comprising one or more compounds or compositions of formula I described above and below and one or more organic solvents. Preferred solvents are aliphatic hydrocarbons, chlorinated hydrocarbons, aromatic hydrocarbons, ketones, ethers and mixtures thereof. Further solvents that may be used include 1,2,4-trimethylbenzene, 1,2,3,4-tetra-methylbenzene, pentylbenzene, mesitylene, cumene, cymene, cyclohexylbenzene, diethylbenzene, tetralin, decalin, 2,6-lutidine, 2-fluoro-m-xylene, 3-fluoro-o-xylene, 2-chlorobenzotrifluoride, N,N-dimethylformamide, 2-chloro-6-fluorotoluene, 2-fluoroanisole, anisole, 2,3-dimethylpyrazine, 4-fluoroanisole, 3-fluoroanisole, 3-trifluoro-methylanisole, 2-methylanisole, phenetole, 4-methylanisole, 3-methylanisole, 4-fluoro-3-methylanisole, 2-fluorobenzonitrile, 4-fluoroveratrol, 2,6-dimethylanisole, 3-fluorobenzonitrile, 2,5-dimethylanisole, 2,4-dimethylanisole, benzonitrile, 3, Examples of suitable solvents include 5-dimethyl-anisole, N,N-dimethylaniline, ethyl benzoate, 1-fluoro-3,5-dimethoxy-benzene, 1-methylnaphthalene, N-methylpyrrolidinone, 3-fluorobenzotrifluoride, benzotrifluoride, dioxane, trifluoromethoxy-benzene, 4-fluorobenzotrifluoride, 3-fluoropyridine, toluene, 2-fluorotoluene, 2-fluorobenzotrifluoride, 3-fluorotoluene, 4-isopropylbiphenyl, phenyl ether, pyridine, 4-fluorotoluene, 2,5-difluorotoluene, 1-chloro-2,4-difluorobenzene, 2-fluoropyridine, 3-chlorofluorobenzene, 1-chloro-2,5-difluorobenzene, 4-chlorofluorobenzene, chlorobenzene, o-dichlorobenzene, 2-chlorofluorobenzene, p-xylene, m-xylene, o-xylene or a mixture of o-, m-, and p-isomers. Solvents with relatively low polarity are generally preferred. For inkjet printing, solvents and solvent mixtures with high boiling points are preferred, while for spin coating, alkylated benzenes such as xylene and toluene are preferred.

[0384] Examples of particularly preferred solvents include, but are not limited to, dichloromethane, trichloromethane, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, 2,4-dimethylanisole, 1-methylnaphthalene, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4-dioxane, acetone, methyl ethyl ketone, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, n-butyl acetate, N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, 1,5-dimethyltetralin, propiophenone, acetophenone, tetralin, 2-methylthiophene, 3-methylthiophene, decalin, indane, methyl benzoate, ethyl benzoate, mesitylene, and / or mixtures thereof.

[0385] The concentration of the compound or polymer in the solution is preferably 0.1 to 10% by weight, more preferably 0.5 to 5% by weight. Optionally, the solution also contains one or more binders to adjust the rheological properties, as described, for example, in WO 2005 / 055248 A1.

[0386] After appropriate mixing and aging, the solution is rated as one of the following categories: complete solution, borderline solution, or insoluble. Contour lines are drawn to outline the solubility parameter—the hydrogen bonding threshold—that separates soluble from insoluble. "Perfect" solvents that fall within the solubility region can be selected from literature values ​​such as those published in "Crowley, JD, Teague, GS Jr, and Lowe, JW Jr., Journal of Paint Technology, 1966, 38(496), 296." Solvent blends may also be used and can be identified as described in "Solvents, W.H. Ellis, Federation of Societies for Coatings Technology, pp. 9-10, 1986." Although such a procedure may result in a blend of "non" solvents that will dissolve both polymers of the present invention, it is desirable to have at least one true solvent in the blend.

[0387] The compounds of formula I can also be used to pattern OSC layers in the devices described above and below. In modern microelectronic applications, it is generally desirable to produce small structures or patterns to reduce cost (more devices per unit area) and power consumption. Patterning of thin layers comprising the compounds of the present invention can be carried out, for example, by photolithography, electron beam lithography, or laser patterning.

[0388] For use as a thin layer in an electronic or electro-optical device, the compound, composition, or formulation of the present invention can be deposited by any suitable method. Liquid coating of the device is preferable to vacuum deposition techniques. Solution deposition methods are particularly preferred. The formulation of the present invention allows the use of many liquid coating techniques. Preferred deposition techniques include, but are not limited to, dip coating, spin coating, inkjet printing, nozzle printing, letterpress printing, screen printing, gravure printing, doctor blade coating, roller printing, reverse roller printing, offset lithography printing, dry offset lithography printing, flexography printing, web printing, spray coating, curtain coating, brush coating, slot die coating, or pad printing.

[0389] Inkjet printing is particularly preferred when high-resolution layers and devices need to be produced. The selected formulations of the present invention can be applied to pre-assembled device substrates by inkjet printing or microdispensing. Preferably, industrial piezoelectric printheads, such as those supplied by Aprion, Hitachi Koki, InkJet Technology, On Target Technology, Picojet, Spectra, Trident, and Xaar, can be used to apply organic semiconductor layers to substrates. Furthermore, semi-industrial printheads, such as those manufactured by Brother, Epson, Konica, Seiko Instruments, and Toshiba TEC, or single-nozzle microdispensers, such as those manufactured by Microdrop and Microfab, can be used.

[0390] To be applied by inkjet printing or microdispensing, the compound or polymer should first be dissolved in a suitable solvent. The solvent must meet the requirements described above and must not have any adverse effects on the selected printhead. Furthermore, the solvent should have a boiling point above 100°C, preferably above 140°C, and more preferably above 150°C, to prevent operability problems caused by the solution drying inside the printhead. In addition to the solvents described above, suitable solvents include substituted and unsubstituted xylene derivatives, di-C 1~2 -Alkylformamides, substituted and unsubstituted anisole and other phenol-ether derivatives, substituted heterocycles such as substituted pyridines, pyrazines, pyrimidines, pyrrolidinones, substituted and unsubstituted N,N-di-C 1~2 - alkylanilines and other fluorinated or chlorinated aromatic compounds.

[0391] Preferred solvents for depositing the compound of Formula I by inkjet printing include benzene derivatives having a benzene ring substituted with one or more substituents, where the total number of carbon atoms in the one or more substituents is at least three. For example, the benzene derivative may be substituted with a propyl group or three methyl groups, where in each case there are at least three carbon atoms in total. Such solvents allow the formation of an inkjet fluid containing the compound or polymer in the solvent, thereby reducing or preventing jet clogging and component separation during spraying. Examples of solvents include those selected from the following list: dodecylbenzene, 1-methyl-4-tert-butylbenzene, terpineol, limonene, isodurene, terpinolene, cymene, and diethylbenzene. The solvent may be a solvent mixture, which is a combination of two or more solvents, each of which preferably has a boiling point above 100°C, more preferably above 140°C. Such solvents also promote film formation in the deposited layer and reduce defects in the layer.

[0392] The inkjet fluid (ie, the mixture of solvent, binder and semiconducting compound) preferably has a viscosity at 20°C of 1 to 100 mPa·s, more preferably 1 to 50 mPa·s, and most preferably 1 to 30 mPa·s.

[0393] The compositions and formulations according to the invention may further comprise one or more further components or additives selected, for example, from surface-active compounds, lubricants, wetting agents, dispersants, hydrophobizing agents, adhesives, flow improvers, antifoaming agents, deaerators, diluents which may be reactive or non-reactive, adjuvants, colorants, dyes or pigments, sensitizers, stabilizers, nanoparticles or inhibitors.

[0394] The compositions of the present invention are useful as charge transport, semiconducting, conductive, photoconductive or light emitting materials in optical, electrooptical, electronic, electroluminescent or photoluminescent components or devices in which the compounds of the present invention are typically applied as thin layers or films.

[0395] Thus, the present invention also provides the use of a semiconductor compound, composition, or layer in an electronic device. The compound or composition can be used as a high-mobility semiconductor material in various devices and apparatuses. The compound or composition can be used, for example, in the form of a semiconductor layer or film. Thus, in another aspect, the present invention provides a semiconductor layer for use in an electronic device, the layer comprising a compound or composition according to the present invention. The layer or film can be less than about 30 μm thick. For various electronic device applications, the thickness can be less than about 1 μm thick. The layer can be deposited on a component of an electronic device, for example, by any of the solution coating or printing techniques described above.

[0396] The present invention further provides an electronic device comprising the compound or composition or organic semiconductor layer according to the present invention. Particularly preferred devices are OFET, TFT, IC, logic circuit, capacitor, RFID tag, OLED, OLET, OPED, OPV, PSC, OPD, solar cell, laser diode, photoconductor, photodetector, electrophotographic device, electrophotographic recording device, organic memory device, sensor device, charge injection layer, Schottky diode, planarization layer, antistatic film, conductive substrate and conductive pattern.

[0397] Particularly preferred electronic devices are OFET, OLED, OPV, PSC and OPD devices, especially OPD, PSC and bulk heterojunction (BHJ) OPV devices.In OFET, for example, the active semiconductor channel between drain and source can comprise the compound or composition of the present invention.As another example, in OLED device, charge (hole or electron) injection or transport layer can comprise the compound or composition of the present invention.

[0398] For use in the photoactive layer of an OPV or OPD device, the compounds according to the invention are preferably used in compositions comprising or containing, more preferably consisting of, one or more p-type (electron donor) semiconductors and one or more n-type (electron acceptor) semiconductors.

[0399] The n-type semiconductor may be constituted, for example, by a compound of formula I: The p-type semiconductor is preferably a conjugated polymer as defined above. The composition may also include a compound of Formula I as an n-type semiconductor, a p-type semiconductor such as a conjugated polymer, and a second n-type semiconductor that is preferably a fullerene or a substituted fullerene.

[0400] Fullerenes include, for example, indene-C, such as ICBA. 60-fullerene bisadducts, or, for example, "PCBM-C" as disclosed in G. Yu, J. Gao, J.C. Hummelen, F. Wudl, A.J. Heeger, Science 1995, Vol. 270, p. 1789 et seq., and having the structure shown below. 60 " or "C 60 (6,6)-Phenyl-butyric acid methyl ester derivatized methanoic acid, also known as PCBM 60 Fullerenes, or e.g., C 61 Fullerene group, C 70 Fullerene group, or C 71 These are structurally similar compounds with fullerene groups, or organic polymers (see, for example, Coakley, KM and McGehee, MD, Chem. Mater. 2004, 16, 4533).

[0401] [ka]

[0402] Preferably, the polymers according to the present invention are mixed with an n-type semiconductor, such as a fullerene or substituted fullerene of formula Full-I, to form the active layer in an OPV or OPD device, wherein:

[0403] [ka]

[0404] C n denotes a fullerene composed of n carbon atoms, optionally with one or more atoms trapped therein; Additions 1 However, fullerene C n is a first addition added to Additions 2 However, fullerene C na second adduct, or a combination of second adducts, attached to k is an integer equal to or greater than 1, l is 0, an integer greater than or equal to 1, or a non-integer greater than 0.

[0405] In formula Full-I and its subformulas, k preferably denotes 1, 2, 3 or 4, very preferably 1 or 2. Fullerene C in formula Full-I and its subformulas n can be composed of any number n of carbon atoms. Preferably, in the compounds of formula XII and its subformulas, fullerene C n The number n of carbon atoms constituting the formula is 60, 70, 76, 78, 82, 84, 90, 94 or 96, and very preferably 60 or 70.

[0406] Fullerene C in formula Full-I and its subformulas n is preferably selected from carbon-based fullerenes, endohedral fullerenes, or mixtures thereof, very preferably carbon-based fullerenes.

[0407] Suitable and preferred carbon-based fullerenes include, but are not limited to, (C 60-Ih )[5,6]fullerene, (C 70-D5h )[5,6]fullerene, (C 76-D2 * )[5,6]fullerene, (C 84-D2 * )[5,6]fullerene, (C 84-D2d )[5,6] fullerene, or a mixture of two or more of the above carbon-based fullerenes.

[0408] The endohedral fullerene is preferably a metallofullerene. Suitable and preferred metallofullerenes include, but are not limited to, La@C 60 , La@C 82 , Y@C 82 , Sc3N@C 80 , Y3N@C 80 , Sc3C2@C 80Or a mixture of two or more of the above metallofullerenes.

[0409] Preferably, fullerene C n is substituted at the [6,6] and / or [5,6] bond, preferably at least one [6,6] bond. The first and second adducts designated as "adducts" in formula Full-I and its subformulas preferably have the following formula:

[0410] [ka]

[0411] [ka]

[0412] is selected from: Ar S1 , Ar S2 denote, independently of one another, an aryl or heteroaryl radical having 5 to 20, preferably 5 to 15, ring atoms, which is monocyclic or polycyclic and optionally substituted with one or more identical or different substituents having one of the meanings of L as defined above and below, R S1 , R S2 , R S3 , R S4 and R S5 are, independently of one another, H, CN or R as defined above and below; S It has one of the meanings.

[0413] Preferred compounds of formula Full-I have the following subformula:

[0414] [ka]

[0415] [ka]

[0416] [ka]

[0417] is selected from: R S1 , R S2 , R S3 , R S4 R S5 and R S6 are, independently of one another, H or R as defined above and below; S It has one of the meanings.

[0418] Most preferably, the fullerene is PCBM-C60, PCBM-C70, bis-PCBM-C60, bis-PCBM-C70, ICMA-c60 (1',4'-dihydro-naphtho[2',3':1,2][5,6]fullerene-C60), ICBA, oQDM-C60 (1',4'-dihydro-naphtho[2',3':1,9][5,6]fullerene-C60-Ih), or bis-oQDM-C60.

[0419] The OPV or OPD device preferably further comprises a first transparent or semitransparent electrode on a transparent or semitransparent substrate on one side of the photoactive layer, and a second metallic or semitransparent electrode on the other side of the photoactive layer.

[0420] More preferably, the OPV or OPD device has a thin film of SiO2 or MoO3 between the photoactive layer and the first or second electrode. x , NiO xas hole transporting and / or electron blocking layers comprising materials such as metal oxides such as, for example, PEDOT:PSS, conjugated polymer electrolytes such as, for example, PEDOT:PSS, conjugated polymers such as, for example, polytriarylamine (PTAA), insulating polymers such as, for example, Nafion, polyethyleneimine or polystyrene sulfonate, organic compounds such as, for example, N,N'-diphenyl-N,N'-bis(1-naphthyl)(1,1'-biphenyl)-4,4'diamine (NPB), N,N'-diphenyl-N,N'-(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), or ZnO, for example. x , TiO x and one or more additional buffer layers acting as hole-blocking and / or electron-transporting layers, including materials such as metal oxides such as CI, ...

[0421] In compositions according to the present invention comprising a compound of formula I and a conjugated polymer, the ratio of polymer to compound of formula I is preferably 5:1 to 1:5 by weight, more preferably 3:1 to 1:3 by weight, and most preferably 2:1 to 1:2 by weight.

[0422] The composition according to the present invention may also contain a polymer binder, preferably in an amount of 0.001 to 95% by weight, such as polystyrene (PS), polydimethylsilane (PDMS), polypropylene (PP), and polymethylmethacrylate (PMMA).

[0423] The binder used in the above-described formulation, which is preferably a polymer, may comprise either an insulating binder or a semiconducting binder, or a mixture thereof, and may be referred to herein as an organic binder, a polymeric binder, or simply a binder.

[0424] Preferably, the polymer binder has a weight average molecular weight in the range of 1000 to 5,000,000 g / mol, in particular 1500 to 1,000,000 g / mol, more preferably 2000 to 500,000 g / mol. Surprising effects are obtained with polymers having a weight average molecular weight of at least 10,000 g / mol, more preferably at least 100,000 g / mol.

[0425] In particular, the polymer has a polydispersity index M in the range of 1.0 to 10.0, more preferably in the range of 1.1 to 5.0, and most preferably in the range of 1.2 to 3. w / M n may have: Preferably, the inert binder is a polymer having a glass transition temperature in the range of -70 to 160° C., preferably 0 to 150° C., more preferably 50 to 140° C. and most preferably 70 to 130° C. The glass transition temperature can be determined by measuring the polymer by DSC (DIN EN ISO 11357, heating rate 10° C. / min).

[0426] The weight ratio of polymer binder to OSC compound, similar to that of formula I, is preferably in the range of 30:1 to 1:30, in particular in the range of 5:1 to 1:20, more preferably in the range of 1:2 to 1:10.

[0427] According to a preferred embodiment, the binder preferably comprises repeat units derived from styrene and / or olefin monomers. Preferred polymer binders may comprise at least 80%, preferably 90%, more preferably 99% by weight of repeat units derived from styrene and / or olefin monomers.

[0428] Styrene monomers are well known in the art and include styrene, substituted styrenes with alkyl substituents in the side chain, such as α-methylstyrene and α-ethylstyrene, substituted styrenes with alkyl substituents on the ring, such as vinyltoluene and p-methylstyrene, and halogenated styrenes, such as monochlorostyrene, dichlorostyrene, tribromostyrene, and tetrabromostyrene.

[0429] Olefin monomers consist of hydrogen and carbon atoms. These monomers include ethylene, propylene, butylene, isoprene, and 1,3-butadiene. According to a preferred embodiment of the present invention, the polymer binder is polystyrene having a weight average molecular weight in the range of 50,000 to 2,000,000 g / mol, preferably in the range of 100,000 to 750,000 g / mol, more preferably in the range of 150,000 to 600,000 g / mol, and most preferably in the range of 200,000 to 500,000 g / mol.

[0430] Further examples of suitable binders are disclosed, for example, in US Patent Application Publication No. 2007 / 0102696 A1. Particularly suitable and preferred binders are described below.

[0431] The binder is preferably capable of forming a film, more preferably a flexible film. Polymers suitable as binders include poly(1,3-butadiene), polyphenylene, polystyrene, poly(α-methylstyrene), poly(α-vinylnaphthalene), poly(vinyltoluene), polyethylene, cis-polybutadiene, polypropylene, polyisoprene, poly(4-methyl-1-pentene), poly(4-methylstyrene), poly(chlorotrifluoroethylene), poly(2-methyl-1,3-butadiene), poly(p-xylylene), poly(α-α-α'-α'-tetrafluoro-p-xylylene), and poly(α-methyl-1,3-butadiene). ethylenediamine), poly[1,1-(2-methylpropane)bis(4-phenyl)carbonate], poly(cyclohexyl methacrylate), poly(chlorostyrene), poly(2,6-dimethyl-1,4-phenylene ether), polyisobutylene, poly(vinylcyclohexane), poly(vinyl cinnamate), poly(4-vinylbiphenyl), 1,4-polyisoprene, polynorbornene, poly(styrene-block-butadiene); 31% by weight of styrene, poly(styrene-block-butadiene-block-styrene); 30% by weight styrene, poly(styrene-co-maleic anhydride) (and ethylene / butylene) 1-1.7% maleic anhydride, poly(styrene-block-ethylene / butylene-block-styrene) triblock polymer 13% styrene, poly(styrene-block-ethylene-propylene-block-styrene) triblock polymer 37% by weight styrene, poly(styrene-block-ethylene / butylene-block-styrene) triblock polymer 29% by weight styrene, poly(1-vinylnaphthalene), poly(1-vinylpyrrolidone-co-styrene) 64% styrene, poly(1-vinylpyrrolidone-co-vinyl acetate) 1.3:1, poly(2-chlorostyrene), poly(2-vinylnaphthalene), poly(2-vinylpyridine-co-styrene) 1:1, poly(4,5-difluoro-2,2-bis(CF3)-1,3-dioxole-co-tetrafluoroethylene) Teflon® (Teflon), poly(4-chlorostyrene), poly(4-methyl-1-pentene), poly(4-methylstyrene), poly(4-vinylpyridine-co-styrene) 1:1, poly(α-methylstyrene), poly(butadiene-graft-poly(methyl acrylate-co-acrylonitrile)) 1:1:1, poly(butyl methacrylate-co-isobutyl methacrylate) 1:1, poly(butyl methacrylate-co-methyl methacrylate) 1:1, poly (cyclohexyl methacrylate), poly(ethylene-co-1-butene-co-1-hexene) 1:1:1, poly(ethylene-co-ethyl acrylate-co-maleic anhydride); 2% anhydride, 32% ethyl acrylate, poly(ethylene-co-glycidyl methacrylate) 8% glycidyl methacrylate, poly(ethylene-co-methyl acrylate-co-glycidyl methacrylate) 8% glycidyl methacrylate 25% methyl acrylate, Poly(ethylene-co-octene) 1:1, poly(ethylene-co-propylene-co-5-methylene-2-norbornene) 50% ethylene, poly(ethylene-co-tetrafluoroethylene) 1:1, Poly(isobutyl methacrylate), poly(isobutylene), poly(methyl methacrylate)-co-(fluorescein O-methacrylate) 80% methyl methacrylate, poly(methyl methacrylate-co-butyl methacrylate) 85% methyl methacrylate, poly(methyl methacrylate-co-ethyl acrylate) 5% ethyl acrylate, poly(propylene-co-butene) 12% 1-butene, poly(styrene-co-allyl alcohol) 40% allyl alcohol , poly(styrene-co-maleic anhydride) 7% maleic anhydride, cumene-terminated poly(styrene-co-maleic anhydride) (1.3:1), poly(styrene-co-methyl methacrylate) 40% styrene, poly(vinyl toluene-co-α-methylstyrene) 1:1, poly-2-vinylpyridine, poly-4-vinylpyridine, poly-α-pinene, polymethyl methacrylate, polybenzyl methacrylate, polyethyl methacrylate, polyethylene, polyethylene terephthalate, poly Polyethylene-co-ethyl acrylate 18% ethyl acrylate, polyethylene-co-vinyl acetate 12% vinyl acetate, polyethylene-graft-maleic anhydride 0.5% maleic anhydride, polypropylene, polypropylene-graft-maleic anhydride 8-10% maleic anhydride, polystyrene poly(styrene-block-ethylene / butylene-block-styrene) graft-maleic anhydride 2% maleic anhydride 1:1:1, branched poly(styrene-block-butadiene) 1:1, poly(styrene-block-butadiene-block-styrene) 30% styrene, poly(styrene-block-isoprene) 10% styrene by weight, poly(styrene-block-isoprene-block-styrene) 17% styrene by weight, poly(styrene-co-4-chloromethylstyrene-co-4-methoxymethylstyrene 2:1:1), polystyrene-co-acrylonitrile 25% acrylonitrile, polystyrene-co-α-methylstyrene 1:1, Polystyrene-co-butadiene 4% butadiene, polystyrene-co-butadiene 45% styrene, polystyrene-co-chloromethylstyrene 1:1, polyvinyl chloride, Polyvinyl cinnamate, polyvinylcyclohexane, polyvinylidene fluoride, Polyvinylidene fluoride-co-hexafluoropropylene estimated 1:1, poly(styrene-block-ethylene / propylene-block-styrene) 30% styrene, poly(styrene-block-ethylene / propylene-block-styrene) 18% styrene, poly(styrene-block-ethylene / propylene-block-styrene) 13% styrene, poly(styrene-block-ethylene-block-ethylene / propylene-block-styrene) 32% styrene, poly(styrene-block-ethylene-block-ethylene / propylene-block-styrene) 30% styrene, poly(styrene-block-ethylene / butylene-block-styrene) 31% styrene, poly(styrene-block-ethylene / butylene-block-styrene) Polystyrene-block-ethylene / butylene-block-styrene) 34% styrene, poly(styrene-block-ethylene / butylene-block-styrene) 30% styrene, poly(styrene-block-ethylene / butylene-block-styrene) 60% styrene, branched or unbranched polystyrene-block-polybutadiene, polystyrene-block(polyethylene-ran-butylene)-block-polystyrene, polystyrene-block-polybutadiene-block-polystyrene, polystyrene-(ethylene-propylene)-diblock-copolymer (e.g., KRATON®-G1701E, Shell), poly(propylene-co-ethylene), and poly(styrene-co-methyl methacrylate).

[0432] Preferred insulating binders for use in the above-described formulations are polystyrene, poly(α-methylstyrene), polyvinyl cinnamate, poly(4-vinylbiphenyl), poly(4-methylstyrene), and polymethyl methacrylate. The most preferred insulating binders are polystyrene and polymethyl methacrylate.

[0433] The binder may also be selected from crosslinkable binders such as acrylates, epoxies, vinyl ethers, thiolenes, etc. The binder may also be mesogenic or liquid crystalline.

[0434] The organic binder may itself be semiconducting, in which case it is referred to herein as a semiconducting binder. The semiconducting binder is more preferably a low dielectric constant binder as defined herein. Semiconducting binders for use in the present invention preferably have a number average molecular weight (M) of at least 1500 to 2000, more preferably at least 3000, even more preferably at least 4000, and most preferably at least 5000. n The semiconductor binder preferably has at least 10 -5 cm 2 V -1 s -1 , more preferably at least 10 -4 cm 2 V -1 s -1 has a charge carrier mobility of

[0435] Preferred semiconducting binders include homopolymers or copolymers (including block-copolymers) containing arylamines (preferably triarylamines). To produce thin layers in BHJ OPV devices, the compounds, compositions, and formulations of the present invention can be deposited by any suitable method. Liquid coating of devices is preferable to vacuum deposition techniques. Solution deposition methods are particularly preferred. The formulations of the present invention allow for the use of many liquid coating techniques. Preferred deposition techniques include, but are not limited to, dip coating, spin coating, inkjet printing, nozzle printing, letterpress printing, screen printing, gravure printing, doctor blade coating, roller printing, reverse roller printing, offset lithography printing, dry offset lithography printing, flexography printing, web printing, spray coating, curtain coating, brush coating, slot die coating, or pad printing. For the fabrication of OPV devices and modules, area printing methods compatible with flexible substrates, such as slot die coating and spray coating, are preferred.

[0436] A suitable solution or formulation must be prepared containing a mixture of the compound of Formula I and the polymer. In preparing the formulation, a suitable solvent must be chosen to ensure complete dissolution of both components, p-type and n-type, and to take into account the boundary conditions (e.g., rheological properties) introduced by the selected printing method.

[0437] Organic solvents are generally used for this purpose. Typical solvents may be aromatic, halogenated or chlorinated solvents (including chlorinated aromatic solvents). Examples include, but are not limited to, chlorobenzene, 1,2-dichlorobenzene, chloroform, 1,2-dichloroethane, dichloromethane, carbon tetrachloride, toluene, cyclohexanone, ethyl acetate, tetrahydrofuran, anisole, 2,4-dimethylanisole, 1-methylnaphthalene, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4-dioxane, acetone, methyl ethyl ketone, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, n-butyl acetate, N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, 1,5-dimethyltetralin, propiophenone, acetophenone, tetralin, 2-methylthiophene, 3-methylthiophene, decalin, indane, methyl benzoate, ethyl benzoate, mesitylene, and combinations thereof.

[0438] The OPV device can be, for example, of any type known from the literature (see, for example, Waldauf et al., Appl. Phys. Lett., 2006, 89, 233517).

[0439] A first preferred OPV device according to the present invention comprises the following layers (in bottom to top order): optionally a substrate, a high work function electrode, preferably comprising a metal oxide such as ITO, which serves as the anode; an optional conductive polymer layer or hole transport layer, preferably comprising an organic polymer or polymer blend, for example PEDOT:PSS (poly(3,4-ethylenedioxythiophene):poly(styrene-sulfonate), or TBD (N,N'-diphenyl-N-N'-bis(3-methylphenyl)-1,1'biphenyl-4,4'-diamine) or NBD (N,N'-diphenyl-N-N'-bis(1-naphthylphenyl)-1,1'biphenyl-4,4'-diamine), a layer, also called "photoactive layer", comprising p-type and n-type organic semiconductors, which can be present, for example, as a p-type / n-type bilayer or different p-type and n-type layers, or as a blend or p-type and n-type semiconductors, forming a BHJ, optionally a layer with electron transport properties, comprising, for example, LiF or PFN, a low work function electrode, preferably comprising a metal such as aluminium, which serves as the cathode; wherein at least one of the electrodes, preferably the anode, is transparent to visible light; The n-type semiconductor is a compound of formula I:

[0440] A second preferred OPV device according to the present invention is an inverted OPV device, comprising the following layers (in bottom to top order): optionally a substrate, a high work function metal or metal oxide electrode, including, for example, ITO, serving as the cathode; Preferably, TiO x , ZnO x a layer having hole-blocking properties, comprising an organic polymer, a polymer blend, a metal or a metal oxide, such as Ca, Mg, poly(ethyleneimine), ethoxylated poly(ethyleneimine) or poly[(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)]; a photoactive layer comprising p-type and n-type organic semiconductors located between electrodes, which can be, for example, a p-type / n-type bilayer or different p-type and n-type layers, or a blend or p-type and n-type semiconductors, forming a BHJ; Preferably, organic polymers or polymer blends, metals or metal oxides, for example PEDOT:PSS, nafion, substituted triarylamine derivatives such as TBD or NBD, or WO x , MoO x , NiO x an optional conductive polymer layer or hole transport layer, comprising Pd or Au; - an electrode containing a high work function metal, such as silver, which acts as an anode wherein at least one of the electrodes, preferably the cathode, is transparent to visible light; The n-type semiconductor is a compound of formula I:

[0441] In the OPV devices of the present invention, the p-type and n-type semiconductor materials are preferably selected from compounds / polymers / fullerene-based materials as described above. When the photoactive layer is deposited on a substrate, it forms a BHJ that phase separates at the nanoscale level. For a description of nanoscale phase separation, see Dennler et al., Proceedings of the IEEE, 2005, 93(8), 1429 or Hoppe et al., Adv. Func. Mater, 2004, 14(10), 1005. An optional annealing step may be necessary to optimize the blend morphology and, therefore, OPV device performance.

[0442] Another approach to optimizing device performance is to prepare formulations for the fabrication of OPV (BHJ) devices that can contain high-boiling additives to appropriately promote phase separation. 1,8-octanedithiol, 1,8-diiodooctane, nitrobenzene, chloronaphthalene, and other additives have been used to obtain high-efficiency solar cells. Examples are disclosed in J. Peet et al., Nat. Mater., 2007, 6, 497 or Frechet et al., J. Am. Chem. Soc., 2010, 132, 7595–7597.

[0443] Another preferred embodiment of the present invention relates to the use of a compound or composition according to the present invention as a dye, hole transport layer, hole blocking layer, electron transport layer and / or electron blocking layer in a DSSC or PSC, and to a DSSC or perovskite-based solar cell (PSC) comprising a compound or composition according to the present invention.

[0444] DSSCs and PSCs can be produced as described in the literature, for example, Chem.Rev. 2010, 110, 6595-6663, Angew.Chem.Int.Ed. 2014, 53, 2-15 or WO 2013171520 A1.

[0445] A preferred OE device according to the present invention is a solar cell, preferably a PSC, which includes a light absorber that is at least partially inorganic, as described below. In solar cells comprising a light absorber according to the invention, there are no limitations as such regarding the choice of the light absorber material, which is at least partly inorganic.

[0446] The term "at least partially inorganic" means that the light absorber material may be selected from metal-organic complexes or materials that are substantially inorganic, preferably having a crystalline structure in which an organic ion can be assigned to a single site in the crystalline structure.

[0447] Preferably, the light absorber contained in the solar cell according to the present invention has an optical band gap of 2.8 eV or less and 0.8 eV or more. Highly preferably, the light absorber in the solar cell according to the present invention has an optical bandgap of less than or equal to 2.2 eV and greater than or equal to 1.0 eV.

[0448] The light absorber used in the solar cell according to the present invention preferably does not contain fullerenes. The chemistry of fullerenes belongs to the field of organic chemistry. Therefore, fullerenes do not meet the definition of "at least partially inorganic" according to the present invention.

[0449] Preferably, the at least partially inorganic light absorber is a material with a perovskite structure or a material with a 2D crystalline perovskite structure. The term "perovskite" as used above and below generally refers to materials having a perovskite crystal structure or a 2D crystalline perovskite structure.

[0450] The term perovskite solar cell (PSC) refers to a solar cell that includes a light absorber that is a material with a perovskite structure or a material with a 2D crystalline perovskite structure.

[0451] At least partially inorganic light absorbers include, but are not limited to, materials with a perovskite crystal structure, materials with a 2D crystalline perovskite structure (e.g., CrystEngComm, 2010, 12, 2646-2662), Sb2S3 (Stibnite), Sb2(S x Se (x-1) ) 3、 PbS x Se (x-1) , CdS x Se (x-1) , ZnTe, CdTe, ZnS x Se (x-1) , InP, FeS, FeS2, Fe2S3, Fe2SiS4, Fe2GeS4, Cu2S, CuInGa, CuIn(Se x S(1-x) )2, Cu3Sb x Bi (x-1)、 (S y Se (y-1) )3, Cu2SnS3, SnS x Se (x-1) , Ag2S, AgBiS2, BiSI, BiSeI, Bi2(S x Se (x-1) )3, BiS (1-x) Se x I, WSe2, AlSb, metal halides (e.g., BiI3, Cs2SnI6), chalcopyrite (e.g., CuIn x Ga (1-x) (S y Se (1-y) )2), kesterite (e.g., Cu2ZnSnS4, Cu2ZnSn(Se x S (1-x) ) 4、 Cu2Zn(Sn 1-x Ge x ) S4) and metal oxides (e.g., CuO, Cu2O) or mixtures thereof.

[0452] Preferably, the at least partially inorganic light absorber is a perovskite. In the above definition of the light absorber, x and y are each independently defined as follows: (0≦x≦1) and (0≦y≦1).

[0453] Highly preferably, the light absorber is a special perovskite, namely a metal halide perovskite as described in detail above and below. Most preferably, the light absorber is an organic-inorganic hybrid metal halide perovskite included in a perovskite solar cell (PSC).

[0454] In one particularly preferred embodiment of the present invention, the perovskite denotes a metal halide perovskite of formula ABX3, wherein: A is a monovalent organic cation, a metal cation, or a mixture of two or more of these cations; B is a divalent cation; X is F, Cl, Br, I, BF4 or a combination thereof.

[0455] Preferably, the monovalent organic cation of the perovskite is selected from alkylammonium (wherein the alkyl group has 1 to 6 C atoms and is linear or branched), formamidinium or guanidinium, or where the metal cation is K + , Cs + or Rb + is selected from.

[0456] Suitable and preferred divalent cations B are Ge 2+ , Sn 2+ or Pb 2+ is. Suitable and preferred perovskite materials are CsSnI3, CH3NH3Pb(I 1-x Cl x )3, CH3NH3PbI 3、 CH3NH3Pb(I 1-x Br x )3, CH3NH3Pb(I 1-x (BF4) x )3, CH3NH3Sn(I 1-x Cl x )3, CH3NH3SnI3 or CH3NH3Sn(I 1-x Br x ) 3, where each x is independently defined as follows: (0 <x≦1)。

[0457] Further suitable and preferred perovskites are of formula Xa (3-x) Xb (x) wherein Xa and Xb are each independently selected from Cl, Br, or I, and x is greater than 0 and less than 3.

[0458] Suitable and preferred perovskites are also disclosed in WO 2013 / 171517, claims 52-71 and claims 72-79, which are incorporated herein by reference in their entirety. The materials are defined as mixed-anion perovskites, containing two or more different anions selected from halide anions and chalcogenide anions. Preferred perovskites are disclosed on page 18, lines 5-17. As described, perovskites typically include CH3NH3PbBrI2, CH3NH3PbBrCl2, CH3NH3PbIBr2, CH3NH3PbICl2, CH3NH3SnF2Br, CH3NH3SnF2I, and (H2N=CH-NH2)PbI 3z Br 3(1-z) where z is greater than 0 and less than 1.

[0459] The present invention further relates to a solar cell comprising a light absorber, preferably a PSC, as described above and below, wherein a compound of formula I is used as a layer between one electrode and the light absorber layer.

[0460] The present invention further relates to a solar cell comprising a light absorber, preferably a PSC, as described above and below, wherein the compound of formula I is included in the electron selective layer. An electron selective layer is defined as a layer that provides high electron conductivity and low hole conductivity to favor electron-charge transport.

[0461] The present invention further relates to a solar cell comprising a light absorber, preferably a PSC, as described above and below, wherein a compound of formula I is used as part of an electron selective layer, as an electron transporting material (ETM), or as a hole blocking material.

[0462] Preferably, the compounds of formula I are used as electron transport materials (ETMs). In an alternative preferred embodiment, the compound of formula I is used as a hole-blocking material.

[0463] The device structure of the PSC device according to the invention can be of any type known from the literature. A first preferred device structure of a PSC device according to the present invention comprises the following layers (in order from bottom to top): - a substrate which may optionally be flexible or rigid and transparent, translucent or opaque and conductive or non-conductive, in any combination; a high work function electrode, preferably comprising a doped metal oxide, such as fluorine-doped tin oxide (FTO), tin-doped indium oxide (ITO), or aluminum-doped zinc oxide; an electron selective layer comprising one or more electron transport materials, at least one of which is a compound of formula I, which may optionally also be a dense layer and / or consist of nanoparticles, preferably a metal oxide such as TiO2, ZnO2, SnO2, Y2O5, Ga2O3, SrTiO3, BaTiO3 or a combination thereof; - a porous framework which may optionally be conductive, semi-conductive or insulating, preferably comprising a metal oxide such as TiO2, ZnO2, SnO2, Y2O5, Ga2O3, SrTiO3, BaTiO3, Al2O3, ZrO2, SiO2 or a combination thereof, and preferably composed of nanoparticles, nanorods, nanoflakes, nanotubes or nanocolumns; a layer comprising an at least partially inorganic light absorber, particularly preferably a metal halide perovskite as described above, which may possibly be a dense or porous layer, optionally partially or completely permeating the underlying layer; optionally a hole selective layer, comprising one or more hole transport materials and optionally also additives such as lithium salts, e.g. LiY (where Y is a monovalent organic anion), preferably bis(trifluoromethylsulfonyl)imide, tertiary amines, e.g. 4-tert-butylpyridine, or any other covalent or ionic compound, e.g. tris(2-(1H-pyrazol-1-yl)-4-tert-butylpyridine)-cobalt(III) tris(bis(trifluoromethylsulfonyl)imide)), which can enhance the properties, e.g. conductivity, of the hole selective layer and / or facilitate its processing; and a back electrode made of metal, for example Au, Ag, Al, Cu, Ca, Ni or a combination thereof, or non-metallic, which may be transparent, semi-transparent or opaque. Includes.

[0464] A second preferred device structure for a PSC device according to the present invention comprises the following layers (in bottom to top order): - a substrate which may optionally be flexible or rigid and transparent, translucent or opaque and conductive or non-conductive, in any combination; a high work function electrode, preferably comprising a doped metal oxide, such as fluorine-doped tin oxide (FTO), tin-doped indium oxide (ITO), or aluminum-doped zinc oxide; - optionally a hole injection layer, which may be a single layer, for example to change the work function of the underlying electrode and / or to modify the surface of the underlying layer and / or to help smooth out a rough surface of the underlying layer; optionally a hole selective layer, comprising one or more hole transport materials and optionally also additives such as lithium salts, e.g. LiY (where Y is a monovalent organic anion), preferably bis(trifluoromethylsulfonyl)imide, tertiary amines, e.g. 4-tert-butylpyridine, or any other covalent or ionic compound, e.g. tris(2-(1H-pyrazol-1-yl)-4-tert-butylpyridine)-cobalt(III) tris(bis(trifluoromethylsulfonyl)imide)), which can enhance the properties, e.g. conductivity, of the hole selective layer and / or facilitate its processing; a layer comprising an at least partially inorganic light absorber, particularly preferably a metal halide perovskite as described or preferably as described above; an electron selective layer comprising one or more electron transport materials, at least one of which is a compound of formula I and which may optionally also be a dense layer and / or be composed of nanoparticles, and which may comprise, for example, a metal oxide such as TiO2, ZnO2, SnO2, Y2O5, Ga2O3, SrTiO3, BaTiO3 or a combination thereof, and / or which may comprise a substituted fullerene, for example [6,6]-phenylC61-butyric acid methyl ester, and / or which may comprise a molecular, oligomeric or polymeric electron transport material, for example 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline, or a mixture thereof; and a back electrode made of metal, for example Au, Ag, Al, Cu, Ca, Ni or a combination thereof, or non-metallic, which may be transparent, semi-transparent or opaque. Includes.

[0465] To fabricate the electron-selective layer in the PSC device of the present invention, the compound of Formula I, optionally in the form of a blend or mixture, together with other compounds or additives, can be deposited by any suitable method. Liquid coating of the device is preferable to vacuum deposition techniques. Solution deposition methods are particularly preferred. Formulations containing the compound of Formula I allow the use of many liquid coating techniques. Preferred deposition techniques include, but are not limited to, dip coating, spin coating, inkjet printing, nozzle printing, letterpress printing, screen printing, gravure printing, doctor blade coating, roller printing, reverse roller printing, offset lithography printing, dry offset lithography printing, flexography printing, web printing, spray coating, curtain coating, brush coating, slot-die coating, or pad printing. In the fabrication of PSC devices and modules, deposition techniques for large-area coating, such as slot-die coating or spray coating, are preferred.

[0466] Formulations that can be used to prepare electron selective layers in optoelectronic devices according to the present invention, preferably in PSC devices, comprise one or more compounds of formula I or the preferred embodiments described above in the form of a blend or mixture, optionally together with one or more further electron transporting materials and / or hole blocking materials and / or binders and / or other additives as described above and below, and one or more solvents.

[0467] The formulations may include, comprise, consist essentially of, or consist of said necessary or optional ingredients described above or below. All compounds or components that may be used in the formulations are known or commercially available, or may be synthesized by known methods.

[0468] The formulation described above is (i) first mixing a compound of formula I, optionally a binder or a precursor of a binder as described above, optionally a further electron transport material, optionally one or more further additives as described above and below, and a solvent or solvent mixture as described above and below; (ii) applying such a mixture to a substrate; and optionally evaporating the solvent to form an electron selective layer according to the present invention. It can be prepared by a method comprising:

[0469] In step (i), the solvent may be a single solvent for the compound of formula I, and the organic binder and / or the additional electron transport material may each be dissolved in a separate solvent, and then the resulting solutions may be mixed to mix the compounds.

[0470] Alternatively, the binder can be formed in situ by mixing or dissolving the compound of Formula I in a binder precursor, such as a liquid monomer, oligomer, or crosslinkable polymer, optionally in the presence of a solvent, depositing the mixture or solution on a substrate, for example, by dipping, spraying, coating, or printing, to form a liquid layer, and then curing the liquid monomer, oligomer, or crosslinkable polymer, for example, by radiation, heat, or electron beam irradiation, to produce a solid layer. If a preformed binder is used, it can be dissolved together with the compound of Formula I in a suitable solvent as described above, and the solution can be deposited on a substrate, for example, by dipping, spraying, coating, or printing, to form a liquid layer, and then removing the solvent to leave a solid layer. It will be understood that a solvent will be selected that is capable of dissolving all components of the formulation and that will produce a consistent, defect-free layer upon evaporation from the solution blend.

[0471] In addition to the aforementioned components, the formulations described above may contain further additives and processing aids, including, inter alia, surface-active substances (surfactants), lubricants and greases, viscosity-adjusting additives, conductivity-enhancing additives, dispersants, hydrophobizing agents, adhesion promoters, flow improvers, antifoaming agents, degassing agents, diluents which may be reactive or non-reactive, fillers, auxiliaries, processing aids, dyes, pigments, stabilizers, sensitizers, nanoparticles and inhibitors.

[0472] Additives may be used to enhance the properties of the electron selective layer and / or the properties of any of the adjacent layers and / or the performance of the optoelectronic devices according to the present invention. Additives may also be used to facilitate the deposition, processing, or formation of the electron selective layer and / or the deposition, processing, or formation of any of the adjacent layers. Preferably, one or more additives are used that enhance the conductivity of the electron selective layer and / or passivate the surface of any of the adjacent layers.

[0473] Suitable methods for incorporating one or more additives include, for example, contacting one or more additives with the materials or formulations described above by exposure to vapors of the additives at atmospheric or reduced pressure, mixing a solution or solid containing one or more additives and the described or preferably above-described materials or formulations, by thermal diffusion of one or more additives into the above-described materials or formulations, or by ion implantation of one or more additives into the above-described materials or formulations.

[0474] The additives used for this purpose can be organic, inorganic, metallic or hybrid materials. The additives can be molecular compounds, such as organic molecules, salts, ionic liquids, coordination complexes or organometallic compounds, polymers or mixtures thereof. The additives can also be particles, such as hybrid or inorganic particles, preferably nanoparticles, or carbon-based materials such as fullerenes, carbon nanotubes or graphene flakes.

[0475] Examples of additives that may enhance conductivity include, for example, halogens (e.g., I2, Cl2, Br2, ICl, ICl3, IBr, and IF), Lewis acids (e.g., PF5, AsF5, SbF5, BF3, BCl3, SbCl5, BBr3, and SO3), protic acids, organic acids, or amino acids (e.g., HF, HCl, HNO3, H2SO4, HClO4, FSO3H, and ClSO3H), transition metal compounds (e.g., FeCl3, FeOCl, Fe(ClO4)3, Fe(4-CH3C6H4SO3)3, TiCl4, ZrCl4, HfCl4, NbF5, NbCl5, TaCl5, MoF5, MoCl5, WF5, WCl6, UF6, and LnCl3 (where Ln is a lanthanide)), anions (e.g., Cl - , Br - , I - , I3 - , HSO4 - , SO4 2- , NO3 - , ClO4 - , BF4 - , PF6 - , AsF6 - , SbF6 - , FeCl4 - , Fe(CN)6 3- , and aryl-SO3 - anions of various sulfonic acids such as + , Li + , Na + , K. + , Rb + , Cs + , Co 3+ and Fe 3+ ), O2, redox active salts (e.g., XeOF4, (NO2 + )(SbF6 - ), (NO2 + )(SbCl6 - ), (NO2 + )(BF4 - ), NOBF4, NOPF6, AgClO4, H2IrCl6 and La(NO3)3 .6H2O), strong electron-accepting organic molecules (e.g., 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ)), transition metal oxides (e.g., WO3, Re2O7, and MoO3), metal-organic complexes of cobalt, iron, bismuth, and molybdenum, (p-BrC6H4)3NSbCl6, bismuth(III) tris(trifluoroacetate), FSO2OOSO2F, acetylcholine, R4N + , (wherein R is an alkyl group), R4P + (R is a linear or branched alkyl group of 1 to 20), R6As + (wherein R is an alkyl group), R3S + (wherein R is an alkyl group) and an ionic liquid (for example, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide). Suitable cobalt complexes include tris(2-(1H-pyrazol-1-yl)-4-tert-butylpyridine)-cobalt(III) tris(bis(trifluoromethylsulfonyl)imide)), as well as the cobalt complex salts described in WO 2012 / 114315, WO 2012 / 114316, WO 2014 / 082706, WO 2014 / 082704, EP 2883881, or JP 2013-131477.

[0476] Suitable lithium salts include lithium bis(trifluoromethylsulfonyl)imide, as well as lithium tris(pentafluoroethyl)trifluorophosphate, lithium dicyanamide, lithium methyl sulfate, lithium trifluoromethanesulfonate, lithium tetracyanoborate, lithium dicyanamide, lithium tricyanomethide, lithium thiocyanate, lithium chloride, lithium bromide, lithium iodide, lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroantimonate, lithium hexafluoroarsenate, or a combination of two or more. A preferred lithium salt is lithium bis(trifluoromethylsulfonyl)imide.

[0477] Preferably, the formulation contains 0.1 mM to 50 mM, preferably 5 to 20 mM, of the lithium salt. Suitable device structures for PSCs comprising compounds of formula NI or I and mixed halide perovskites are described in WO 2013 / 171517, claims 52-71 and claims 72-79, which are incorporated herein by reference in their entirety.

[0478] Suitable device structures for PSCs comprising compound formulas and dielectric frameworks together with perovskites are described in WO 2013 / 171518, claims 1-90 or WO 2013 / 171520, claims 1-94, which are incorporated herein by reference in their entirety.

[0479] Suitable device structures for PSCs comprising compounds of Formula I, semiconductors and perovskites are described in WO 2014 / 020499, claims 1 and 3-14, which is incorporated herein by reference in its entirety. The surface-enhancing framework structures described therein comprise nanoparticles, e.g., porous TiO, applied to and / or fixed to a support layer.

[0480] Suitable device structures for PSCs comprising compounds of formula I and including planar heterojunctions are described in WO 2014 / 045021, claims 1-39, which is incorporated herein by reference in its entirety. Such devices are characterized by having a thin film of light-absorbing or light-emitting perovskite disposed between n-type (electron-conducting) and p-type (hole-conducting) layers. Preferably, the thin film is a compact thin film.

[0481] The present invention relates to a method for preparing a PSC as described above or below, comprising the steps of: - providing first and second electrodes; providing an electron selective layer comprising a compound of formula I; The present invention further relates to a method comprising:

[0482] The invention further relates to a tandem device comprising at least one device according to the invention as described above and below. Preferably, the tandem device is a tandem solar cell.

[0483] The tandem device or tandem solar cell according to the present invention may have two semi-cells, where one of the semi-cells comprises the compound, oligomer or polymer in the active layer as described or preferably as described above. There is no limitation on the choice of other type of semi-cell, which may be any other type of device or solar cell known in the art.

[0484] There are two different types of tandem solar cells known in the art. The so-called two-terminal or monolithic tandem solar cell has only two connections. The two subcells (or synonymously, semi-cells) are connected in series. Therefore, the current generated in both subcells is the same (current matching). The increase in power conversion efficiency is due to the increase in voltage as the voltage of the two subcells increases. Another type of tandem solar cell is the so-called four-terminal or stacked tandem solar cell. In this case, both subcells are operated independently. Therefore, both subcells can be operated at different voltages and can also generate different currents. The power conversion efficiency of a tandem solar cell is the sum of the power conversion efficiencies of the two subcells.

[0485] The present invention further relates to a module comprising a device according to the invention as described above or preferably as described above. The compounds and compositions of the present invention may also be used as dyes or pigments in other applications, for example, as ink dyes, laser dyes, fluorescent markers, solvent dyes, food dyes, contrast agents or pigments in coloring paints, inks, plastics, fabrics, cosmetics, foods and other materials.

[0486] The compounds and compositions of the present invention are also suitable for use in the semiconductor channel of an OFET. Thus, the present invention also provides an OFET comprising a gate electrode, an insulating (or gate insulator) layer, a source electrode, a drain electrode, and an organic semiconductor channel connecting the source and drain electrodes, wherein the organic semiconductor channel comprises the compounds and compositions of the present invention. Other features of OFETs are well known to those skilled in the art.

[0487] OFETs in which an OSC material is disposed as a thin film between a gate dielectric and drain and source electrodes are generally known and are described, for example, in U.S. Pat. Nos. 5,892,244, 5,998,804, 6,723,394, and the references cited in the Background Art section. Due to advantages such as low-cost manufacturing using the solubility properties of the compounds according to the invention and thus the processability of larger surfaces, preferred applications of these OFETs include integrated circuits, TFT displays, and security applications.

[0488] The gate, source and drain electrodes and insulating and semiconducting layers in an OFET device can be arranged in any order, provided that the source and drain electrodes are separated from the gate electrode by an insulating layer, the gate electrode and semiconducting layer both contact the insulating layer, and the source and drain electrodes both contact the semiconducting layer.

[0489] The OFET device according to the present invention preferably comprises: - a source electrode, - drain electrode, gate electrode, -semiconductor layer, one or more gate insulator layers, optionally a substrate Includes. The semiconducting layer here preferably comprises a compound of formula I.

[0490] The OFET device can be a top-gate or bottom-gate device. Suitable structures and methods for fabricating OFET devices are known to those skilled in the art and are described in the literature, for example, in US Patent Application Publication No. 2007 / 0102696 A1.

[0491] The gate insulator layer preferably comprises a fluoropolymer, such as, for example, commercially available Cytop 809M® or Cytop 107M® (manufactured by Asahi Glass). Preferably, the gate insulator layer is deposited, for example, by spin coating, doctor blading, wire bar coating, spray or dip coating, or other known methods, from a formulation comprising an insulator material and one or more solvents containing one or more fluoro atoms (fluorosolvents), preferably perfluorosolvents. A suitable perfluorosolvent is, for example, FC75® (available from Acros, catalog number 12380). Other suitable fluoropolymers and fluorosolvents are known in the prior art, such as, for example, the perfluoropolymers Teflon AF 1600 or 2400 (DuPont) or Fluoropel (Cytonix) or the perfluorosolvent FC 43 (Acros, No. 12377). Particularly preferred are organic dielectric materials ("low-k materials") with a low dielectric constant (or permittivity) of 1.0 to 5.0, very preferably 1.8 to 4.0, as disclosed, for example, in U.S. Patent Application Publication No. 2007 / 0102696 A1 or U.S. Patent No. 7,095,044.

[0492] In security applications, OFETs and other devices comprising the semiconductor material according to the present invention, such as transistors or diodes, can be used in RFID tags or security marks to authenticate and prevent counterfeiting of securities such as banknotes, credit cards or ID cards, national identification cards, licenses or any product having monetary value, such as stamps, tickets, stocks, checks, etc.

[0493] Alternatively, the compounds and compositions (hereinafter referred to as "materials") according to the present invention can be used in OLEDs, for example, as active display materials in flat panel display applications or as backlights for flat panel displays such as liquid crystal displays. A typical OLED is realized using a multilayer structure. An emissive layer is generally inserted between one or more electron transport layers and / or hole transport layers. By applying a voltage, electrons and holes as charge carriers migrate toward the emissive layer, where their recombination causes excitation and, therefore, luminescence of lumophor units contained in the emissive layer. Depending on their electrical and / or optical properties, the materials according to the present invention can be used in one or more charge transport layers and / or in the emissive layer. Furthermore, when the materials according to the present invention exhibit electroluminescent properties themselves or contain electroluminescent groups or compounds, their use in the emissive layer is particularly advantageous. The selection, characterization and processing of suitable monomeric, oligomeric and polymeric compounds or materials for use in OLEDs is generally known to those skilled in the art; see, for example, Mueller et al., Synth. Metals, 2000, 111-112, 31-34; Alcala, J. Appl. Phys., 2000, 88, 7124-7128 and references cited therein.

[0494] According to another use, the materials according to the invention, in particular those exhibiting photoluminescent properties, can be used, for example, as material for light sources in display devices, as described in EP 0 889 350 A1 or by C. Weder et al., Science, 1998, 279, 835-837.

[0495] A further aspect of the present invention relates to both the oxidized and reduced forms of the material according to the present invention. The loss or gain of electrons leads to the formation of highly delocalized ionic forms with high conductivity. This can occur upon exposure to common dopants. Suitable dopants and doping methods are known to those skilled in the art, for example, from EP 0 528 662, U.S. Pat. No. 5,198,153 or WO 96 / 21659.

[0496] The doping process typically refers to treating a semiconductor material with an oxidizing or reducing agent in a redox reaction to form delocalized ionic centers in the material, with the corresponding counterions coming from the applied dopant. Suitable doping methods include, for example, exposure to doping vapors at atmospheric or reduced pressure, electrochemical doping in a solution containing the dopant, thermal diffusion of the dopant into contact with the semiconductor material, and ion implantation of the dopant into the semiconductor material.

[0497] When electrons are used as carriers, suitable dopants include, for example, halogens (e.g., I2, Cl2, Br2, ICl, ICl3, IBr, and IF), Lewis acids (e.g., PF5, AsF5, SbF5, BF3, BCl3, SbCl5, BBr3, and SO3), protic acids, organic acids, or amino acids (e.g., HF, HCl, HNO3, H2SO4, HClO4, FSO3H, and ClSO3H), transition metal compounds (e.g., FeCl3, FeOCl, Fe(ClO4), Fe(4-CH3C6H4SO3), TiCl4, ZrCl4, HfCl4, NbF5, NbCl5, TaCl5, MoF5, MoCl5, WF5, WCl6, UF6, and LnCl3 (where Ln is a lanthanide), anions (e.g., Cl - , Br - , I - , I3 - , HSO4 - , SO4 2- , NO3 - , ClO4 - , BF4 - , PF6 -, AsF6 - , SbF6 - , FeCl4 - , Fe(CN)6 3- , and aryl-SO3 - When holes are used as carriers, examples of dopants are cations (e.g., H + , Li + , Na + , K. + , Rb + and Cs + ), alkali metals (e.g., Li, Na, K, Rb, and Cs), alkaline earth metals (e.g., Ca, Sr, and Ba), O2, XeOF4, (NO2 + )(SbF6 - ), (NO2 + )(SbCl6 - ), (NO2 + )(BF4 - ), AgClO4, H2IrCl6, La(NO3)3 . 6H2O, FSO2OOSO2F, Eu, acetylcholine, R4N + , (wherein R is an alkyl group), R4P + (wherein R is an alkyl group), R6As + (wherein R is an alkyl group), and R3S + (wherein R is an alkyl group).

[0498] Conductive forms of the materials of the present invention may be used as organic "metals" in applications including, but not limited to, charge injection layers and ITO planarization layers in OLED applications, films for flat panel displays and touch screens, antistatic films, patterns or tracts in electronic applications such as printed conductive substrates, printed circuit boards and capacitors, etc.

[0499] The materials according to the invention may also be suitable for use in organic plasmon-emitting diodes (OPEDs), as described, for example, in Koller et al., Nat. Photonics, 2008, 2, 684.

[0500] According to another use, the material of the present invention can be used alone or together with other materials in or as an alignment layer in an LCD or OLED device, as described, for example, in U.S. Patent Application Publication No. 2003 / 0021913. The use of the charge transport compound of the present invention can increase the conductivity of the alignment layer. When used in an LCD, this increased conductivity can reduce deleterious residual DC effects in switchable LCD cells, suppress image sticking, or, for example, in a ferroelectric LCD, reduce residual charge caused by switching the spontaneous polarization charge of the ferroelectric LC. When used in an OLED device containing a light-emitting material disposed on the alignment layer, this increased conductivity can promote the electroluminescence of the light-emitting material.

[0501] Materials according to the present invention having mesogenic or liquid crystalline properties can be formed into oriented anisotropic films as described above, which are particularly useful as alignment layers for inducing or promoting alignment in a liquid crystalline medium provided on said anisotropic film.

[0502] According to another use, the material according to the invention is suitable for use in liquid crystal (LC) windows, also known as smart windows. The materials according to the present invention may also be combined with photoisomerisable compounds and / or chromophores in or for use as a photoalignment layer, as described in US Patent Application Publication No. 2003 / 0021913 A1.

[0503] According to another use, the materials according to the invention, especially their water-soluble derivatives (e.g., with polar or ionic side groups) or ionically doped forms, can be used as chemical sensors or materials for detecting and identifying DNA sequences. Such uses are described, for example, in L. Chen, DW McBranch, H. Wang, R. Helgeson, F. Wudl, and DG Whitten, Proc. Natl. Acad. Sci. USA, 1999, 96, 12287; D. Wang, X. Gong, P.S. Heeger, F. Rininsland, G.C. Bazan, and A.J. Heeger. Heeger, Proc. Natl. Acad. Sci. USA, 2002, 99, 49; N. DiCesare, M.R. Pinot, K.S. Schanze, and J.R. Lakowicz, Langmuir, 2002, 18, 7785; D.T. McQuade, A.E. Pullen, and T.M. Swagger, Chem. Rev., 2000, 100, 2537.

[0504] Unless the context clearly indicates otherwise, as used herein, plural forms of the terms herein are to be construed as including the singular and vice versa. Throughout the description and claims of this specification, the terms "comprise" and "contain" and variations of these terms, such as "comprising" and "comprises," mean "including but not limited to" and are not intended to exclude (or exclude) other elements.

[0505] It will be understood that variations to the above-described embodiments of the invention may be made while still falling within the scope of the invention. Each feature disclosed herein, unless otherwise stated, may be replaced by an alternative feature serving the same, equivalent, or similar purpose. Thus, unless otherwise stated, each feature disclosed is only one example of a generic series of equivalent or similar features.

[0506] All of the features disclosed herein may be combined in any combination, except for combinations in which at least some of such features and / or steps are mutually exclusive. In particular, preferred features of the invention are applicable to all aspects of the invention and may be used in any combination. Similarly, features described in non-essential combinations may be used separately (not in combination).

[0507] Above and below, percentages are by weight and temperatures are given in °C unless otherwise stated. The present invention will now be described in more detail with reference to the following examples, which are illustrative only and do not limit the scope of the invention.

[0508] (Example) Example 1 Molecular structures were generated using the Firefly QC package (Alex A. Granovsky), which is based in part on the GAMESS (US) source code (MW Schmidt, K.K. Baldridge, J.A. Boatz, S.T. Elbert, M.S. Gordon, J.H. Jensen, S. Koseki, N. Matsunaga, K.A. Nguyen, S. Su, T.L. Windus, M. Dupuis, J.A. Montgomery, J. Comput. Chem. 14, 1347-1363 (1993)). A. Granovsky, Firefly version 8, see www.classic.chem.msu.su / gran / firefly / index.html, using B3LYP / 6-31G * To reduce calculation time, alkyl chains were represented by methyl groups, which do not dramatically change the calculated energy levels, and do not suggest that methyl groups are preferred. E HOMO and E LUMO are defined as the eigenvalues ​​of the highest occupied and lowest unoccupied Kohn-Sham orbitals, respectively, and are used as approximations of the ionisation potential (IP) and electron affinity (EA), respectively. E g is |E LUMO -E HOMO is the transport bandgap of the material, defined as |S0-S1|, and is the vertical excitation energy from the ground state S0 to the first singlet excited state S1, which is the optical bandgap E g It is used as a measure of (opt).

[0509] E of donor and acceptor materials in bulk heterojunctions and device performance HOMO , E LUMO and E g The approximate relationship between the electron affinity (E) and the donor affinity (E) is known as the Scharber model [MC Scharber, D. Muehlbacher, M. Koppe, P. Denk, C. Waldauf, A.J. Heeger, C.J. Brabec, Adv. Mater. 2006, 18, 789-794]. It is widely accepted that when the donor material in a donor-acceptor blend absorbs light and forms an excited state, the excited electron must jump to an adjacent acceptor site to form a free carrier. The driving force for this process is the relationship between the excited state of the donor material and the electron affinity (E) of the acceptor material. LUMO The energy difference between the charge carrier and the charge carrier (estimated by ) has been experimentally found to be at least about 0.35 eV for efficient charge generation [D. Veldman, SCJ Meskers, RAJ Janssen, Adv. Funct. Mater. 2009, 19, 1939-1948; M.C. Scharber, NS Sariciftci, Progr. Polym. Sci. 38 (2013) 1929-1940]. Therefore, the E LUMO Tuning of E is of utmost importance; lowering its value increases the driving force for charge generation and may allow the use of lower bandgap donor materials, while E LUMO Increasing the E can hinder charge generation. In the OSC materials of the present invention, due to their small optical band gap, another mechanism is also possible: light absorption by the acceptor, followed by the E of the donor and acceptor, respectively. HOMOHole injection into the donor material is driven by the energy difference between the HOMO energy and the donor material [W. Zhao, D. Qian, S. Zhang, S. Li, O. Inganas, F. Gao, and J. Hou, Advanced Materials 2016, DOI: 10.1002 / adma.201600281]. This mechanism is responsible for significant external quantum efficiency beyond the absorption edge of the donor material, and preserving this advantage in the acceptor material requires careful tuning of the HOMO energy. Comparative Example C1 Compound C1 shown below is calculated as a control.

[0510] [Table 1]

[0511] Examples 1 to 74 E of compound C1 HOMO , E LUMO , E g and calculated values ​​of S0-S1 (experimentally determined IP, EA and E g ) is compared to the calculated values ​​for compounds 1-3 of formula I.

[0512] [Table 2-1]

[0513] [Table 2-2]

[0514] [Table 2-3]

[0515] [Table 2-4]

[0516] [Table 2-5]

[0517] [Table 2-6]

[0518] [Table 2-7]

[0519] [Table 2-8]

[0520] [Table 2-9]

[0521] [Table 2-10]

[0522] [Table 2-11]

[0523] [Table 2-12]

[0524] Example 75 Intermediate 1

[0525] [ka]

[0526] -78 °C in anhydrous tetrahydrofuran (20 cm 3A solution of 2,7-dibromo-4,4,9,9-tetrakis(4-octylphenyl)-4,9-dihydro-thieno[3',2':4,5]cyclopenta[1,2-b]thieno[2'',3'':3',4']cyclopenta[1',2':4,5]thieno[2,3-d]thiophene (0.5 g, 0.40 mmol) in 1,2-dibromo-4,4,9,9-tetrakis(4-octylphenyl)-4,9-dihydro-thieno[3',2':4,5]cyclopenta[1,2-b]thieno[2'',3'':3',4']cyclopenta[1',2':4,5]thieno[2,3-d]thiophene (0.5 g, 0.40 mmol) was treated with n-butyllithium (0.50 cm) for 15 min. 3 , 1.3 mmol, 2.5 M in hexane) is added dropwise. After the addition, the reaction mixture is stirred at −78° C. for 60 min before being diluted with anhydrous diethyl ether (20 cm 3 ) in N,N-dimethylformamide (0.8 cm 3 A solution of dichloromethane (60 cm 3 , 10 mmol) is added in one portion. The mixture is then warmed to 23° C. over 17 hours. 3 ) and water (250 cm 3 ) is added and the mixture is stirred for 30 min at 23°C. The product is extracted with dichloromethane (3 x 60 cm 3 The combined organic matter is extracted with brine (30 cm 3 ), dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography (40-60 petroleum:diethyl ether; 9.5:0.5) to give Intermediate 1 (0.13 g, 27%) as an orange-yellow crystalline solid. 1 H NMR (400MHz, CDCl3) 9.81(2H,s), 7.69(2H,s), 7.12(16H,m), 2.52-2.61(8H,m), 1.30(48H,bs), 0.79-0.92(12H,m). compound 75

[0527] [ka]

[0528] Chloroform (12cm 3 To a degassed solution of intermediate 1 (0.13 g, 0.11 mmol) and 3-(dicyanomethylidene)indan-1-one (1.5 g, 0.77 mmol) in 10 mL of HCl was added pyridine (0.6 cm 3, 8 mmol) is added. The mixture is then degassed with nitrogen for 30 minutes and then heated at 70 °C for 15 hours. The reaction mixture is cooled to 23 °C and the solvent is removed under reduced pressure. The crude product is purified by column chromatography (40-60 petroleum:chloroform; 1:1) to give compound 75 (1.1 g, 65%) as a dark blue crystalline solid. 1 H NMR (400MHz, CDCl3)8.87(2H,s), 8.69(2H,d,J 7.6), 7.91(2H,d,J 7.1), 7.68-7.79(6H,m), 7.08-7.18(16H,m), 2.60(8H,t,J 7.7), 1.62(8H,q,J 7.1Hz), 1.21-1.39(40H,m), 0.88(12H,t,J 6.5). Example 76 Intermediate 2

[0529] [ka]

[0530] Anhydrous tetrahydrofuran (100 cm 3 A solution of 2,7-dibromo-4,4,9,9-tetrakis(4-octylphenyl)-4,9-dihydro-thieno[3',2':4,5]cyclopenta[1,2-b]thieno[2'',3'':3',4']cyclopenta[1',2':4,5]thieno[2,3-d]thiophene (2.00 g, 1.61 mmol) in ...6 cm) was added to the solution for 10 min. 3 , 6.5 mmol, 2.5 M in hexanes) is added. The mixture is stirred at −78° C. for 1 h and then tributyltin chloride (2.0 cm 3 , 7.4 mmol) is added and the mixture is stirred overnight at 23° C. Methanol (10 cm 3 ) is added and the material is concentrated under reduced pressure. The crude product is then diluted with pentane (20 cm 3 ), anhydrous magnesium sulfate was added, filtered and the solid was dissolved in more pentane (3 × 10 cm 3 The filtrate was then concentrated under reduced pressure and the solid was washed with methanol (3 × 20 cm3 ) and the product is collected by filtration to give Intermediate 2 (2.57 g, 96%) as a yellow waxy solid. 1 H NMR (400MHz, CDCl3, 45℃) 7.16(8H,d,J 8.2), 7.06(10H,d,J 7.8), 2.55(8H,t,J 7.8), 1.53-1.67(20H,m), 1.22-1.41(56H,m), 1.07-1.14(8H,m), 0.84-0.97(30H,m). Intermediate 3

[0531] [ka]

[0532] Anhydrous toluene (36 cm 3 To a degassed solution of intermediate 2 (500 mg, 0.30 mmol) and 7-bromo-benzo[1,2,5]thiadiazole-4-carbaldehyde (161 mg, 0.66 mmol) in HCl (250 mL), tris(dibenzylideneacetone)dipalladium(0) (22 mg, 0.02 mmol) and tris(o-tolyl)phosphine (28 mg, 0.09 mmol) are added. After the reaction mixture is degassed for 30 min, it is heated at 80 °C for 1.5 h. After cooling to 23 °C, the mixture is concentrated under reduced pressure. The crude product is then extracted with methanol (3 × 25 cm 3 ) and the solid is filtered to give Intermediate 3 (357 mg, 84%) as a blue crystalline solid. 1 H NMR (400MHz, CDCl3) 10.69(2H,s), 8.33(2H,s), 8.19(2H,d,J 7.8), 7.95(2H,d,J 7.6), 7.25(8H,d,J 8.3), 7.14(8H,d,J 8.3), 2.58(8H,t,J 7.8), 1.58-1.64(8H,m), 1.20-1.38(40H,m), 0.86(12H,t,J 6.8). compound 76

[0533] [ka]

[0534] Anhydrous chloroform (27 cm 3 To a solution of intermediate 3 (357 mg, 0.25 mmol) in pyridine (1.4 cm 3 , 17 mmol) is added. The mixture is degassed with nitrogen before 3-ethyl-2-thioxo-thiazolidin-4-one (286 mg, 1.77 mmol) is added. After further degassing, the reaction mixture is heated at reflux for 2 days. Additional degassed anhydrous chloroform (20 cm 3 ) is added and the reaction is heated at reflux for an additional 24 hours. Additional 3-ethyl-2-thioxo-thiazolidin-4-one (286 mg, 1.77 mmol) is added and the reaction is heated at reflux for an additional 24 hours, after which the reaction is cooled to 23° C., concentrated under reduced pressure, and methanol (4×20 cm 3 ), followed by diethyl ether (3 × 20 cm 3 The triturated material is then triturated with 2-butanone / water (4:1) (70 cm 3 ), heated to 90°C, cooled to 0°C, the solid collected by filtration and added to more cold 2-butanone (4 x 10 cm 3 ) to give compound 76 (233 mg, 54%) as a green / black powder. 1 H NMR (400MHz, CDCl3) 8.50(2H,s), 8.27(2H,s), 7.89(2H,d,J 7.8), 7.66(2H,d,J 7.8), 7.24(8H,d,J 8.1), 7.13(8H,d,J 8.3), 4.25(4H,q,J 6.9), 2.57(8H,t,J 7.7), 1.58-1.63(8H,m), 1.20-1.37(46H,m), 0.86(12H,t,J 6.7). Example 77 compound 77

[0535] [ka]

[0536] Anhydrous chloroform (13 cm 3To a solution of intermediate 3 (170 mg, 0.12 mmol) in pyridine (0.7 cm 3 , 8.7 mmol) is added. The mixture is then degassed with nitrogen before 3-(dicyanomethylidene)indan-1-one (164 mg, 0.84 mmol) is added. The solution is then further degassed before heating at reflux for 40 minutes. The reaction is then diluted with methanol (150 cm 3 ), the precipitated product was collected by filtration and added to methanol (5 cm 3 The solid is then passed through a silica plug (dichloromethane) to give compound 77 (36 mg, 17%) as a black solid. 1 H NMR (400MHz, CDCl3)9.56(2H,s), 9.26(2H,d,J 8.1), 8.72(2H,d,J 7.8), 8.36(2H,s), 7.93(4H,d,J 7.8), 7.73-7.84(4H,m), 7.22-7.25(8H,m), 7.14(8H,d,J 8.1), 2.57(8H,t,J 7.7), 1.57-1.64(8H,m), 1.24(40H,m), 0.85(12H,t,J 6.5). Example 78 Intermediate 4

[0537] [ka]

[0538] Anhydrous toluene (41 cm 3 To a solution of 2,8-dibromo-6,12-dihydro-6,6,12,12-tetrakis(4-dodecylphenyl)indeno[1,2-b]indeno[2',1':4,5]thieno[2,3-d]thiophene (500 mg, 0.34 mmol) in 1,2-dioxolan-2-yl-thiophen-2-yl-stannane (0.4 cm 3, 0.9 mmol) is added and the solution is degassed with nitrogen. Tris(dibenzylideneacetone)dipalladium(0) (25 mg, 0.03 mmol) and tris(o-tolyl)phosphine (31 mg, 0.10 mmol) are then added and, after further degassing, the reaction mixture is heated at 80° C. for 24 h. The reaction mixture is then concentrated under reduced pressure and methanol (3×50 cm 3 The solid was then eluted through a silica plug (40-60 petroleum:dichloromethane; 4:1 to 0:1) and triturated with 2-propanol (100 cm) at 80 °C. 3 ), cooled to 0° C. and collected by filtration to give Intermediate 4 (454 mg, 82%) as a sticky yellow solid. 1 H NMR (400MHz, CHCl3) 7.61(2H,s), 7.52(2H,d,J 8.1), 7.35(2H,d,J 8.1), 7.18(8H,d,J 7.9), 7.14(2H,d,J 3.7), 7.09(10H,d,J 8.1), 6.09(2H,s), 4.10-4.19(4H,m), 4.00-4.09(4H,m), 2.55(8H,t,J 7.8), 1.57-1.63(8H,m), 1.21-1.36(72H,m), 0.87(12H,t,J 6.7). Intermediate 5

[0539] [ka]

[0540] Concentrated hydrochloric acid (0.2 cm 3 , 1.8 mmol, 32%) in tetrahydrofuran (20 cm 3 A solution of intermediate 4 (454 mg, 0.28 mmol) in water (0.5 cm 3 ) is added dropwise and the reaction mixture is stirred for 2 h. 3 ) is added and the reaction mixture is stirred for a further hour. Then, more water (50 cm 3 ) was added and the solution was diluted with ethyl acetate (50 cm 3 , then 25cm 3 The combined organic extracts are then extracted with water (50 cm 3) and salt water (50cm 3 ), and the aqueous layer was washed with more ethyl acetate (25 cm 3 The combined organic extracts are then dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product is then purified by filtration with 40-60 ml of petroleum (125 cm) at 70 °C. 3 ) and acetone (10 cm 3 The mixture is then cooled to 0°C, filtered, and the solid is mixed with 40-60 petroleum (3 × 10 cm) 3 ) to give Intermediate 5 (191 mg, 45%) as a yellow solid. 1 H NMR (400MHz, CDCl3)9.86(2H,s), 7.68-7.72(4H,m), 7.63(2H,d,J 8.1), 7.41(2H,d,J 7.8), 7.36(2H,d,J 3.9), 7.18(8H,d,J 8.1), 7.11(8H,d,J 8.1), 2.56(8H,t,J 7.8), 1.58-1.64(8H,m), 1.19-1.37(72H,m), 0.87(12H,t,J 6.6). compound 78

[0541] [ka]

[0542] Anhydrous chloroform (13 cm 3 To a solution of intermediate 5 (191 mg, 0.13 mmol) in pyridine (0.7 cm 3 , 8.7 mmol) is added. The mixture is then degassed with nitrogen before 3-(dicyanomethylidene)indan-1-one (172 mg, 0.89 mmol) is added. The solution is then further degassed and stirred at 23° C. for 200 minutes. The reaction mixture is then degassed with methanol (200 cm 3 ) and the resulting precipitate was collected by filtration and diluted with methanol (3 × 10 cm 3 The solid is then washed with diethyl ether (4 × 10 cm 3 ) and the solid is collected by filtration to give compound 78 (158 mg, 67%) as a black solid.1 H NMR (400MHz, CDCl3) 8.86(2H,s), 8.67-8.72(2H,m), 7.92-7.97(2H,m), 7.83(2H,d,J 4.4), 7.71-7.81(8H,m), 7.42-7.47(4H,m), 7.22(8H,d,J 8.2), 7.13(8H,d,J 8.3), 2.58(8H,t,J 7.7), 1.59-1.65(8H,m), 1.18-1.39(72H,m), 0.87(12H,t,J 6.9). Example 79 Intermediate 6

[0543] [ka]

[0544] Anhydrous toluene (150 cm 3 To a solution of 2,7-dibromo-4,4,9,9-tetrakis(4-octylphenyl)-4,9-dihydro-thieno[3',2':4,5]cyclopenta[1,2-b]thieno[2'',3'':3',4']cyclopenta[1',2':4,5]thieno[2,3-d]thiophene (500 mg, 0.34 mmol) in 2,7-dibromo-4,4,9,9-tetrakis(4-octylphenyl)-4,9-dihydro-thieno[3',2':4,5]cyclopenta[1,2-b]thieno[2'',3'':3',4']cyclopenta[1',2':4,5]thieno[2,3-d]thiophene (500 mg, 0.34 mmol) was added tributyl-(5-[1,3]dioxolan-2-yl-thiophen-2-yl)-stannane (0.88 cm 3 , 1.94 mmol) is added and the solution is degassed with nitrogen. Tris(dibenzylideneacetone)dipalladium (59 mg, 0.03 mmol) and tris(o-tolyl)phosphine (74 mg, 0.24 mmol) are then added and, after further degassing, the reaction mixture is heated at 80° C. for 17 h. The reaction mixture is then concentrated under reduced pressure and methanol (5×20 cm 3 ) and collect the solid by filtration to give Intermediate 6 (1.1 g, 99%) as an orange solid. 1H NMR (400MHz, CDCl3)7.12-7.19(10H,m), 7.09(8H,d,J 7.8), 7.00-7.05(4H,m), 6.08(2H,s), 4.08-4.17(4H,m), 3.99-4.08(4H,m), 2.56(8H,t,J 7.8), 1.52-1.63(8H,m), 1.22-1.35(40H,m), 0.87(12H,t,J 6.5). Intermediate 7

[0545] [ka]

[0546] Concentrated hydrochloric acid (0.5 cm 3 , 4.07 mmol, 32%) at 23 °C in tetrahydrofuran (57 cm 3 A solution of intermediate 6 (1.1 g, 0.81 mmol) in water (0.5 cm 3 ) is added dropwise and the reaction mixture is stirred for 1 hour. 3 ) is added and the reaction mixture is stirred for a further 17 hours. Then, more water (100 cm 3 ) was added and the solution was diluted with ethyl acetate (50 cm 3 , then 25cm 3 The combined organic extracts are then extracted with water (50 cm 3 ) and salt water (50cm 3 ), and the aqueous layer was washed with more ethyl acetate (20 cm 3 The combined organic extracts are then dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The crude product is then extracted with methanol (3 x 15 cm 3 ), collected by filtration, and the solid was filtered with 40-60 petroleum (3 × 15 cm 3 ) to give Intermediate 7 (291 mg, 28%) as an orange solid. 1H NMR(400MHz, CDCl3)9.83(2H,s), 7.64(2H,d,J 3.9), 7.32(2H,s), 7.20(2H,d,J 3.9), 7.16(8H,d,J 8.1), 7.11(8H,d,J 8.0), 2.57(8H,t,J 7.6), 1.54-1.64(8H,m), 1.20-1.38(40H,m), 0.82-0.92(12H,m). compound 79

[0547] [ka]

[0548] Anhydrous chloroform (23 cm 3 To a solution of intermediate 7 (287 mg, 0.22 mmol) in pyridine (1.3 cm 3 , 16 mmol) is added. The mixture is then degassed with nitrogen before 3-(dicyanomethylidene)indan-1-one (300 mg, 1.54 mmol) is added. The solution is then further degassed and stirred at 23 °C for 3.25 h. The reaction mixture is then degassed with methanol (300 cm 3 ), the mixture was concentrated under reduced pressure, and the resulting solid was extracted with methanol (3 × 25 cm 3 ) and collected by filtration. The filtered solid is then triturated with diethyl ether (2 x 10 cm 3 ) and acetone (3 × 10 cm 3 The partially purified product is then subjected to column chromatography eluting with a gradient solvent system (40-60 petroleum:dichloromethane; 9.5:0.5 to 2:3) to give compound 79 (86 mg, 24%) as a green / black solid. 1 H NMR (400MHz, CDCl3)8.83(2H,s), 8.69(2H,d,J 7.6), 7.92(2H,d,J 6.6), 7.69-7.79(6H,m), 7.54(2H,s), 7.29(2H,d,J 4.4), 7.11-7.20(16H,m), 2.59(8H,t,J 7.7), 1.58-1.64(8H,m), 1.21-1.38(40H,m), 0.87(12H,t,J 6.5). Example 80 Intermediate 8

[0549] [ka]

[0550] Tetrahydrofuran (25 cm) cooled to -78 °C 3 A solution of 2,7-dibromo-4,4,9,9-tetrakis(3-octylphenyl)-4,9-dihydro-thieno[3',2':4,5]cyclopenta[1,2-b]thieno[2'',3'':3',4']cyclopenta[1',2':4,5]thieno[2,3-d]thiophene (1.00 g, 0.77 mmol) in 1,2 ... 3 , 2.30 mmol, 2.5 M in hexanes) is added dropwise. The reaction is stirred for 1 hour and N,N-dimethylformamide (1.13 cm 3 The reaction is quenched with water (50 cm 3 ) and quenched with dichloromethane (3 × 30 cm 3 The combined organic phases are extracted with water (2 x 20 cm 3 ), dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product is purified by flash chromatography eluting with a gradient solvent system (40-60 petroleum:dichloromethane; 6:4 to 4:6) to give Intermediate 8 (330 mg, 36%) as an orange oil. 1 H NMR (400MHz, CDCl3)9.73(2H,s), 7.62(2H,s), 7.14(4H,t,J 8.0), 6.65-6.77(m, 12H), 3.80(8H,t,J 6.6), 1.58-1.69(8H,m), 1.27-1.38(8H,m), 1.01-1.30(32H,m), 0.71-0.87(12H,m). compound 80

[0551] [ka]

[0552] Chloroform (8.25 cm 3 To a degassed solution of intermediate 8 (330 mg, 0.27 mmol) and 3-(dicyanomethylidene)indan-1-one (373 mg, 1.92 mmol) in 10 mL of HCl was added pyridine (0.55 cm 3 , 6.86 mmol) is added and the mixture is stirred at 23° C. for 2 hours. 3 ) was added, and the resulting suspension was filtered and 3 The resulting solid is purified by column chromatography eluting with a gradient solvent system (40-60 petroleum:dichloromethane; 1:1 to 3:7) to give compound 80 (321 mg, 75%) as a blue solid. 1 H NMR (400MHz, CDCl3) 8.79(2H,s), 8.53-8.67(2H,m), 7.83(2H,m), 7.61-7.73(6H,m), 7.18(4H,m), 6.67-6.81(12H,m), 3.83(8H,t,J 6.7), 1.68(8H,m), 1.33(8H,m), 1.12-1.29(32H,m), 0.78(12H,t,J 6.7). Example 81 Intermediate 9

[0553] [ka]

[0554] Anhydrous tetrahydrofuran (173 cm) at 5°C 3 To a solution of 2,5-dichloro-thieno[3,2-b]thiophene (17.3 g, 82.7 mmol) in ethyl chloroformate (23.7 cm 3 , 248 mmol) was added. Then, 2,2,6,6-tetramethylpiperidinyl magnesium chloride lithium chloride complex (207 cm 3 A solution of 1.0 M tetrahydrofuran (207 mmol) is added dropwise over 1 hour. The reaction is allowed to warm slowly to 23°C and stirred for 42 hours. Water (200 cm 3) was added, the mixture was stirred for 10 min, the solid was collected by filtration and water (2 x 100 cm 3 The solid is washed with acetone (200 cm 3 ), the solid was collected by filtration and diluted with acetone (2 × 100 cm 3 ) to give the intermediate (26.6 g, 91%) as a white solid. 1 H NMR (400MHz, CDCl3) 4.46(4H,q,J 7.1), 1.47(6H,t,J 7.1). Intermediate 10

[0555] [ka]

[0556] Trimethyl-(5-tributylstannanyl-thiophen-2-yl)-silane (30.5 g, 61.7 mmol), intermediate 9 (10.0 g, 28.3 mmol) and tetrakis(triphenylphosphine)palladium(0) (657 mg, 0.57 mmol) were dissolved in anhydrous toluene (100 cm 3 ) and heated at 100°C for 18 hours. The reaction was cooled to 23°C and added to methanol (250cm 3 The suspension is cooled in an ice bath and the solid is collected by filtration and added with methanol (200 cm 3 The crude product was purified by flash chromatography on a silica pad (dichloromethane) followed by elution with 40:60 petroleum:dichloromethane; 60:40 to give Intermediate 10 (7.68 g, 46%) as a yellow solid. 1 H NMR (400MHz, CDCl3) 7.42(2H,d,J 3.5), 7.02(2H,d,J 3.5), 4.19(4H,q,J 7.1), 1.19(6H,t,J 7.1), 0.15(18H,s). Intermediate 11

[0557] [ka]

[0558] Anhydrous tetrahydrofuran (73 cm 3 A solution of 1-bromo-4-octyloxy-benzene (14.1 g, 49.5 mmol) in 1-bromo-4-octyloxy-benzene (58.2 cm) was added over 20 min to t-butyllithium (58.2 cm). 3 , 99.0 mmol, 1.7 M in pentane) is added dropwise. The reaction is warmed to -28°C to -35°C over 30 minutes. A second portion of 1-bromo-4-octyloxy-benzene (3.0 g, 11 mmol) is added and the reaction mixture is stirred for 30 minutes. The reaction is cooled to -78°C and anhydrous tetrahydrofuran (30 cm 3 A solution of Intermediate 10 (4.89 g, 8.25 mmol) in water (50 cm) is added rapidly. The reaction is warmed to 23° C. and stirred for 60 h. 3 ) was added, and the organic matter was dissolved in ether (300 cm 3 The organic phase is extracted with water (3 × 100 cm 3 ), dried over anhydrous magnesium sulfate, filtered, and the solvent removed under reduced pressure. The crude product is purified by column chromatography using a gradient solvent system (40-60 petroleum:dichloromethane; 9:1 to 8:2) to give Intermediate 11 (3.17 g, 29%) as a light brown solid. 1 H NMR (400MHz, CDCl3)7.16-7.23(8H,m), 6.88(2H,d,J 3.4), 6.78-6.85(8H,m), 6.51(2H,d,J 3.4), 3.97(8H,t,J 6.6), 3.37(2H,s), 1.75-1.84(8H,m), 1.27-1.52(40H,m), 0.82-0.95(12H,m), 0.25(18H,s). Intermediate 12 - Route A

[0559] [ka]

[0560] Tetrahydrofuran (25 cm) cooled to -78 °C 3A solution of 2,7-dibromo-4,4,9,9-tetrakis(4-(octyloxy)phenyl)-4,9-dihydro-thieno[3',2':4,5]cyclopenta[1,2-b]thieno[2'',3'':3',4']cyclopenta[1',2':4,5]thieno[2,3-d]thiophene (1.00 g, 0.77 mmol) in 1,2 ... 3 , 2.30 mmol, 2.5 M in hexanes) is added dropwise. The reaction is stirred for an additional hour and N,N-dimethylformamide (1.13 cm 3 , 23.0 mmol) in one portion. The reaction is warmed to 23° C. and stirred for 18 hours. The reaction is quenched with water (50 cm 3 ) and quenched with dichloromethane (3 × 30 cm 3 The resulting organic phase is extracted with water (2 × 20 cm 3 ), dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product is purified by flash chromatography eluting with a gradient solvent system (40-60 petroleum:dichloromethane; 6:4 to 4:6) to give Intermediate 12 (330 mg, 36%) as an orange oil. 1 H NMR (400MHz, CDCl3)9.72(2H,s), 7.58(2H,s), 7.00-7.08(8H,m), 6.69-6.82(8H,m), 3.83(8H,t,J 6.5), 1.61-1.71(8H,m), 1.34(8H,m), 1.11-1.33(32H,m), 0.72-0.90(12H,m). Intermediate 12 - Route B

[0561] [ka]

[0562] Toluene (240 cm 3 To a degassed solution of intermediate 11 (6.00 g, 4.52 mmol) in toluene (200 cm3), amberlyst 15 strong acid (24 g) is added, and the mixture is further degassed and purged, then heated at 75° C. for 18 h. The solution is cooled to about 50° C., filtered, and the solid is extracted with toluene (200 cm3).3 The filtrate is concentrated and washed with 80-100% petroleum (3 x 30 cm 3 ) and the solid is collected by filtration. The solid is triturated with chloroform (120 cm 3 ), N,N-dimethylformamide (5.3 g, 72 mmol) is added, and the solution is cooled to 0°C. Phosphorus(V) oxychloride (10.4 g, 67.9 mmol) is added over 10 minutes. The reaction mixture is then heated at 65°C for 18 hours. Aqueous sodium acetate (150 cm3) is added. 3 , 2M) is added at 65°C and the reaction mixture is stirred for 1 hour. Saturated aqueous sodium acetate is added until the mixture reaches pH 6 and the reaction is stirred for an additional 30 minutes. The aqueous phase is washed with chloroform (2 x 25 cm 3 ), and the combined organic layers were extracted with water (50 cm 3 ), dried over anhydrous magnesium sulfate, filtered, and the solvent removed under reduced pressure. The solid was triturated in 80-100 petrol, and the solid was collected by filtration to give Intermediate 12 (3.06 g, 56%) as an orange oil. 1 H NMR (400MHz, CDCl3)9.72(2H,s), 7.58(2H,s), 7.00-7.08(8H,m), 6.69-6.82(8H,m), 3.83(8H,t,J 6.5), 1.61-1.71(8H,m), 1.34(8H,m), 1.11-1.33(32H,m), 0.72-0.90(12H,m). compound 81

[0563] [ka]

[0564] Chloroform (8.25 cm 3 To a degassed solution of intermediate 12 (330 mg, 0.27 mmol) and 3-(dicyanomethylidene)indan-1-one (373 mg, 1.92 mmol) in 10 mL of HCl was added pyridine (0.55 cm 3 , 6.86 mmol) is added and the mixture is stirred at 23° C. for 4 hours. 3) was added, and the resulting suspension was filtered and 3 The crude product is purified by column chromatography (40-60 petroleum:dichloromethane; 1:1) to give compound 81 (141 mg, 33%) as a blue solid. 1 H NMR (400MHz, CDCl3) 8.79(2H,s), 8.60(2H,m), 7.75-7.91(2H,m), 7.67(4H,m), 7.61(s, 2H), 7.04-7.12(8H,m), 6.74-6.81(8H,m), 3.85(8H,t,J 6.5), 1.68(8H,m), 1.11-1.43(40H,m), 0.72-0.84(12H,m). Example 82 Intermediate 13

[0565] [ka]

[0566] Anhydrous tetrahydrofuran (135 cm) cooled to −78 °C 3 A solution of 1-bromo-3,5-dihexyl-benzene (9.00 g, 27.7 mmol) in 1,2-dichloro-3,5-dihexyl-benzene (11.1 cm) was added to the solution of n-butyllithium (11.1 cm) over 10 min. 3 A solution of 5-bromo-2-[5-(4-bromo-2-methoxycarbonyl-phenyl)thieno[3,2-b]thiophen-2-yl]benzoate (3.13 g, 5.53 mmol) is added dropwise. The reaction is stirred for 1 hour and methyl 5-bromo-2-[5-(4-bromo-2-methoxycarbonyl-phenyl)thieno[3,2-b]thiophen-2-yl]benzoate (3.13 g, 5.53 mmol) is added in one portion. The reaction is warmed to 23° C. and stirred for 18 hours. The reaction is diluted with diethyl ether (50 cm 3 ) and water (100cm 3 The organic phase is separated into water (30 cm 3 ), salt water (30cm 3 ), dried over anhydrous magnesium sulfate, filtered and concentrated under reduced pressure. The crude product was triturated with 40-60 ml petrol and the solid was extracted with toluene (50 cm 3The resulting material is suspended in toluene (2.5 g). p-Toluenesulfonic acid (2.5 g) is added and the reaction mixture is stirred for 17 hours. The suspension is filtered, concentrated under reduced pressure, and purified by flash chromatography eluting with a 40:60 mixture of DCM and petroleum ether. The resulting material is triturated in acetone, and the solid is collected to give Intermediate 12 (2.71 g, 34%) as a yellow solid. 1 H NMR (400MHz, CDCl3) 7.42(2H,d,J 1.7), 7.32(2H,dd,J 8.1, 1.8), 7.11(2H,d,J 8.1), 6.80(4H,t,J 1.5), 6.71(8H,d,J 1.5), 2.40(16H,t,J 7.7), 1.38-1.48(16H,m), 1.11-1.24(48H,m), 0.70-0.79(24H,m). Intermediate 14

[0567] [ka]

[0568] Toluene (12.5 cm 3 ) in a 100 mL flask. 3 To a degassed solution of bis(dibenzylideneacetone)palladium(0) (16 mg, 0.02 mmol) and tris(o-tolyl)phosphine (16 mg, 0.05 mmol) is added bis(dibenzylideneacetone)palladium(0) (16 mg, 0.02 mmol), and the mixture is further degassed. The reaction is then heated to an external temperature of 140 °C for 6 h. The reaction mixture is allowed to cool and concentrated under reduced pressure. The crude product is purified by flash chromatography eluting with a gradient solvent system (40-60 petroleum:dichloromethane; 1:9 to 3:10). The resulting oil is dissolved in chloroform (30 cm 3 ) and 2.5N hydrochloric acid solution (10 cm) was added for 18 hours. 3The organic phase is concentrated under reduced pressure and the residue is purified by flash chromatography eluting with a gradient solvent system (40:60 petroleum:dichloromethane; 1:4 to 1:4). The resulting solid is triturated in acetone and the solid is collected by filtration to give Intermediate 14 (170 mg, 65%) as a yellow solid. 1 H NMR (400MHz, CDCl3)9.78(2H,s), 7.59-7.65(4H,m), 7.55(2H,dd,J 8.0, 1.6), 7.31(2H,d,J 8.0), 7.24(2H,d,J 3.9), 6.82(4H,s), 6.78(8H,s), 2.41(16H,t,J 7.6), 1.39-1.49(16H,m), 1.17(48H,m), 0.69-0.85(24H,m). compound 82

[0569] [ka]

[0570] Chloroform (4.25 cm 3 To a degassed solution of intermediate 14 (170 mg, 0.11 mmol) and 3-(dicyanomethylidene)indan-1-one (153 mg, 0.79 mmol) in 10 mL of pyridine (0.63 cm 3 , 7.86 mmol) is added and the mixture is stirred at 23° C. for 18 hours. 3 ) was added, and the resulting suspension was filtered and 3 The resulting solid is purified by column chromatography eluting with a gradient solvent system (40-60 petroleum:dichloromethane; 1:1 to 2:3) to give compound 82 (32 mg, 15%) as a blue solid. 1H NMR (400MHz, CD2Cl2) 8.75(2H,s), 8.55-8.64(2H,m), 7.82-7.87(2H,m), 7.64-7.80(10H,m), 7.25-7.49(4H,m), 6.80-6.87(12H,m), 2.42(16H,t,J 7.6), 1.47(16H,m), 1.11-1.23(48H,m), 0.67-0.75(m, 24H). Example 83 Intermediate 15

[0571] [ka]

[0572] 1-Bromo-3-hexyl-benzene (6.39 g, 26.5 mmol) and anhydrous tetrahydrofuran (45 cm) at −78 °C 3 ) was added to a solution of n-butyllithium (10.6 cm) for 10 min. 3 A solution of methyl 5-bromo-2-[5-(4-bromo-2-methoxycarbonyl-phenyl)thieno[3,2-b]thiophen-2-yl]benzoate (3.00 g, 5.3 mmol) is added dropwise. The reaction mixture is stirred for 1 hour and methyl 5-bromo-2-[5-(4-bromo-2-methoxycarbonyl-phenyl)thieno[3,2-b]thiophen-2-yl]benzoate (3.00 g, 5.3 mmol) is added in one portion. The reaction is warmed to 23 °C and stirred for 17 hours. The reaction is diluted with diethyl ether (100 cm 3 ) and water (100cm 3 The organic phase is separated into water (2 × 50 cm 3 ), salt water (20cm 3 ), dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting oil was triturated with 40-60 ml petroleum and the solid was extracted with toluene (40 cm 3 The resulting material is triturated in acetone at 50° C. and then filtered at 0° C. to give Intermediate 15 (1.28 g, 22%) as a yellow solid. 1H NMR (400MHz, CDCl3) 7.51(2H,d,J 1.7), 7.41(2H,dd,J 8.1, 1.8), 7.13-7.25(6H,m), 7.04-7.12(8H,m), 6.92-6.98(4H,m), 2. 50-2.59(m, 8H), 1.54(8H,m), 1.18-1.24(m, 24H), 0.79-0.88(m, 12H). Intermediate 16

[0573] [ka]

[0574] Toluene (12.5 cm 3 To a degassed solution of intermediate 15 (250 mg, 0.22 mmol), tributyl-(5-[1,3]dioxolan-2-yl-thiophen-2-yl)-stannane (277 mg, 0.52 mmol), and tris(o-tolyl)phosphine (21 mg, 0.07 mmol) in 10 mL of HCl was added bis(dibenzylideneacetone)palladium(0) (21 mg, 0.02 mmol). The solution was then further degassed and heated to an external temperature of 140 °C for 6 h. The reaction mixture was concentrated under reduced pressure and purified by flash chromatography eluting with a gradient solvent system (40-60 petroleum:dichloromethane; 1:1 to 1:3). The resulting oil was extracted with chloroform (10 cm 3 ) and 2.5N hydrochloric acid (10 cm 3 The organic phase is stirred with water (10 cm 3 ) and salt water (20cm 3 ) and then concentrated under reduced pressure. The resulting solid is triturated in acetone to give intermediate 1638 (75 mg, 28%) as a yellow solid. 1H NMR (400MHz, CDCl3)9.86(2H,s), 7.67-7.74(4H,m), 7.63(2H,m), 7.41(2H,d,J 8.0), 7.34(2H,d,J 3.9), 7.06-7.23(12H,m), 6.98-7.06(4H,m), 2.56(8H,t,J 7.6), 1.55(8H,m), 1.19-1.33(m, 24H), 0.82(12H,m). compound 83

[0575] [ka]

[0576] Chloroform (1.9 cm 3 To a degassed solution of intermediate 16 (75 mg, 0.06 mmol) and 3-(dicyanomethylidene)indan-1-one (87 mg, 0.45 mmol) in 10 mL of pyridine (0.36 cm 3 , 4.46 mmol) is added and the reaction mixture is stirred at 23° C. for 18 hours. 3 ) was added, and the resulting suspension was filtered and 3 The resulting solid is purified by column chromatography eluting with a gradient solvent system (40-60 petroleum:dichloromethane; 1:1 to 2:3) to give compound 83 (63 mg, 65%) as a blue solid. 1 H NMR (400MHz CD2Cl2) 8.75(2H,s), 8.60(2H,dd,J 7.1, 11.4), 7.84(2H,dd,J 6.9, 1.8), 7.63-7.80(8H,m), 7.44(2H,d,J 8.4), 7.39(2H,d,J 4.2), 7.08-7.15(8H,m), 7.04(4H,d,J 7.6), 6.96(4H,m), 2.49(8H,t,J 7.6), 1.49(8H,t,J 4.2), 1.09-1.26(24H,m), 0.68-0.76(12H,m). Example 84 compound 84

[0577] [ka]

[0578] Anhydrous chloroform (34 cm 3 To a solution of intermediate 3 (450 mg, 0.32 mmol) in pyridine (1.8 cm 3 , 22 mmol) is added. The mixture is then degassed with nitrogen before adding malononitrile (148 mg, 2.24 mmol). The solution is then further degassed and stirred at 23° C. for 41 hours. The reaction mixture is then degassed with methanol (350 cm 3 ) plus additional methanol (2 × 10 cm 3 ) and dichloromethane (2 × 5 cm 3 ), then wash with more methanol (35 cm 3 ) was added and the mixture was stirred at 23°C for 50 min, then filtered and the solid was dissolved in methanol (3 x 20 cm 3 ), 40~60 oil (3×20cm 3 ), 80~100 oil (3×20cm 3 ), cyclohexane (3 x 20 cm 3 ), diethyl ether (4 × 20 cm 3 ) and acetone (4 × 20 cm 3 ) to give compound 84 (429 mg, 89%) as a black solid. 1 H NMR(400MHz, CDCl3)8.75(2H,s), 8.68(2H,d,J 8.1), 8.29(2H,s), 7.78(2H,d,J 7.8), 7.24(8H,d,J 8.4), 7.14(8H,d,J 8.3), 2.58(8H,t,J 7.7), 1.56-1.65(8H,m), 1.20-1.37(40H,m), 0.85(12H,t,J 6.9). Example 85 compound 85

[0579] [ka]

[0580] Chloroform (5cm 3To a degassed solution of intermediate 12 (200 mg, 0.17 mmol) and 2-(3-ethyl-4-oxo-thiazolidin-2-ylidene)-malononitrile (225 mg, 1.16 mmol) in 2-(3-ethyl-4-oxo-thiazolidin-2-ylidene)-malononitrile (225 mg, 1.16 mmol) was added pyridine (0.94 cm 3 , 12 mmol) followed by piperidine (992 mg, 11.7 mmol) was added. The reaction was stirred at 23° C. for 18 hours and then methanol (50 cm 3 ), filtered, and purified by flash chromatography eluting with a gradient solvent system (40-60 petroleum:dichloromethane; 3:2 to 2:3). The isolated material was then washed with acetone (10 cm 3 ) and the solid is collected by filtration to give compound 85 (48 mg, 19%) as a blue solid. 1 H NMR (400MHz, CDCl3) 7.97(2H,s), 7.30(2H,s), 7.01-7.08(8H,m), 6.72-6.79(8H,m), 4.24(4H,q,J 7.1), 3.84(8H,t,J 6.5), 1.67(8H,q,J 6.8), 1.30-1.40(14H,m), 1.11-1.28(32H,m), 0.76-0.84(12H,m). Example 86 Intermediate 17

[0581] [ka]

[0582] Anhydrous N,N-dimethylformamide (100 cm) was added at 0 °C. 3 To a solution of 3-methoxy-thiophene (25.0 g, 219 mmol) in anhydrous N,N-dimethylformamide (150 cm) was added over 20 min. 3 A solution of 1-bromo-pyrrolidine-2,5-dione (39.0 g, 219 mmol) in diethyl ether (100 cm) is added dropwise and the reaction is stirred for 65 hours at 23°C. The reaction mixture is then diluted with diethyl ether (100 cm). 3 ) and diluted with salt water (250 cm 3 ) and washed with water (250 cm 3) and the organic layer is separated. The aqueous layer is then diluted with diethyl ether (2 × 100 cm 3 , then 50cm 3 ) and the combined organic extracts were washed with brine (3 × 100 cm 3 ), and the aqueous layer was washed with diethyl ether (50 cm 3 The combined organic extracts are then dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product is purified by a silica plug eluting with a gradient solvent system (40-60 petroleum:dichloromethane; 1:0 to 4:1). The product-containing fractions are concentrated under reduced pressure at 23 °C and quickly placed in an ice-water bath. The crude product is then extracted with anhydrous tetrahydrofuran (150 cm 3 ) is added and the flask is placed under a nitrogen atmosphere. With stirring at 0°C, additional anhydrous tetrahydrofuran (150 cm 3 ) was added, and the solution was cooled to −78° C. and lithium diisopropylamide (120 cm 3 , 240 mmol, 2.0 M in tetrahydrofuran / heptane / ethylbenzene) is added dropwise over 40 min. The reaction mixture is stirred at −78° C. for 2 h, after which the reaction is cooled to −78° C. with anhydrous N,N-dimethylformamide (202 cm). 3 The reaction is then quenched by the dropwise addition of ice (600 cm). 3 ), followed by pentane (400cm 3 The pentane layer was isolated and the aqueous layer was diluted with pentane (2 x 100 cm 3 The combined pentane extracts are then extracted with 20% by weight citric acid solution (2 x 150 cm 3 ), water (150cm 3 ) and salt water (150cm 3 ), and the aqueous layer was washed with pentane (50 cm 3The combined pentane extracts are then dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product is then purified by column chromatography eluting with a gradient solvent system (40-60 petroleum:dichloromethane; 1:0 to 3:2) to afford Intermediate 17 (1.96 g, 4%) as a yellow solid. 1 H NMR (400MHz, CDCl3) 9.84(1H,s), 6.90(1H,s), 3.96(3H,s). Intermediate 18

[0583] [ka]

[0584] Anhydrous toluene (45 cm 3 To a degassed solution of Intermediate 2 (700 mg, 0.42 mmol) and 2-bromo-3-methoxythiophene-5-carboxaldehyde (205 mg, 0.93 mmol) in HCl (2 mL), tris(dibenzylideneacetone)dipalladium (31 mg, 0.03 mmol) and tris(o-tolyl)phosphine (39 mg, 0.13 mmol) are added. The reaction is then further degassed for 20 minutes before heating to 80° C. for 17 hours. The reaction mixture is then concentrated under reduced pressure and diluted with methanol (5×20 cm 3 ) and the solid is filtered. The crude product is then purified by silica plug eluting with a gradient solvent system (40-60 petroleum:dichloromethane; 1:1 to 1:4, then dichloromethane:methanol; 1:0 to 9.5:0.5). Final purification is achieved by column chromatography eluting with a gradient solvent system (40-60 petroleum:dichloromethane; 2:3 to 1:4, then dichloromethane:methanol; 1:0 to 9:1) to afford intermediate 18 (134 mg, 23%) as a dark brown solid. 1H NMR (400MHz, CDCl3)9.92(2H,s), 7.31(2H,s), 7.12-7.17(8H,m), 7.08-7.12(8H,m), 6.84(2 H,s), 4.01(6H,s), 2.53-2.60(8H,m), 1.54-1.64(8H,m), 1.20-1.37(40H,m), 0.87(12H,t,J 6.9). compound 86

[0585] [ka]

[0586] Anhydrous chloroform (10 cm 3 To a solution of intermediate 18 (134 mg, 0.10 mmol) in pyridine (0.6 cm 3 , 6.9 mmol) is added. The mixture is then degassed with nitrogen before 3-(dicyanomethylidene)indan-1-one (134 mg, 0.69 mmol) is added. The solution is then further degassed and stirred at 23 °C for 20 min before being added with more anhydrous degassed chloroform (5 cm 3 ) is added and the reaction is stirred for an additional 3 hours and 20 minutes. The reaction mixture is then diluted with methanol (250 cm 3 ) plus methanol (2 × 10 cm 3 ) and dichloromethane (2 × 5 cm 3 ), then wash with more methanol (50 cm 3 ) was added, the solid was filtered, and then more methanol (10 × 10 cm 3 The crude product is then purified by column chromatography using a gradient solvent system (chloroform, then dichloromethane:methanol; 9.5:0.5) and methanol (3 × 10 cm 3 The filtered solid was partially purified by final purification by trituration with 40-60 petroleum (3 × 10 cm) 3 ), cyclohexane (3 × 10 cm 3 ) and diethyl ether (3 × 10 cm 3 ) to give compound 86 (58 mg, 34%) as a black solid. 1H NMR (400MHz, CDCl3)9.16(2H,s), 8.62-8.67(2H,m), 7.82-7.87(2H,m), 7.63-7.7 2(4H,m), 7.58(2H,s), 7.12-7.19(16H,m), 6.89(2H,s), 4.13(6H,s), 2.59(8H,t,J 7.7), 1.57-1.65(8H,m), 1.22-1.36(40H,m), 0.87(12H,t,J 6.8). Example 87 Intermediate 19

[0587] [ka]

[0588] -78 °C in anhydrous tetrahydrofuran (70 cm 3 A solution of 1-bromo-4-hexyl-benzene (10.0 g, 41.5 mmol) in 1-bromo-4-hexyl-benzene (16.6 cm) was treated with n-butyllithium (16.6 cm) over 10 min. 3 , 41.5 mmol, 2.5 M in hexanes) is added in one portion. The reaction is stirred for 1 hour and methyl 5-bromo-2-[5-(4-bromo-2-methoxycarbonyl-phenyl)thieno[3,2-b]thiophen-2-yl]benzoate (4.70 g, 8.29 mmol) is added in one portion. The reaction is warmed to 23 °C and stirred for 17 hours. The reaction is diluted with diethyl ether (100 cm 3 ) and water (100cm 3 The organic phase is separated into water (2 × 50 cm 3 ), salt water (20cm 3 ), dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting oil was triturated with 40-60 ml petroleum and the solid was extracted with toluene (40 cm 3 ), p-toluenesulfonic acid (2.0 g) is added, and the reaction mixture is stirred at 23° C. for 17 hours. The suspension is filtered and concentrated under reduced pressure. The resulting material is triturated in acetone at 50° C. and then filtered at 0° C. to give Intermediate 19 (3.4 g, 37%) as a yellow solid. 1H NMR (400MHz, CDCl3) 7.52(2H,d,J 1.7), 7.40(2H,dd,J 8.1, 1.8), 7.21(2H,d,J 8.1), 7.06-7.15(m, 16H), 2.52-2.61(m, 8H), 1.58(8H,m), 1.22-1.40(24H,m), 0.83-0.92(12H,m). Intermediate 20

[0589] [ka]

[0590] Toluene (12.5 cm 3 To a degassed solution of intermediate 19 (250 mg, 0.22 mmol), tributyl-(5-[1,3]dioxolan-2-yl-thiophen-2-yl)-stannane (273 mg, 0.51 mmol) and tris(o-tolyl)phosphine (2 mg, 0.01 mmol) in 10 mL of HCl (200 mL), bis(dibenzylideneacetone)palladium(0) (20 mg, 0.02 mmol) is added. The solution is further degassed and heated to an external temperature of 140° C. for 18 hours. Methanol (20 cm 3 ) was added, the suspension was stirred for 30 min, filtered and the solid was dissolved in methanol (20 cm 3 The resulting solid is purified by flash chromatography eluting with 40:60 petrol followed by dichloromethane. The resulting solid is washed with chloroform (30 cm 3 ) and dissolved in hydrochloric acid (10 cm 3 The organic phase is stirred with water (10 cm 3 ), dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and then triturated in acetone to give Intermediate 20 (160 mg, 61%) as a yellow solid. 1H NMR (400MHz, CDCl3)9.78(2H,s), 7.59-7.66(4H,m), 7.55(2H,dd,J 8.0, 1.5), 7.33(2H,d,J 7.9), 7.28(2H,d,J 3.9), 7.11(8H,d,J 8.0), 7.03(8H,d,J 8.0), 2.49(8H,t,J 7.9), 1.51(8H,m), 1.23(24H,m), 0.71-0.83(12H,m). compound 87

[0591] [ka]

[0592] Chloroform (12.3 cm 3 To a degassed solution of intermediate 20 (170 mg, 0.14 mmol) and 3-(dicyanomethylidene)indan-1-one (196 mg, 0.101 mmol) in methanol (30 cm), pyridine (799 mg, 10 mmol) was added and stirred at 23° C. for 18 hours. 3 ) was added, the resulting suspension was filtered and the solid was extracted with methanol (30 cm 3 The solid is washed with acetone (10 cm 3 ), filtered, and diluted with acetone (30 cm 3 ) to give compound 87 (214 mg, 97%) as a blue solid. 1 H NMR (400MHz, CDCl3) 8.87(2H,s), 8.69-8.74(2H,m), 7.92-8.00(2H,m), 7.85(2H,d,J 4.3), 7.72-7.82(8H,m), 7.41-7.50(m, 4H), 7.22(8H,d,J 8.2), 7.14(8H,d,J 8.1), 2.58(8H,t,J 7.9), 1.57(8H,m), 1.24-1.40(24H,m), 0.82-0.91(12H,m). Example 88 compound 88

[0593] [ka]

[0594] Anhydrous chloroform (28 cm 3 To a solution of Intermediate 1 (303 mg, 0.27 mmol) in HCl was added piperidine (0.1 cm 3 , 1.0 mmol) is added. The mixture is then degassed with nitrogen before adding 2-(3-ethyl-4-oxothiazolidin-2-ylidene)malononitrile (134 mg, 0.69 mmol). The solution is then further degassed and stirred at 23° C. for 17 hours. The reaction mixture is then degassed with methanol (300 cm 3 ) plus methanol (3 × 5 cm 3 ) and dichloromethane (5 cm 3 ), then filter the precipitate and wash with methanol (2 × 10 cm 3 The filtered solid is washed with additional methanol (3 × 10 cm 3 ) and the crude product is purified by column chromatography eluting with a gradient solvent system (40-60 petroleum:dichloromethane; 1:1 to 2:3). Final purification is achieved by eluting with methanol (3 × 10 cm 3 The filtered solid was triturated with 40-60 ml of petroleum (3 × 10 cm 3 ), diethyl ether (10 cm 3 ) and acetone (10 cm 3 ) to give compound 88 (144 mg, 36%) as a dark blue / black solid. 1 H NMR (400MHz, CDCl3) 8.05(2H,s), 7.41(2H,s), 7.10-7.16(16H,m), 4.32(4H,q,J 7.1), 2.58(8H,t,J 7.8), 1.56-1.64(8H,m), 1.40(6H,t,J 7.1), 1.22-1.36(40H,m), 0.87(12H,t,J 6.9). Example 89 Intermediate 21

[0595] [ka]

[0596] -78 °C in anhydrous tetrahydrofuran (60 cm 3 A solution of 1-bromo-3,5-dihexyl-benzene (14.5 g, 44.6 mmol) in 1,2-dichloro-3,5-dihexyl-benzene (17.8 cm) was treated with n-butyllithium (17.8 cm) over 10 min. 3 , 44.6 mmol, 2.5 M in hexanes) is added dropwise. The reaction is stirred for 2 hours and ethyl 2-[5-(3-ethoxycarbonyl-2-thienyl)thieno[3,2-b]thiophen-2-yl]thiophene-3-carboxylate (4.00 g, 8.92 mmol) is added. The reaction is warmed to 23°C and stirred for 17 hours. Water (100 cm 3 ) was added and the product was separated by adding ether (100 cm 3 The organic phase is extracted with water (2 × 50 cm 3 ), dried over anhydrous magnesium sulfate, filtered, and the solvent removed under reduced pressure. The crude product is purified by flash chromatography eluting with 40-60 petrol and then dichloromethane. The solid is purified by toluene (40 cm 3 ), p-toluenesulfonic acid (2.0 g) is added and the reaction mixture is heated at 60° C. for 4 hours. The solid is collected by filtration and diluted with toluene (50 cm 3 ) and purified by flash chromatography using a gradient solvent system (40-60 petroleum:dichloromethane; 1:0 to 95:5) to give Intermediate 21 (2.5 g, 21%) as a light brown oil. 1 H NMR (400MHz, CDCl3) 7.07(2H,d,J 4.9), 6.96(2H,d,J 4.9), 6.78(4H,d,J 1.6), 6.74(8H,d,J 1.5), 2.40(16H,t,J 8.0), 1.40-1.48(16H,m), 1.10-1.26(48H,m), 0.69-0.82(24H,m). Intermediate 22

[0597] [ka]

[0598] Intermediate 21 (0.50 g, 0.38 mmol), anhydrous N,N-dimethylformamide (0.40 cm 3 , 5.2 mmol) chloroform (20 cm 3 ) to phosphorus oxychloride (0.47 cm 3 The reaction is heated at 70° C. for 18 hours, then cooled to 60° C. and saturated aqueous sodium acetate (7 cm 3 ) is added and the mixture is stirred for 1 hour. The organic phase is separated and water (20 cm 3 ), dried over anhydrous sodium sulfate, filtered, and the solvent removed under reduced pressure. The solid was dissolved in acetone (3 × 5 cm 3 ) to afford Intermediate 22 (400 mg, 76%) as a light orange solid. 1 H NMR (400MHz, CD2Cl2)9.78(2H,s), 7.64(2H,s), 6.90(4H,d,J 1.6), 6.78(8H,d,J 1.6), 2.46(16H,d,J 7.9), 1.42-1.51(16H,m), 1.17-1.28(48H,m), 0.76-0.85(24H,m). compound 89

[0599] [ka]

[0600] 2-(3-oxo-indan-1-ylidene)-malononitrile (100 mg, 0.5 mmol), intermediate 22 (100 mg, 0.07 mmol) and chloroform (10 cm 3 ) was added to a degassed mixture of pyridine (0.41 cm 3 , 5.1 mmol) is added and the mixture is further degassed. The reaction mixture is stirred for 4 hours and methanol (40 cm 3 ) is added and the suspension is filtered. The solid is then dissolved in methanol (40 cm 3 ) to give compound 89 (101 mg, 84%) as a dark blue solid. 1H NMR (400MHz, CDCl3) 8.87(2H,s), 8.64-8.71(2H,m), 7.84-7.96(2H,m), 7.67-7.79(6H,m), 6.93-6.98(4H,m), 6.77-6.83(8H,m), 2.52(16H,t,J 7.8), 1.53(16H,d,J 7.9), 1.21-1.35(46H,m), 0.80-0.88(24H,m). Example 90 Intermediate 23

[0601] [ka]

[0602] Anhydrous tetrahydrofuran (100 cm 3 A solution of triisopropyl-thieno[3,2-b]thiophen-2-yl-silane (11.86 g, 40.0 mmol) in 1,2-dichloro-3,4-dichloro-2,5-dichloro-1,6-dichloro-2,5 ... 3 , 52.0 mmol, 2.5 M in hexanes) is added dropwise. After the addition, the reaction mixture is stirred at −78° C. for 120 min, and then tributyltin chloride (15.8 cm 3 , 56.0 mmol) is added in one portion. The mixture is then warmed to 23°C over 17 hours and the solvent is removed under reduced pressure. The crude product is obtained by eluting 40-60% petroleum (250 cm). 3 ) and filtered through a zeolite plug (50 g). The plug was filtered with an additional 40-60 ml of petroleum (250 cm 3 The solvent is removed under reduced pressure to give Intermediate 23 (23.1 g, 99%) as a clear oil. 1 H-NMR (400MHz, CD2Cl2) 7.27(1H,d J 0.7), 7.1(1H,s), 1.35-1.63(9H,m), 1.17-1.34(12H,m), 0.98-1.13(18H,m), 0.65-0.91(12H,m). Intermediate 24

[0603] [ka]

[0604] Intermediate 9 (7.5 g, 21 mmol), Intermediate 23 (17.8 g, 30.4 mm) and anhydrous toluene (300 cm 3 The mixture is degassed with nitrogen for 25 minutes. To the mixture is added tetrakis(triphenylphosphine)palladium(0) (500 mg, 0.43 mmol) and the mixture is further degassed for 15 minutes. The mixture is stirred at 85° C. for 17 hours. The reaction mixture is filtered hot through a plug of Celite (50 g) and diluted with hot toluene (100 cm 3 ) and thoroughly wash the mixture. Remove the solvent under reduced pressure at 100 cm 3 The mixture is reduced to rt and cooled in an ice bath to form a suspension. The product is filtered and diluted with water (100 cm 3 ) and methanol (100 cm 3 ), collected and dried under vacuum to give Intermediate 24 (9.5 g, 71%) as a yellow crystalline solid. 1 H-NMR (400MHz, CDCl3) 7.75(2H,d,J 0.7), 7.30(2H,d,J 0.7), 4.36(4H,q,J 7.2), 1.23-1.43(12H,m), 1.07(36H,d,J 7.3). Intermediate 25

[0605] [ka]

[0606] Anhydrous tetrahydrofuran (167 cm 3 A suspension of 1-bromo-4-dodecyloxy-benzene (10.6 g, 30.9 mmol) in tert-butyllithium (36.4 cm) was added over 60 min. 3 , 61.8 mmol, 1.7 M in pentane) is added dropwise. After the addition, the reaction mixture is stirred at -78°C for 120 minutes. Intermediate 24 (6.0 g, 6.9 mmol) is added in one portion. The mixture is then warmed to 23°C over 17 hours. Diethyl ether (200 cm 3 ) and water (200 cm 3) is added and the mixture is stirred for 30 min at 23°C. The product is extracted with diethyl ether (3 x 200 cm 3 The combined organics are dried over anhydrous magnesium sulfate, filtered, and the solvent is removed under reduced pressure. The crude product is purified using silica gel column chromatography (40-60 petroleum:diethyl ether; 7:3). The solid is purified using methanol (200 cm 3 ) and collected by filtration to give Intermediate 25 (10.3 g, 82%) as a cream solid. 1 H NMR (400MHz, CDCl3)7.15-7.23(10H,m), 6.77-6.85(8H,m), 6.65(2H,d,J 0.7), 3.45(2H,s), 3.95(8H,s), 1.71-1.85(8H,m), 1.20-1.52(72H,m), 1.11(36H,d,J 7.3), 0.82-0.95(12H,m). Intermediate 26

[0607] [ka]

[0608] Anhydrous toluene (250 cm) was added at 0 °C for 60 min. 3 Nitrogen gas is bubbled through a solution of intermediate 25 in 200 ml of acetone (200 cm). Amberlyst 15 strong acid (50 g) is added and the mixture is degassed for an additional 30 minutes. The resulting suspension is stirred at 70°C for 2 hours. The reaction mixture is cooled to 23°C, filtered and the solvent is removed under reduced pressure. The crude product is extracted with acetone (200 cm). 3 ) and the solid is filtered to give Intermediate 26 (4.2 g, 89%) as a dark orange solid. 1 H NMR (400MHz, CDCl3)7.28(4H,m), 7.16-7.24(8H,m), 6.75-6.93(8H,m), 3.91(8H,t,J 6.5), 1.67-1.82(8H,m), 1.37-1.48(8H,m), 1.19-1.37(64H,m), 0.80-1.00(12H,m). Intermediate 27

[0609] [ka]

[0610] Anhydrous tetrahydrofuran (24 cm 3 To a solution of intermediate 26 (0.6 g, 0.41 mmol) in n-butyllithium (0.7 cm) was added over 10 min. 3 N,N-dimethylformamide (0.16 cm 3 , 1.6 mmol, 2.5 M in hexane) is added dropwise. After the addition, the reaction mixture is stirred at −78° C. for 60 min. 3 , 2.4 mmol) is added in one portion and the mixture is allowed to warm to 23° C. over 2 hours. Diethyl ether (50 cm 3 ) and water (50 cm 3 ) is added and the mixture is stirred for 30 min at 23°C. The product is extracted with diethyl ether (3 x 100 cm 3 ) and extract with HCl. The combined organics are dried over anhydrous magnesium sulfate, filtered, and the solvent is removed under reduced pressure. The crude product is purified using silica gel column chromatography (40-60 petroleum:dichloromethane; 8:2) to give intermediate 27 (380 mg, 61%) as a dark red oil. 1 H NMR (400MHz, CDCl3)9.90(2H,s), 7.94(2H,s), 7.08-7.23(8H,m), 6.78-6.93(8H,m), 3.91(8H,t,J 6.5), 1.65-1.85(8H,m), 1.17-1.51(72H,m), 0.82-0.96(12H,m). compound 90

[0611] [ka]

[0612] Anhydrous chloroform (26 cm 3 To a solution of intermediate 27 (370 mg, 0.24 mmol) in pyridine (1.4 cm 3, 17 mmol) is added. The mixture is then degassed with nitrogen before 3-(dicyanomethylidene)indan-1-one (280 mg, 1.4 mmol) is added. The solution is then further degassed and stirred at 23° C. for 20 min. The mixture is stirred at 40° C. for 2 h, and then the solvent is removed under reduced pressure. The crude product is extracted with ethanol (200 cm 3 ) to produce a heavy suspension which was collected by filtration and the solid was triturated with acetone (50 cm 3 The crude product was washed with dichloromethane (20 cm 3 ) and dissolved in acetone (250 cm 3 ) to form a suspension. The solid is collected by filtration to give compound 90 (437 mg, 96%) as a gray solid. 1 H NMR(400MHz, CDCl3)8.87(2H,s), 8.63-8.74(2H,m), 8.13(2H,s), 7.87-7.97(2H,m), 7.68-7.82(4H,m), 7.23(8H,d,J 8.8), 6.90(8H,d,J 9.0), 3.92(8H,t,J 6.5), 1.69-1.84(8H,m), 1.16-1.52(72H,m), 0.80-0.97(12H,m). Example 91 Intermediate 28

[0613] [ka]

[0614] Anhydrous tetrahydrofuran (47 cm 3 To a solution of intermediate 26 (1.6 g, 1.1 mmol) in n-butyllithium (1.7 cm) was added over 20 min. 3 , 4.3 mmol, 2.5 M in hexane) is added dropwise. After the addition, the reaction mixture is stirred at −78° C. for 60 minutes. Tributyltin chloride (1.3 cm 3 , 4.9 mmol) is added in one portion and the mixture is then warmed to 23°C over 72 hours. The solvent is removed under reduced pressure. The crude product is purified by passing through a zeolite plug (40-60 petroleum) followed by ethanol (2 x 100 cm3 ) to give Intermediate 28 (2.0 g, 88%) as a dark red oil. 1 H NMR (400MHz, CDCl3) 7.28(2H,s), 7.18-7.24(8H,m), 6.79-6.87(8H,m), 3.91(8H,t,J 6.6), 1.51-1.83(32H,m), 1.20-1.48(114H,m), 1.07-1.18(15H,m), 0.76-1.03(69H,m). compound 91

[0615] [ka]

[0616] Intermediate 28 (700 mg, 0.34 mmol), 2-(7-bromo-benzo[1,2,5]thiadiazol-4-ylmethylene)-malononitrile (218 mg, 0.75 mmol), tri-o-tolyl-phosphine (31 mg, 0.75 mmol) and anhydrous toluene (41 cm 3 The mixture is degassed with nitrogen for 10 minutes. To the mixture is added tris(dibenzylideneacetone)dipalladium(0) (25 mg, 0.03 mmol) and the mixture is further degassed for 15 minutes. The mixture is stirred at 80° C. for 17 hours and the solvent is removed under reduced pressure. Dichloromethane (200 cm 3 ) and water (200 cm 3 ) is added and the mixture is stirred for 30 min at 23°C. The product is extracted with dichloromethane (3 x 100 cm 3 ) The combined organics are dried over anhydrous magnesium sulfate, filtered, and the solvent is removed under reduced pressure. The crude product is dissolved in dichloromethane and precipitated into acetone. The solid is collected by filtration to give compound 91 (451 mg, 70%) as a gray solid. 1H NMR (400MHz, CD2Cl2) 8.55-8.74(6H,m), 7.83(2H,d,J 7.8), 7.14(8H,d,J 8.8), 6.77(8H,d,J 8.8), 3.82(8H,t,J 6.6), 1.58-1.69(8H,m), 1.07-1.40(72H,m), 0.68-0.85(12H,m). Example 92 Intermediate 29

[0617] [ka]

[0618] Anhydrous chloroform (875 cm 3 To a solution of 7-bromo-benzo[1,2,5]thiadiazole-4-carbaldehyde (2.0 g, 8.2 mmol) in pyridine (46.5 cm 3 , 576 mmol) is added. The mixture is then degassed with nitrogen before 3-(dicyanomethylidene)indan-1-one (4.0 g, 21 mmol) is added. The solution is then further degassed and stirred for 20 minutes. The mixture is stirred at 40° C. for 17 hours. The solid is collected by filtration and diluted with acetone (200 cm 3 ), water (200cm 3 ), diethyl ether (200 cm 3 ) and dichloromethane (200cm 3 ) to give Intermediate 29 (3.0 g, 86%) as a pale yellow solid with very limited solubility. Compounds 92 and 93

[0619] [ka]

[0620] Intermediate 28 (700 mg, 0.34 mmol), Intermediate 29 (356 mg, 0.85 mmol), tri-o-tolyl-phosphine (31 mg, 0.10 mmol) and anhydrous toluene (36 cm 3The mixture is degassed with nitrogen for 10 minutes. To the mixture is added tris(dibenzylideneacetone)dipalladium(0) (25 mg, 0.03 mmol) and the mixture is further degassed for 15 minutes. The mixture is stirred at 80° C. for 17 hours and the solvent is removed under reduced pressure. The crude product is obtained by eluting the mixture with acetone (200 cm 3 ) to form a suspension and the solid is collected by filtration. The crude product is purified using silica gel column chromatography eluting with 40-60 petroleum:dichloromethane; 8:2 to give compound 92 (217 mg, 30%) and compound 93 (136 mg, 22%) as a dark gray solid. Compound 92: 1 H NMR (400MHz, CD2Cl2)9.32-9.52(2H,m), 9.15(2H,d,J 8.1), 8.52-8.75(4H,m), 7.61-7.98(8H,m), 7.16(8H,d,J 8.8), 6.79(8H,d,J 8.8), 3.83(8H,t,J 6.5), 1.56-1.73(8H,m), 0.94-1.38(72H,m), 0.77(12H,t,J 6.6).Compound 93: 1 H NMR (400MHz, CD2Cl2)9.41(1H,s), 9.14(1H,d,J 8.0), 8.56-8.71(2H,m), 7.57-7.97(4H,m), 7.02-7.30(10H,m), 6.74(8H,dd,J 9.0 18.1), 3.70-3.91(8H,m), 1.54-1.72(8H,m), 1.06-1.72(72H,m), 0.70-0.84(12H,m). Example 94 Intermediate 30

[0621] [ka]

[0622] -78 °C in anhydrous tetrahydrofuran (50 cm 3 A solution of 1-bromo-3,5-bis-hexyloxy-benzene (8.96 g, 25.1 mmol) in 1,2-dichloro-3,5-bis-hexyloxy-benzene (10.0 cm 3, 25.1 mmol) is added dropwise. The mixture is stirred at −78° C. for 2 hours, then methyl 5-bromo-2-[5-(4-bromo-2-methoxycarbonyl-phenyl)-3a,6a-dihydrothieno[3,2-b]thiophen-2-yl]benzoate (2.85 g, 5.0 mmol) is added in one portion. The mixture is warmed to 23° C. and stirred for 17 hours. The reaction is cooled to 100° C. with water (100 cm 3 ) and carefully pour into dichloromethane (2 × 100 cm 3 The combined organic layers were dried over anhydrous magnesium sulfate, filtered, and the solvent was removed under reduced pressure. The residue was purified by column chromatography (40-60 petroleum:dichloromethane; 6:4). The intermediate diol (3.42 g, 3.65 mmol) was dissolved in toluene (200 cm 3 ) and p-toluenesulfonic acid monohydrate (1.39 g, 7.30 mmol) is added. The mixture is stirred at 50° C. for 90 minutes and the mixture is allowed to cool to 23° C. Water (100 cm 3 ) was added, and the organic layer was diluted with water (100 cm 3 ) and salt water (100cm 3 The organic layer is dried over anhydrous magnesium sulfate, filtered, and the solvent is removed under reduced pressure. The crude product is triturated in ice-cold acetone, and the solid is collected by filtration to give Intermediate 30 (3.08 g, 87%) as a yellow solid. 1 H NMR (400MHz, CDCl3) 7.54(2H,d,J 1.8), 7.39(2H,dd,J 8.1, 1.8), 7.17(2H,d,J 8.1), 6.32(12H,bs), 3.83(16H,td,J 6.6, 1.6), 1.69(16H,p,J 6.8), 1.37(16H,tq,J 9.2, 4.9, 2.9), 1.29(32H,dp, J 7.4, 4.6, 3.8), 0.80-0.91(24H,m). Intermediate 31

[0623] [ka]

[0624] Toluene (50 cm 3 ) and N,N-dimethylformamide (10 cm 3 Intermediate 30 (1.04 g, 0.66 mmol), 2-tributylstannanyl-thiazole (0.62 cm 3 To a degassed solution of tetrakis(triphenylphosphine)palladium(0) (76.1 mg, 0.07 mmol) is added (tetrakis(triphenylphosphine))palladium(0) (76.1 mg, 0.07 mmol) and the mixture is stirred at 110 °C for 5 days. The mixture is cooled to 23 °C and the solvent is removed under reduced pressure. The crude product is purified by column chromatography using a gradient solvent system (40-60 petroleum:dichloromethane:6.5:4.5 to 3:7) to give intermediate 31 (973 mg, 93%) as a yellow oil. 1 H NMR (400MHz, CDCl3) 8.07(2H,d,J 1.5), 7.94(2H,dd,J 8.0, 1.5), 7.82(2H,d,J 3.3), 7.40(2H,d,J 7.9), 7.27(2H,d,J 3.2), 6.43(8H,d,J 2.2), 6.34(4H,t,J 2.2), 3.86(16H,td,J 6.6, 1.8), 1.65-1.73(16H,m), 1.25-1.42(48H,m), 0.81-0.89(24H,m). Intermediate 32

[0625] [ka]

[0626] Anhydrous tetrahydrofuran (100 cm 3 To a stirred solution of intermediate 31 (973 mg, 0.61 mmol) in HCl was added n-butyllithium (0.98 cm 3 , 2.5 mmol, 2.5 M in hexanes) is added dropwise. The reaction mixture is stirred for 2 h and then anhydrous N,N-dimethylformamide (0.21 cm 3 The mixture was warmed to 23°C and stirred for 4 hours, and methanol (3 cm 3 ) is added. The mixture is diluted with EtO (100 cm 3 ) and diluted with water (2 × 100 cm 3). The organic layer is dried over anhydrous magnesium sulfate, filtered, and the solvent is removed under reduced pressure. The crude product is purified by column chromatography using a gradient solvent system (40-60 petroleum:dichloromethane:4:6 to 1:9) to give Intermediate 32 (680 mg, 67%) as a red oil. 1 H NMR (400MHz, CDCl3) 10.01(2H,s), 8.37(2H,s), 8.12(2H,d,J 1.5), 7.99(2H,dd,J 8.0, 1.6), 7.42(2H,d,J 8.0), 6.40(8H,d,J 2.2), 6.34(4H,t,J 2.2), 3.85(16H,td,J 6.6, 1.7), 1.64-1.73(16H,m), 1.22-1.47(48H,m), 0.80-0.89(24H,m). compound 94

[0627] [ka]

[0628] Intermediate 32 (200 mg, 0.12 mmol), 3-ethyl-2-thioxo-thiazolidin-4-one (59 mg, 0.36 mmol) and anhydrous N,N-dimethylformamide (10 cm 3 To a degassed solution of 1,2-dichloromethane (2×100 cm ), potassium carbonate (50 mg, 0.36 mmol) was added and the mixture was stirred for 16 h. Dichloromethane was added and the organic layer was washed with water (2×100 cm ). 3 ), salt water (100cm 3 ), dried over anhydrous magnesium sulfate, filtered, and the solvent removed under reduced pressure. The residue is triturated in acetone, and the solid is collected by filtration to give compound 94 (69 mg, 29%) as a shiny red solid. 1H NMR (400MHz, CDCl3)8.11(2H,d,J 1.7), 8.05(2H,s), 7.96(2H,dd,J 8.0, 1.7), 7.89(2H,s), 7.42(2H,d,J 8.0), 6.41(8H,d,J 2.2), 6.35(4H,t,J 2.2), 4.19(4H,q,J 7.1), 3.82-3.90(16H,m), 1.33-1.42(16H,m), 1.38(16H,dq,J 14.2, 6.6), 1.20-1.32(38H,m), 0.85(24H,t,J 6.8). Example 95 compound 95

[0629] [ka]

[0630] A mixture of intermediate 28 (500 mg, 0.24 mmol), 5-[1-(7-bromo-benzo[1,2,5]thiadiazol-4-yl)-meth-(E)-ylidene]-3-ethyl-2-thioxo-thiazolidin-4-one (197 mg, 0.51 mmol), tri-o-tolyl-phosphine (22 mg, 0.07 mmol) and anhydrous toluene (26 cm 3 The mixture is degassed with nitrogen for 10 minutes. To the mixture is added tris(dibenzylideneacetone)dipalladium(0) (18 mg, 0.02 mmol) and the mixture is further degassed for 15 minutes. The mixture is stirred at 90°C for 17 hours and the solvent is removed under reduced pressure. The crude product is obtained by eluting the mixture with acetone (200 cm 3 ) to form a suspension and the solid is collected by filtration. The crude product is purified using silica gel column chromatography eluting with 40-60 petroleum:dichloromethane; 1:1 to give compound 95 (193 mg, 38%) as a dark green solid. 1H NMR (400MHz, CD2Cl2) 8.57(2H,s), 8.34(2H,s), 7.79(2H,d,J 7.8), 7.58(2H,d,J 7.8), 7.15(8H,d,J 8.8), 6.77(8H,d,J 8.6), 4.13(4H,q,J 7.3), 3.81(8H,t,J 6.5), 1.63(8H,quin,J 6.9), 0.96-1.38(78H,m), 0.77(12H,t,J 6.6). Example 96 compound 96

[0631] [ka]

[0632] Chloroform (19cm 3 ) and pyridine (1 cm 3 To a degassed solution of intermediate 32 (192 mg, 0.12 mmol) in HCl (100 mL), 2-(3-oxo-indan-1-ylidene)-malononitrile (68 mg, 0.35 mmol) is added and the mixture is stirred for 2 hours. 3 , 2M) was added and the mixture was diluted with dichloromethane (50 cm 3 The organic layer was diluted with water (50 cm 3 ) and salt water (50cm 3 ), dried over anhydrous magnesium sulfate, filtered, and the solvent removed under reduced pressure. The residue is triturated in acetone, and the solid is collected by filtration to give compound 96 (182 mg, 78%) as a blue powder. 1H NMR (400MHz, CDCl3) 8.90(2H,s), 8.74(2H,d,J 7.2), 8.41(2H,s), 8.28(2H,d,J 1.6), 8.14(2H,dd,J 8.0, 1.6), 7.95(2H,d,J 7.2), 7.76-7.86(4H,m), 7.45(2H,d,J 8.1), 6.43(8H,d,J 2.2), 6.36(4H,t,J 2.2), 3.88(16H,td,J 6.6, 1.7), 1.67-1.74(16H,m), 1.35-1.42(16H,m), 1.23-1.31(32H,m), 0.84(24H,t,J 7.0). Example 97 Intermediate 33

[0633] [ka]

[0634] Intermediate 28 (400 mg, 0.19 mmol), 2-bromo-thiazole-5-carbaldehyde (112 mg, 0.58 mmol), tri-o-tolyl-phosphine (18 mg, 0.06 mmol) and anhydrous toluene (40 cm 3 The mixture is degassed with nitrogen for 10 minutes. To the mixture is added tris(dibenzylideneacetone)dipalladium(0) (14 mg, 0.02 mmol) and the mixture is further degassed for 15 minutes. The mixture is stirred at 90°C for 17 hours and the solvent is removed under reduced pressure. The crude product is extracted with acetone (200 cm 3 ) and the solid is collected by filtration to give Intermediate 33 (158 mg, 48%) as a dark purple solid. 1 H-NMR (400MHz, CD2Cl2)9.89(2H,s), 8.21(2H,s), 7.82(2H,s), 7.08(8H,d,J 8.6), 6.68-6.81(8H,m), 3.81(8H,t,J 6.4), 1.64(8H,brs), 1.10-1.36(72H,m), 0.78(12H,t,J 6.5). compound 97

[0635] [ka]

[0636] Anhydrous chloroform (9 cm 3 To a solution of intermediate 32 (150 mg, 0.09 mmol) in pyridine (0.5 cm 3 , 6.2 mmol) is added. The mixture is then degassed with nitrogen before 3-(dicyanomethylidene)indan-1-one (120 mg, 0.62 mmol) is added. The solution is then further degassed and stirred at 23° C. for 20 min before the solvent is removed under reduced pressure. The crude product is extracted with ethanol (200 cm 3 ) and the solid is collected by filtration. The crude product is purified using silica gel column chromatography eluting with 40-60 petroleum:dichloromethane; 6:4 to give compound 97 (17 mg, 9%) as a green solid. 1 H NMR (400MHz, CD2Cl2)8.75(2H,s), 8.61(2H,d,J 7.3), 8.25(2H,s), 7.94(2H,s), 7.85(2H,d,J7.3), 7.70(4H,quin,J 7.5), 7.02-7.16(8H,d,J 8.8), 6.77(8H,d,J 9.0), 3.82(8H,t,J 6.4), 1.58-1.66(8H,m), 1.07-1.39(72H,m), 0.70-0.84(12H,m). Example 98 compound 98

[0637] [ka]

[0638] Intermediate 32 (169 mg, 0.10 mmol), pyridine (2 cm 3 ) and chloroform (10 cm 3 To a degassed solution of 1-ethyl-4-methyl-2,6-dioxo-1,2,5,6-tetrahydro-pyridine-3-carbonitrile (55 mg, 0.31 mmol) was added and the mixture was stirred for 20 hours. 3, 2M) was added and the mixture was diluted with dichloromethane (50 cm 3 The organic layer was diluted with water (50 cm 3 ) and salt water (50cm 3 ), dried over anhydrous magnesium sulfate, filtered, and the solvent removed under reduced pressure. The crude product is purified by column chromatography using a gradient solvent system (40-60 petroleum:dichloromethane:2:8 to 0:1) followed by recrystallization (ethanol / dichloromethane) to give compound 98 (69 mg, 34%) as a lustrous blue solid. 1 H NMR (400MHz, CDCl3) 8.39(2H,s), 8.24(2H,d,J 1.5), 8.14(2H,dd,J 8.1, 1.5), 7.90(2H,s), 7.43(2H,d,J 8.0), 6.42(8H,d,J 2.1), 6.35(4H,t,J 2.1), 4.07(4H,q,J 7.1), 3.87(16H,t,J 6.8), 2.65(6H,s), 1.66-1.73(16H,m), 1.32-1.43(16H,m), 1.23-1.30(38H,m), 0.85(24H,t,J 6.9). Example 99 Intermediate 34

[0639] [ka]

[0640] Anhydrous tetrahydrofuran (47 cm 3 To a solution of intermediate 21 (1.60 g, 1.2 mmol) in n-butyllithium (1.96 cm) was added over 20 min. 3 , 4.9 mmol, 2.5 M in hexane) is added dropwise. After the addition, the reaction mixture is stirred at −78° C. for 60 min, and then tributyltin chloride (1.5 cm 3 , 5.5 mmol) is added in one portion. The mixture is then warmed to 23 °C over 72 h and the solvent is removed under reduced pressure. The crude product is purified by passing through a zeolite plug (40-60 petroleum) and then diluted with ethanol (2 × 100 cm 3) to give a mixture of Intermediate 34 and tributyltin chloride (2.7 g) as a dark brown oil. 1 H NMR (400MHz, CD2Cl2) 6.99(2H,s), 6.64-6.85(12H,m), 2.38(16H,t,J 7.7), 0.57-1.69(98H,m). Intermediate 35

[0641] [ka]

[0642] Intermediate 34 (1.5 g, 0.48 mmol), 7-bromo-benzo[1,2,5]thiadiazole-4-carbaldehyde (232 mg, 0.96 mmol), tri-o-tolyl-phosphine (44 mg, 0.14 mmol) and anhydrous toluene (51 cm 3 The mixture is degassed with nitrogen for 10 minutes. Tris(dibenzylideneacetone)dipalladium(0) (35 mg, 0.04 mmol) is added to the mixture, and the mixture is further degassed for 15 minutes. The mixture is stirred at 100 °C for 17 hours, and the solvent is removed under reduced pressure. The crude product is purified using silica gel column chromatography eluting with 40-60 petroleum:dichloromethane; 7:3 to give intermediate 35 (650 mg, 84%) as a dark blue solid. 1 H NMR (400MHz, CDCl3) 10.67-10.73(2H,m), 8.34(2H,s), 8.20(2H,d,J 7.6), 7.93(2H,d,J 7.6), 6.94(12H,s), 2.54(16H,t,J 7.7), 1.51-1.64(16H,m), 1.20-1.36(48H,m), 0.77-0.88(24H,m). compound 99

[0643] [ka]

[0644] Anhydrous chloroform (33 cm) at −30 °C 3To a solution of intermediate 35 (500 mg, 0.31 mmol) in pyridine (1.7 cm 3 , 22 mmol) is added. The mixture is then degassed with nitrogen before 3-(dicyanomethylidene)indan-1-one (417 mg, 2.15 mmol) is added. The solution is then further degassed and stirred at -30 °C for 30 min. The ice bath is removed, the reaction is warmed to 20 °C over 60 min, and the solvent is removed under reduced pressure. The crude product is triturated with ethanol, and the solid is collected by filtration. The crude product is purified using silica gel column chromatography eluting with 40-60 petroleum:dichloromethane; 1:1 to give compound 99 (205 mg, 34%) as a green solid. 1 H NMR (400MHz, CDCl3)9.61(2H,s), 9.32(2H,d,J 8.1), 8.75(2H,d,J 7.8), 8.39(2H,s), 7.94-8.03(4H,m), 7.76-7.91(4H,m), 6.95(12H,s), 2.56(16H,t,J 7.7), 1.48-1.68(m, 16H), 1.20-1.40(48H,m), 0.76-0.95(24H,m). Example 100 Intermediate 36

[0645] [ka]

[0646] Intermediate 13 (350 mg; 0.22 mmol), tributyl-thiophen-2-yl-stannane (248 mg, 0.66 mmol) and anhydrous toluene (20 cm 3To a degassed solution of 36 (216 mg, 61%), tris(dibenzylideneacetone)dipalladium(0) (10 mg, 0.01 mmol) and 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (42 mg, 0.09 mmol) were added, and the mixture was stirred at 80 °C for 17 h. The mixture was cooled to 23 °C, and the solvent was removed under reduced pressure. The crude product was purified by column chromatography using a gradient solvent system (40-60 petroleum:dichloromethane:9:1 to 1:1), followed by trituration in ice-cold acetone. The solid was collected by filtration to give Intermediate 36 (216 mg, 61%) as a yellow powder. 1 H NMR (400MHz, CDCl3) 7.68(2H,d,J 1.6), 7.53(2H,dd,J 7.9, 1.6), 7.32(2H,d,J 7.9), 7.20-7.26(4H,m), 7.04(2H,dd,J 5.1, 3.6), 6.41(8H,d,J 2.2), 6.32(4H,t,J 2.2), 3.84(16H,td,J 6.6, 2.2), 1.62-1.73(16H,m), 1.32-1.42(16H,m), 1.27(32H,dq,J 7.3, 3.7, 3.0), 0.82-0.88(24H,m). Intermediate 37

[0647] [ka]

[0648] Anhydrous N,N-dimethylformamide (1 cm) was added at 0 °C. 3 ) and anhydrous chloroform (10 cm 3 ) was added to a mixture of phosphoroxychloride (0.04 cm 3 , 0.41 mmol) is added. The mixture is warmed to 23° C. and stirred for 1 h, then cooled to 0° C., whereupon Intermediate 36 (216 mg, 0.14 mmol) is added. The mixture is then stirred at 60° C. for 17 h. The mixture is cooled to 23° C. and saturated aqueous sodium bicarbonate (50 cm 3 ) and stirred at 23°C for 30 minutes. The aqueous layer was poured into dichloromethane (100 cm 3The organic layer is extracted with brine (50 cm 3 ), dried over anhydrous magnesium sulfate, filtered, and the solvent removed under reduced pressure. The crude product is purified by column chromatography using a gradient solvent system (40-60 petroleum:dichloromethane:1:1 to 0:1) to give intermediate 37 (49 mg, 22%) as a red solid. 1 H NMR (400MHz, CDCl3)9.86(2H,s), 7.73(2H,d,J 1.7), 7.70(2H,d,J 4.0), 7.61(2H,dd,J 8.0, 1.7), 7.37(2H,d,J 8.0), 7.34(2H,d,J 4.0), 6.39(8H d,J 2.2), 6.34(4H,t,J 2.2), 3.85(16H,m), 1.69(16H,p, J 6.8), 1.23-1.45(48H,m), 0.76-0.92(24H,m). compound 100

[0649] [ka]

[0650] Intermediate 37 (59 mg, 0.04 mmol), anhydrous chloroform (10 cm 3 ) and anhydrous pyridine (2 cm 3 To a degassed solution of 2-(3-oxo-indan-1-ylidene)-malononitrile (21 mg, 0.11 mmol) was added and the reaction mixture was stirred at 0° C. for 2 hours. The reaction was diluted with aqueous hydrochloric acid (5 cm 3 The reaction mixture is quenched by the addition of dichloromethane (50 cm 3 ) was added, and the organic layer was diluted with water (2 × 50 cm 3 ) and salt water (50cm 3 ), dried over anhydrous magnesium sulfate, filtered, and the solvent removed under reduced pressure. The residue is triturated in acetone, and the solid is collected by filtration to give compound 100 (18 mg, 25%) as a black powder. 1H NMR (400MHz, CDCl3) 8.86(2H,s), 8.69-8.73(2H,m), 7.91-7.94(2H,m), 7.88(2H,d,J 1.6), 7.84(2H,d,J 4.3), 7.73-7.81(6H,m), 7.46(2H,d,J 4.2), 7.40(2H,d,J 8.0), 6.42(8H,d,J 2.2), 6.36(4H,t,J 2.2), 3.88(16H,td,J 6.5, 1.8), 1.71(16H,p,J 6.7), 1.31-1.47(16H,m), 1.22-1.32(32H,m), 0.79-0.88(24H,m). Example 101 Intermediate 38

[0651] [ka]

[0652] Anhydrous tetrahydrofuran (48 cm 3 A suspension of 1-bromo-4-dodecylbenzene (3.626 g, 11.15 mmol) in tert-butyllithium (13 cm) was added over 30 min. 3 , 22 mmol, 1.7 M in pentane) is added dropwise. After 40 minutes, the reaction is allowed to warm to -30°C, and then the reaction mixture is cooled back to -78°C. Additional 1-bromo-4-dodecylbenzene (362 mg, 1.11 mmol) is added, and after 15 minutes, ethyl 2-[5-(3-ethoxycarbonyl-2-thienyl)thieno[3,2-b]thiophen-2-yl]thiophene-3-carboxylate (1.00 g, 2.23 mmol) is added in one portion to the reaction mixture. The mixture is then allowed to stir at -78°C for 20 minutes, after which water (100 cm) is removed and the mixture is allowed to warm to 23°C. 3 ) is added and the mixture is stirred for 5 minutes. Then, diethyl ether (50 cm 3 The organic layer is extracted with saturated ammonium chloride solution (100 cm 3 ), water (100cm 3 ) and salt water (100cm 3), dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography eluting with a gradient solvent system (40-60 petroleum:dichloromethane; 1:0 to 3:2) and methanol (3 × 10 cm 3 The filtered solid was purified by final purification, which was carried out by trituration with 40-60 petroleum (2 × 10 cm 3 ), diethyl ether (10 cm 3 ) and acetone (10 cm 3 ) to give Intermediate 38 (2.09 g, 70%) as a yellow solid. 1 H NMR (400MHz, CDCl3)7.12-7.17(10H,m), 7.07-7.12(8H,m), 6.64(2H,s), 6.45(2H,d,J 5.2), 3.24(2H,s), 2.60(8H,t,J 7.7), 1.57-1.65(8H,m), 1.25-1.35(72H,m), 0.89(12H,t,J 6.8). Intermediate 39

[0653] [ka]

[0654] Anhydrous toluene (17 cm 3 A degassed solution of intermediate 38l (1.00 g, 0.75 mmol) in toluene (18 cm 3 A degassed suspension of Amberlist 15 strong acid (4.00 g) in toluene (3×50 cm ) is added and the reaction is stirred at 50° C. for 80 minutes. After the mixture is cooled to 23° C., the solids are removed by filtration and diluted with toluene (3×50 cm ). 3 ) and diethyl ether (3 × 50 cm 3 ), and the filtrate is concentrated under reduced pressure. Purification is carried out by column chromatography eluting with a gradient solvent system (40-60 petroleum:dichloromethane; 1:0 to 4:1) to give intermediate 39 (582 mg, 60%) as a brown oil. 1H NMR (400MHz, CD2Cl2)7.23(2H,d,J 4.9), 7.11-7.16(8H,m), 7.05-7.10(10H,m), 2.54(8H,t,J 7.8), 1.53-1.61(8H,m), 1.22-1.33(72H,m), 0.87(12H,t,J 6.9). Intermediate 40

[0655] [ka]

[0656] Anhydrous tetrahydrofuran (27 cm 3 To a solution of intermediate 39 (582 mg, 0.45 mmol) in n-butyllithium (0.43 cm) was added over 5 min. 3 , 1.1 mmol, 2.5 M in hexanes) is added. The mixture is stirred at −78° C. for 45 min before further n-butyllithium (0.10 cm 3 The mixture is stirred for a further 5 minutes before adding tributyltin chloride (0.42 cm 3 , 1.56 mmol) is added and the mixture is stirred for 17 hours at 23° C. Methanol (15 cm 3 ) is added and the material is concentrated under reduced pressure. The crude product is then taken up in pentane and the suspension is filtered through Celite, washing thoroughly with more pentane. The filtrate is then concentrated under reduced pressure and the solid is extracted with methanol (3 x 10 cm 3 ) and the product is collected by filtration to give Intermediate 40 (790 mg, 94%) as a brown sticky solid. 1 H NMR (400MHz, CDCl3)7.13-7.18(8H,m), 7.03-7.09(10H,m), 2.54(8H,t,J 7.8), 1.51-1.60(20H,m), 1.21-1.38(84H,m), 1.06-1.13(12H,m), 0.85-0.91(30H,m). Intermediate 41

[0657] [ka]

[0658] Anhydrous toluene (28 cm 3 To a degassed solution of intermediate 40 (438 mg, 0.23 mmol) and 7-bromo-benzo[1,2,5]thiadiazole-4-carbaldehyde (124 mg, 0.51 mmol) in HCl (20 mL), tris(dibenzylideneacetone)dipalladium (17 mg, 0.02 mmol) and tris(o-tolyl)phosphine (21 mg, 0.07 mmol) are added. The reaction mixture is degassed for an additional 20 min before it is heated at 80 °C for 17 h. After cooling to 23 °C, the mixture is concentrated under reduced pressure. The crude product is then extracted with methanol (3 × 10 cm). 3 ) and the solid was triturated with acetone (3 × 10 cm 3 ) to give Intermediate 41 (320 mg, 84%) as a blue / black solid. 1 H NMR (400MHz, CDCl3) 10.69(2H,s), 8.33(2H,s), 8.19(2H,d,J 7.6), 7.94(2H,d,J 7.8), 7.22-7.27(8H,m), 7.11-7.17(8H,m), 2.58(8H,t,J 7.9), 1.51-1.65(8H,m), 1.18-1.38(72H,m), 0.86(12H,t,J 6.9). Compound 101

[0659] [ka]

[0660] Anhydrous chloroform (21 cm 3 To a solution of intermediate 41 (319 mg, 0.20 mmol) in anhydrous pyridine (1.1 cm 3, 14 mmol) is added. The mixture is then degassed with nitrogen before 3-(dicyanomethylidene)indan-1-one (266 mg, 1.37 mmol) is added and the reaction is cooled to -40 °C. The solution is further degassed and warmed with stirring for 10 minutes before being held at -15 to -20 °C. After 5 hours, the reaction mixture is then degassed with dichloromethane (10 cm 3 ) and methanol (2 × 10 cm 3 ), while washing with methanol (100 cm 3 ) and add more methanol (50 cm 3 ) is added and the suspension is filtered. The crude product is purified by column chromatography eluting with a gradient solvent system (40-60 petroleum:dichloromethane; 1:0 to 1:1) to give compound 101 (24 mg, 6%) as a black solid. 1 H NMR (400MHz, CDCl3)9.58(2H,s), 9.28(2H,d,J 8.1), 8.73(2H,d,J 7.8), 8.37(2H,s), 7.94(4H,d,J 7.6), 7.74-7.85(4H,m), 7.23-7.27(8H,m), 7.15(8H,d,J 8.3), 2.58(8H,t,J 7.8), 1.53-1.65(8H,m), 1.18-1.38(72H,m), 0.83-0.90(12H,m). Example 102 Compound 102

[0661] [ka]

[0662] Intermediate 12 (100 mg, 0.08 mmol) and a 2:3 regiomeric mixture of 2-(5-methyl-3-oxo-indan-1-ylidene)-malononitrile and 2-(6-methyl-3-oxo-indan-1-ylidene)-malononitrile (121 mg, 0.58 mmol) in chloroform (2.5 cm 3 ), pyridine (0.47 cm 3, 5.8 mmol) is added. The solution is bubbled with nitrogen for 10 minutes and then stirred at 23° C. for 3 hours. Methanol (20 cm 3 ) was added, the suspension was filtered, and methanol (20 cm 3 The resulting solid is washed with methyl ethyl ketone (5 cm) at 95°C for 2 hours. 3 ), cooled to 23°C and the solid collected by filtration. The solid was dissolved in methyl ethyl ketone (5 cm 3 ) to give compound 102 (107 mg, 81%) as a dark blue solid. 1 H NMR (400MHz, CD2Cl2) 8.85(2H,m), 8.40-8.66(2H,m), 7.49-7.93(6H,m), 7.20(8H,d,J 8.6), 6.87(8H,d,J 8.5), 3.95(8H,t,J 6.5), 2.54-2.61(6H,m), 1.73-1.82(8H,m), 1.41-1.52(8H,m), 1.24-1.40(32H,m), 0.90(12H,t,J 6.6). Example 103 Intermediate 42

[0663] [ka]

[0664] Anhydrous tetrahydrofuran (91 cm 3 A suspension of 1-bromo-4-dodecyloxybenzene (7.25 g, 21.2 mmol) in 1-bromo-4-dodecyloxybenzene (25 cm ) was treated with tert-butyllithium (25 cm ) over 30 min. 3, 42 mmol, 1.7 M in pentane) is added dropwise. After 2 hours, the reaction mixture is warmed to -30°C and then cooled back down to -78°C. Additional 1-bromo-4-dodecyloxybenzene (720 mg, 2.11 mmol) and, after 10 minutes, ethyl 2-[5-(3-ethoxycarbonyl-2-thienyl)thieno[3,2-b]thiophen-2-yl]thiophene-3-carboxylate (1.91 g, 4.25 mmol) are added in one portion to the reaction mixture. The mixture is then allowed to stir for 17 hours until the temperature reaches 23°C. Water (50 cm 3 ) and diethyl ether (25 cm 3 ) is added and the organic layer is extracted. The remaining aqueous layer is then diluted with diethyl ether (50 cm 3 ), and the combined organic extracts were extracted with brine (75 cm 3 ), dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product was purified by column chromatography eluting with a gradient solvent system (40-60 petroleum:dichloromethane; 1:0 to 3:7) to afford Intermediate 42 (4.10 g, 69%) as a brown oil that solidified to a yellow / brown solid on standing. 1 H NMR (400MHz, CDCl3)7.09-7.17(10H,m), 6.79-6.85(8H,m), 6.76(2H,s), 6.43(2H,d,J 5.1), 3.95(8H,t,J 6.6), 3.25(2H,s), 1.73-1.83(8H,m), 1.41-1.50(8H,m), 1.24-1.39(64H,m), 0.89(12H,t,J 6.9). Intermediate 43

[0665] [ka]

[0666] Anhydrous toluene (20 cm 3 To a degassed solution of intermediate 42 (1.20 g, 0.85 mmol) in toluene (20 cm 3A degassed suspension of Amberlist 15 strong acid (5.00 g) in toluene (3 x 50 cm) is added and the reaction mixture is stirred at 100°C for 3 hours. The solids are removed by filtration and diluted with toluene (3 x 50 cm). 3 ) and diethyl ether (3 × 50 cm 3 ), and the filtrate is concentrated under reduced pressure. Purification is carried out by column chromatography eluting with a gradient solvent system (40-60 petroleum:dichloromethane; 1:0 to 3:7) to give intermediate 43 (221 mg, 19%) as a brown oil. 1 H NMR (400MHz, CDCl3)7.12-7.19(10H,m), 7.04(2H,d,J 4.9), 6.75-6.82(8H,m), 3.89(8H,t,J 6.48), 1.74(8H,quin,J 7.1), 1.37-1.46(8H,m), 1.19-1.36(64H,m), 0.88(12H,t,J 6.9). Intermediate 44

[0667] [ka]

[0668] Anhydrous tetrahydrofuran (22 cm 3 To a solution of intermediate 43 (493 mg, 0.36 mmol) in n-butyllithium (0.43 cm) was added over 5 min. 3 , 1.1 mmol, 2.5 M in hexane) is added. The mixture is stirred at -78 °C for 1 h. Tributyltin chloride (0.34 cm 3 , 1.3 mmol) is added and the mixture is stirred for 17 hours at 23° C. Methanol (15 cm 3) is added and the material is concentrated under reduced pressure. The crude product is then taken up in pentane and the suspension is filtered through Celite, washing thoroughly with additional pentane. The filtrate is then concentrated under reduced pressure to give the crude product, 2,7-bis(tributylstannyl)-4,4,9,9-tetrakis(4-dodecyloxyphenyl)-4,9-dihydro-thieno[3',2':4,5]cyclopenta[1,2-b]thieno[2'',3'':3',4']cyclopenta[1',2':4,5]thieno[2,3-d]thiophene (948 mg, 0.49 mmol) as a dark brown oil, which is used without further purification. Anhydrous toluene (43 cm) 3 To a degassed solution of 2,7-bis(tributylstannyl)-4,4,9,9-tetrakis(4-dodecyloxyphenyl)-4,9-dihydro-thieno[3',2':4,5]cyclopenta[1,2-b]thieno[2'',3'':3',4']cyclopenta[1',2':4,5]thieno[2,3-d]thiophene (701 mg, 0.36 mmol) and 7-bromo-benzo[1,2,5]thiadiazole-4-carbaldehyde (192 mg, 0.79 mmol) in HCl (200 mL), tris(dibenzylideneacetone)dipalladium (26 mg, 0.03 mmol) and tris(o-tolyl)phosphine (33 mg, 0.11 mmol) were added. The reaction mixture was degassed for an additional 20 minutes, and then heated at 80 °C for 17 hours. After cooling to 23°C, the mixture is concentrated under reduced pressure. The crude product is extracted with methanol (4 x 10 cm 3 ) and the solid is filtered. The crude product is then partially purified twice by column chromatography eluting with two gradient solvent systems (40-60 petroleum:dichloromethane; 1:0 to 1:4) (40-60 petroleum:diethyl ether; 1:0 to 9:1) to isolate partially pure fractions. Final purification is then achieved by trituration with warm acetone and warm diethyl ether to afford intermediate 44 (255 mg, 42%) as a blue / black solid. 1H NMR (400MHz, CDCl3) 10.69(2H,s), 8.31(2H,s), 8.19(2H,d,J 7.8), 7.94(2H,d,J 7.6), 7.22-7.27(8H,m), 6.82-6.88(8H,m), 3.91(8H,t,J 6.5), 1.75(8H,quin,J 7.2), 1.37-1.46(8H,m), 1.20-1.35(64H,m), 0.87(12H,t,J 6.9). compound 103

[0669] [ka]

[0670] Anhydrous chloroform (16 cm 3 To a solution of intermediate 44 (255 mg, 0.15 mmol) in pyridine (0.85 cm 3 , 11 mmol) is added. The mixture is then degassed with nitrogen and cooled to -40 °C. 3-(dicyanomethylidene)indan-1-one (205 mg, 1.05 mmol) is added and the solution is further degassed with stirring for 10 min, warmed and then kept at -15 to -20 °C. After 4 h, the reaction mixture is then diluted with methanol (2 × 10 cm 3 ) and dichloromethane (10 cm 3 ), while washing with methanol (100 cm 3 ) and add more methanol (50 cm 3 ) was added and the suspension was stirred for 10 minutes, then the solid was collected by vacuum filtration and the solid was diluted with more methanol (3 x 10 cm 3 The crude product is purified by silica plug (40-60 petroleum:dichloromethane; 1:4) and the product is concentrated under reduced pressure. The solid is then washed with methanol (3 × 10 cm 3 ), collected by filtration, and then diluted with cyclohexane (3 × 10 cm 3 ), diethyl ether (3 × 10 cm 3 ), acetone (3 x 10 cm 3 ), methyl ethyl ketone (10 cm 3) and ethyl acetate (3 × 10 cm 3 ) to give compound 103 (203 mg, 66%) as a partially pure black solid. 1 H NMR (400MHz, CDCl3)9.58(2H,s), 9.28(2H,d,J 8.6), 8.74(2H,d,J 7.8), 8.36(2H,s), 7.93-8.00(4H,m), 7.75-7.86(4H,m), 7.23-7.27(8H,m), 6.83-6.89(8H,m), 3.92(8H,t,J 6.5), 1.70-1.80(8H,m), 1.38-1.46(8H,m), 1.18-1.37(64H,m), 0.87(12H,t,J 6.9). Example 104 Intermediate 45

[0671] [ka]

[0672] Anhydrous tetrahydrofuran (150 cm 3 To a solution of 6-bromo-benzo[b]thiophene (9.09 g, 42.6 mmol) in 2,4-dichloro-1,3-dichloro- ... 3 , 46.9 mmol, 2.0 M in tetrahydrofuran / heptane / ethylbenzene) is added dropwise. The mixture is stirred at -30°C for 1 hour, then triisopropylsilyl trifluoromethanesulfonate (14.4 g, 46.9 mmol) is added in one portion. The mixture is warmed to 23°C and stirred for 15 hours. Water (150 cm 3 ) was added and the mixture was diluted with diethyl ether (100 cm 3 The aqueous layer was diluted with diethyl ether (2 × 50 cm 3 The combined organic layers were extracted with brine (50 cm 3 ), dried over anhydrous magnesium sulfate, filtered and the solvent removed under reduced pressure. The residue slowly crystallized, which was dissolved in ethanol (150 cm 3 ) to afford Intermediate 45 (11.5 g, 72%) as an off-white solid. 1H NMR (400MHz, CDCl3) 8.04(1H,d,J 1.8), 7.69(1H,d,J 8.5), 7.46(1H,s), 7.46(1H,dd,J 8.6, 1.9), 1.37-1.47(3H,m), 1.16(18H,d,J 7.5). Intermediate 46

[0673] [ka]

[0674] Anhydrous tetrahydrofuran (100 cm 3 To a solution of intermediate 45 (5.00 g, 13.5 mmol) in HCl was added n-butyllithium (6.0 cm 3 , 14.9 mmol; 2.5 M in hexanes) is added dropwise. The mixture is stirred at −78° C. for 2 h and then tributyl(chloro)stannane (4.0 cm 3 , 15 mmol) is added. The mixture is stirred at -78°C for 30 min, then it is warmed to 23°C and stirred for 20 h. Water (100 cm 3 ) was added and the mixture was diluted with diethyl ether (100 cm 3 The aqueous layer was diluted with diethyl ether (2 × 50 cm 3 The combined organic layers were extracted with brine (50 cm 3 ), dried over anhydrous magnesium sulfate, filtered, and the solvent is removed under reduced pressure to give 8.90 g of crude intermediate 46 as a yellow oil. The residue is used in the next step without further purification. 1 H NMR (400MHz, CDCl3) 8.01(1H,d,J 0.9), 7.82(1H,dd,J 7.7, 0.7), 7.49(1H,d,J 0.9), 7.43(1H,dd,J 7.7, 0.7), 1.54-1.67(9H,m), 1.33-1.44(12H,m), 1.17(18H,d,J 7.3), 0.92(12H,t,J 7.3). Intermediate 47

[0675] [ka]

[0676] Anhydrous toluene (60 cm 3 ) and anhydrous N,N-dimethylformamide (10 cm 3 To a degassed solution of intermediate 9 (1.80 g, 5.10 mmol) and intermediate 46 (7.8 g, 12 mmol, 90% purity) in HCl (250 mg, 1.78 mmol), 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (850 mg, 1.78 mmol) and tris(dibenzylideneacetone)dipalladium(0) (187 mg, 0.20 mmol) are added, and the mixture is stirred at 80°C for 20 hours. The reaction mixture is cooled to 23°C, and the solvent is removed under reduced pressure. The residue is dissolved in ice-cold diethyl ether (50 cm 3 ), and the solid was removed by filtration. 3 ) to give Intermediate 47 (3.01 g, 68%) as a yellow solid. 1 H NMR (400MHz, CDCl3) 8.15(2H,d,J 1.6), 7.90(2H,d,J 8.2), 7.62(2H,dd,J 8.2, 1.6), 7.57(2H,s), 4.34(4H,q,J 7.1), 1.40-1.49(6H,m), 1.32(6H,t,J 7.1), 1.19(36H,d,J 7.5). Intermediate 48

[0677] [ka]

[0678] -78 °C in anhydrous tetrahydrofuran (60 cm 3 A solution of 1-bromo-4-octyloxy-benzene (2.48 g, 8.71 mmol) in n-butyllithium (3.48 cm 3 , 8.71 mmol, 2.5 M in hexanes) is added dropwise. The mixture is stirred for 2 hours before adding Intermediate 47 (1.50 g, 1.74 mmol). The cooling bath is removed and the mixture is allowed to warm to 23° C. over 17 hours. The reaction mixture is diluted with water (100 cm 3) and poured into dichloromethane (150 cm 3 The aqueous layer was diluted with dichloromethane (2 × 50 cm 3 The combined organic layers were extracted twice with brine (50 cm 3 ), dried over anhydrous magnesium sulfate, filtered and the solvent removed under reduced pressure. The residue was extracted with anhydrous toluene (300 cm 3 ) and 4-methylbenzenesulfonic acid hydrate (662 mg, 3.48 mmol) is added. The mixture is stirred at 80° C. for 4 hours. After cooling to 23° C., the reaction is diluted with saturated aqueous sodium bicarbonate (50 cm 3 ) and quenched by the addition of water (50 cm 3 ) and dichloromethane (150 cm 3 The aqueous layer was diluted with dichloromethane (50 cm 3 The combined organic layers were extracted with brine (50 cm 3 ), dried over anhydrous magnesium sulfate, filtered, and the solvent removed under reduced pressure. The residue was diluted with anhydrous tetrahydrofuran (40 cm 3 ) and tetrabutylammonium fluoride (2.73 g, 10.4 mmol) is added. The mixture is stirred for 2 hours and then water (50 cm 3 ) and dichloromethane (100 cm 3 The aqueous layer was diluted with dichloromethane (50 cm 3 The combined organic layers were extracted with brine (50 cm 3 ), dried over anhydrous magnesium sulfate, filtered, and the solvent removed under reduced pressure. The residue is purified by column chromatography using a gradient solvent system (40-60 petroleum:dichloromethane; 19:1 to 7:3) to give intermediate 48 (990 mg, 45%) as a yellow sticky solid. 1H NMR (400MHz, CDCl3) 7.80(2H,d,J 8.1), 7.47(2H,d,J 8.0), 7.36(2H,d,J 5.5), 7.28(2H,d,J 7.27), 7.16-7.23(8H,m), 6.77-6.84(8H,m), 3.90(8H,t,J 6.5), 1.69-1.78(8H,m), 1.37-1.46(8H,m), 1.22-1.36(32H,m), 0.88(12H,t,J 7.0). Intermediate 49

[0679] [ka]

[0680] -78 °C in anhydrous tetrahydrofuran (20 cm 3 To a stirred solution of intermediate 48 (574 mg, 0.46 mmol) in HCl was added n-butyllithium (0.74 cm 3 , 1.8 mmol, 2.5 M in hexanes) is added dropwise. The mixture is stirred for 1 h and then anhydrous N,N-dimethylformamide (0.14 cm 3 , 1.8 mmol) is added. The mixture is warmed to 23°C and stirred for 3 hours. The reaction mixture is diluted with saturated aqueous ammonium chloride (20 cm 3 ) and poured into dichloromethane (100 cm 3 The aqueous layer was diluted with dichloromethane (20 cm 3 The combined organic layers were extracted with brine (50 cm 3 ), dried over anhydrous magnesium sulfate, filtered, and the solvent removed under reduced pressure. The residue is purified by column chromatography using a gradient solvent system (cyclohexane:dichloromethane; 3:7 to 2:3) to give intermediate 49 (280 mg; 46%) as an orange solid. 1H NMR (400MHz, CDCl3) 10.02(2H,s), 8.03(2H,s), 7.94(2H,d,J 8.2), 7.54(2H,d,J 8.1), 7.14-7.24(8H,m), 6.79-6.85(8H,m), 3.90(8H,t,J 6.5), 1.67-1.79(8H,m), 1.39-1.44(8H,m), 1.20-1.36(32H,m), 0.88(12H,t,J 7.1). Compound 104

[0681] [ka]

[0682] Pyridine (2 cm 3 ) and chloroform (18 cm 3 To a degassed solution of intermediate 49 (250 mg, 0.19 mmol) in a mixture of 2-(3-oxo-indan-1-ylidene)-malononitrile (112 mg, 0.58 mmol) is added and the mixture is stirred at 0° C. for 3 h. The reaction is diluted with aqueous hydrochloric acid (10 cm 3 The reaction mixture was quenched by the addition of dichloromethane (20 cm 3 The combined organic layers were extracted with brine (50 cm 3 ), dried over anhydrous magnesium sulfate, filtered, and the solvent removed under reduced pressure. The residue is purified by column chromatography using a gradient solvent system (40-60 petroleum:dichloromethane; 3:2 to 3:7). The solid is dissolved in ice-cold acetone (30 cm 3 ) and diethyl ether (20 cm 3 ) to give compound 104 (135 mg, 42%) as a blue solid. 1H NMR (400MHz, CD2Cl2)8.85(2H,s), 8.67(2H,d,J 7.5), 8.24(2H,s), 7.95(4H,t,J 9.2), 7.75-7.83(4H,m), 7.59(2H,d,J 8.3), 7.23(8H,d,J 8.4), 6.83(8H,d,J 8.4), 3.87(8H,t,J 6.6), 1.63-1.74(8H,m), 1.31-1.39(8H,m), 1.18-1.31(32H,m), 0.82(12H,t,J 7.0). Example 105 Intermediate 50

[0683] [ka]

[0684] 7-Bromo-benzo[1,2,5]thiadiazole-4-carbaldehyde (500 mg, 2.0 mmol) and 3-ethyl-2-thioxo-thiazolidin-4-one (2.32 g, 14.4 mmol) in chloroform (220 cm 3 ), pyridine (5.8 cm 3 , 72 mmol) is added and the reaction mixture is further degassed for 30 min. The reaction is then heated at 60° C. for 7 h. The reaction is cooled to 23° C., filtered and the solid is extracted with dichloromethane (100 cm 3 ) to give Intermediate 50 (534 mg, 67%) as a green / brown solid. 1 H NMR (400MHz, CDCl3) 8.44(1H,s), 7.98(1H,d,J 7.7), 7.55(1H,d,J 7.7), 4.25(2H,q,J 7.2), 1.33(3H,t,J 7.1). Intermediate 51

[0685] [ka]

[0686] Anhydrous tetrahydrofuran (200 cm 3To a solution of intermediate 13 (3.09 g, 1.96 mmol) in HCl was added n-butyllithium (3.1 cm 3 , 7.8 mmol, 2.5 M in hexane) is added dropwise and the mixture is stirred for 90 minutes. 3 , 8.8 mmol) is added and the reaction mixture is warmed to 23° C. and stirred for 15 h. 3 ), then add water (50 cm 3 ) and diethyl ether (100 cm 3 The aqueous layer was diluted with diethyl ether (2 × 20 cm 3 The combined organic layers are dried over anhydrous magnesium sulfate, filtered, and the solvent is removed under reduced pressure. The solid is then extracted with 40-60 petroleum (2 × 10 cm) water. 3 ) and taken up in dichloromethane. Evaporation of the solvent under reduced pressure gives a yellow oil which slowly crystallizes at 23°C. 3 ) to give Intermediate 51 (2.95 g, 75%) as a yellow solid. 1 H NMR (400MHz, CDCl3) 7.57(s, 2H), 7.36(2H,d,J 7.4), 7.32(2H,d,J 7.4), 6.39(8H,d,J 2.2), 6.32(4H,d,J 2.2), 3.73-3.91(16H,m), 1.60-1.74(16H,m), 1.43-1.55(12H,m), 1.34-1 .42(16H,m), 1.20-1.34(44H,m), 0.92-1.12(12H,m), 0.84-0.89(30H,m). compound 105

[0687] [ka]

[0688] Anhydrous toluene (18 cm 3 ) and anhydrous N,N-dimethylformamide (2 cm 3To a degassed solution of intermediate 51 (300 mg, 0.15 mmol) and intermediate 50 (174 mg, 0.45 mmol) in a mixture of 2-dicyclohexylphosphino-2',4',6'-triisopropylbiphenyl (57 mg, 0.12 mmol) and tris(dibenzylideneacetone)dipalladium(0) (13 mg, 0.01 mmol) were added, and the reaction mixture was heated at 80 °C for 5 days. The reaction mixture was cooled to 23 °C, and the solvent was removed under reduced pressure. The residue was purified by column chromatography using a gradient solvent system (40-60 petroleum:dichloromethane; 7:3 to 1:4). The solid was recrystallized (ethanol / dichloromethane) to give compound 105 (20 mg, 6%) as a dark red solid. 1 H NMR (400MHz, CDCl3) 8.55(2H,s), 8.20(2H,d,J 1.6), 8.02(2H,dd,J 8.0, 1.6), 7.83(2H,d,J 7.6), 7.76(2H,d,J 7.6), 7.54(2H,d,J 7.9), 6.50(8H,d,J 2.2), 6.37(4H,t,J 2.2), 4.27(4H,q,J 7.1), 3.78-3.97(16H,m), 1.64-1.77(16H,m), 1.33-1.43(22H,m), 1.26-1.31(32H,m), 0.83-0.89(24H,m). Example 106 compound 106

[0689] [ka]

[0690] A degassed mixture of intermediate 12 (100 mg, 0.08 mmol) and 2-(5,6-difluoro-3-oxo-indan-1-ylidene)-malononitrile (96 mg, 0.42 mmol) was added to chloroform (2.5 cm 3 ) and dissolved in pyridine (0.47 cm 3 , 5.8 mmol) is added. The solution is stirred at 23°C for 6 hours. Methanol (35 cm 3 ) was added, the solid was collected by filtration and 3The solid is washed with acetone (2 cm 3 ), filtered, and added to acetone (2 × 1 cm 3 ) to give compound 106 (133 mg, 98%) as a dark blue solid. 1 H NMR (400MHz, CDCl3) 8.77(2H,s), 8.46(2H,dd,J 9.5, 6.5), 7.55-7.65(4H,m), 7.02-7.11(8H,m), 6.71-6.81(8H,m), 3.85(8H,t,J 6.5), 1.62-1.74(8H,m), 1.35(8H,p, J 7.3, 6.8), 1.13-1.31(32H,m), 0.73-0.84(12H,m). Example 107 Compound 107

[0691] [ka]

[0692] Pyridine (1cm 3 ) and chloroform (10 cm 3 To a degassed solution of intermediate 49 (215 mg; 0.17 mmol; 1.00 equiv.) in a mixture of 2-(5-methyl-3-oxo-indan-1-ylidene)-malononitrile and 2-(6-methyl-3-oxo-indan-1-ylidene)-malononitrile (103 mg, 0.50 mmol) is added an equimolar mixture of 2-(5-methyl-3-oxo-indan-1-ylidene)-malononitrile and the mixture is stirred for 4 h. The reaction is diluted with aqueous hydrochloric acid (10 cm 3 The reaction mixture was quenched by the addition of dichloromethane (20 cm 3 The combined organic layers were extracted with brine (50 cm 3 ), dried over anhydrous magnesium sulfate, filtered, and the solvent removed under reduced pressure. The residue is purified by column chromatography using a gradient solvent system (cyclohexane:dichloromethane; 3:7 to 1:4). The solid is dissolved in acetone (30 cm 3 ) and filtered off to give compound 107 (73 mg, 23%) as a blue powder. 1H NMR (400MHz, CDCl3) 8.84(2H,d,J 2.5), 8.59(1H,d,J 8.1), 8.50(1H,s), 8.29(2H,s), 7.94(2H,d,J 8.2), 7.86(1H,d,J 7.8), 7.77(1H,d,J 1.6), 7.55(2H,d,J 8.2), 7.28(8H,d,J 8.7), 6.87(8H,d,J 8.7), 3.91 8H,(t,J 6.5), 1.67-1.80(8H,m), 1.35-1.47(8H,m), 1.18-1.35(32H,m), 0.87(12H,t,J 6.6). Example 108 Intermediate 52

[0693] [ka]

[0694] Intermediate 9 (7.1 g, 20 mmol), trimethyl-(5-tributylstannanyl-thiophen-2-yl)-silane (10 g, 23 mmol) and anhydrous toluene (300 cm 3 The mixture is degassed with nitrogen for 25 minutes. Tetrakis(triphenylphosphine)palladium(0) (0.5 g, 0.4 mmol) is added to the mixture, and the mixture is further degassed for 15 minutes. The mixture is stirred at 85 °C for 17 hours. The reaction mixture is filtered hot through a plug of Celite and washed thoroughly with hot toluene. The crude product is purified using silica gel column chromatography (40-60 petroleum:dichloromethane:4:1) to give intermediate 52 (2.3 g, 21%) as a pale yellow solid. 1 H-NMR (400MHz, CDCl3) 7.40(1H,d,J 3.7), 6.99-7.03(1H,m), 4.13-4.29(4H,m), 1.15-1.28(6H,m), 0.10-0.37(9H,s). Intermediate 53

[0695] [ka]

[0696] Intermediate 52 (2.2 g, 4.6 mmol), Intermediate 23 (3.4 g, 5.8 mmol) and anhydrous toluene (300 cm 3 The mixture is degassed with nitrogen for 25 minutes. To the mixture is added tetrakis(triphenylphosphine)palladium(0) (0.5 g, 0.4 mmol) and the mixture is further degassed for 15 minutes. The mixture is stirred at 85° C. for 17 hours. The reaction mixture is filtered hot through a plug of Celite and washed thoroughly with hot toluene. The crude product is purified by filtration with acetone (100 cm ) for 1 hour. 3 ) to form a heavy suspension. The solid is collected by filtration to give Intermediate 53 (3.2 g, 75%) as a light brown solid. 1 H NMR (400MHz, CDCl3) 7.80-7.86(1H,s), 7.65(1H,d,J 3.4), 7.38(1H,s), 7.24(1H,d,J 3.4), 4.43(4H,m), 1.31-1.51(10H,m), 1.15(18H,d,J 7.3), 0.38(9H,s). Intermediate 54

[0697] [ka]

[0698] Anhydrous tetrahydrofuran (100 cm 3 A solution of 1-bromo-3,5-dihexyl-benzene (4.9 g, 15 mmol) in 1,2-dichloro-3,5-dihexyl-benzene (4.9 g, 15 mmol) was treated with n-butyllithium (6.0 cm) over 30 min. 3 , 15.0 mmol, 2.5 M in hexanes) is added dropwise. After the addition, the reaction mixture is stirred at -78°C for 120 min. Intermediate 53 (2.2 g, 3.0 mmol) is added and the mixture is warmed to 23°C over 17 h. Diethyl ether (100 cm 3 ) and water (100 cm 3 ) is added and the mixture is stirred for 30 min at 23°C. The product is extracted with diethyl ether (3 x 100 cm 3The organics are combined, dried over anhydrous magnesium sulfate, filtered and the solvent is removed under reduced pressure to give Intermediate 54 (2.30 g, 47%) as a brown oil. 1 H NMR (400MHz, CD2Cl2) 7.21(1H,s), 7.06(1H,s), 6.80-7.03(12H,m), 6.42-6.55(2H,m), 3.36(2H,d,J 4.4), 2.44-2.62(16H,m), 1.48-1.65(16H,m), 1.24-1.35(49H,m), 1.11-1.17(18H,m), 0.83-0.94(24H,m), 0.26(9H,s). Intermediate 55

[0699] [ka]

[0700] Anhydrous diethyl ether (100 cm) was added at 0°C for 60 min. 3 Nitrogen gas is bubbled through a suspension of amberlyst 15 strong acid (8.8 g) in toluene (2.2 g, 1.4 mmol). The mixture is degassed for an additional 30 min while intermediate 54 (2.2 g, 1.4 mmol) is added. The resulting suspension is stirred at 23° C. for 2 h. The reaction mixture is filtered and the solvent is removed under reduced pressure. The crude product is dissolved in anhydrous tetrahydrofuran (50 cm 3 ) and tetrabutylammonium fluoride (2.7 cm 3 , 2.7 mmol, 1 M in tetrahydrofuran) is added. The mixture is stirred for 1 hour. Diethyl ether (100 cm 3 ) and water (200 cm 3 ) is added and the mixture is stirred for 30 min. The product is extracted with diethyl ether (3 × 100 cm 3 ) and extract with HCl. The organics are combined, dried over anhydrous magnesium sulfate, filtered, and the solvent is removed under reduced pressure. The crude product is purified using silica gel column chromatography (40-60 petroleum:dichloromethane; 9:1) to give intermediate 55 (1.0 g, 54%) as a dark orange solid. 1H NMR (400MHz, CDCl3)7.25-7.31(1H,m), 7.21-7.25(1H,m), 7.17(1H,d,J 4.9), 7.05(1H,d,J 4.9), 6.81-6.91(12H,m), 2.40-2.57(16H,m), 1.54(16H,d,J 6.8), 1.25(48H,d,J 7.3), 0.85(24H,q,J 6.2). Intermediate 56

[0701] [ka]

[0702] Anhydrous tetrahydrofuran (22 cm 3 To a solution of intermediate 55 (500 mg, 0.37 mmol) in n-butyllithium (0.6 cm) was added over 10 min. 3 N,N-dimethylformamide (0.15 cm 3 , 1.5 mmol, 2.5 M in hexane) is added dropwise. After the addition, the reaction mixture is stirred at −78° C. for 60 min. 3 , 2.2 mmol) is added and the mixture is allowed to warm to 23° C. over 17 hours. Diethyl ether (50 cm 3 ) and water (50 cm 3 ) is added and the mixture is stirred for 30 min at 23°C. The product is extracted with diethyl ether (3 x 100 cm 3 ) and extract with HCl. The combined organics are dried over anhydrous magnesium sulfate, filtered, and the solvent is removed under reduced pressure. The crude product is purified using silica gel column chromatography (40-60 petroleum:dichloromethane; 8:2) to give intermediate 56 (95 mg, 18%) as a dark red oil. 1 H NMR (400MHz, CDCl3)9.70-9.85(1H,s), 9.69-9.75(1H,s), 7.83-7.87(1H,s), 7.56(1H,s), 6.83(4H,s), 6.71(8H,dd,J 12.8, 1.3), 2.29-2.53(16H,m), 1.36-1.55(16H,m), 1.05-1.27(48H,m), 0.76(24H,q,J 6.8). compound 108

[0703] [ka]

[0704] Anhydrous chloroform (40 cm 3 To a solution of intermediate 56 (100 mg, 0.07 mmol) in pyridine (0.4 cm 3 , 4.5 mmol) is added. The mixture is then degassed with nitrogen before 2-(5,6-difluoro-3-oxo-indan-1-ylidene)-malononitrile (65 mg, 0.28 mmol) is added. The solution is then further degassed and stirred at 0° C. for 30 min. The ice bath is removed and the reaction is allowed to warm to 40° C. over 120 min. The mixture is then degassed with 2-propanol (300 cm 3 ) to form a suspension and the solid is collected by filtration. The crude product is diluted with dichloromethane (100 cm 3 ), and then dissolved in ethanol (300 cm 3 ) to produce a heavy suspension which is collected by filtration to give compound 108 (82 mg, 63%) as a blue / green solid. 1 H NMR (400MHz, CD2Cl2) 8.77(2H,s), 8.42(2H,dt,J 9.8, 6.1), 8.06(1H,s), 7.67(1H,s), 7.56(2H,dt,J 11.4, 7.6), 6.66-6.96(12H,m), 2.32-2.56(16H,m), 1.35-1.57(16H,m), 1.05-1.26(48H,m), 0.63-0.80(24H,m). Example 109 Intermediate 57

[0705] [ka]

[0706] Anhydrous tetrahydrofuran (22 cm 3 To a solution of intermediate 55 (500 mg, 0.37 mmol) in n-butyllithium (0.6 cm) was added over 10 min.3 , 1.5 mmol, 2.5 M in hexane) is added dropwise. After the addition, the reaction mixture is stirred at −78° C. for 60 min before tributyltin chloride (0.4 cm 3 , 1.6 mmol) is added. The mixture is then warmed to 23°C for 72 hours. The solvent is removed under reduced pressure and the residue is passed through a zeolite plug (40-60 petroleum). The crude product is dissolved in ethanol (100 cm 3 ), stirred for 30 minutes, and the solvent was decanted. This procedure was repeated twice to give partially purified intermediate 57 (860 mg) as a dark red oil. 1 H NMR (400MHz, CD2Cl2) 7.02-7.16(1H,m), 6.82-6.93(1H,m), 6.57-6.72(12H,m), 2.20-2.32(16H,m), 0.96-1.53(48H,m), 0.54-0.78(24H,m). Intermediate 58

[0707] [ka]

[0708] Intermediate 57 (712 mg, 0.37 mmol), 2-bromo-thiazole-5-carbaldehyde (178 mg, 0.73 mmol), tri-o-tolyl-phosphine (34 mg, 0.11 mmol) and anhydrous toluene (39 cm 3 The mixture is degassed with nitrogen for 10 minutes. To the mixture is added tris(dibenzylideneacetone)dipalladium(0) (27 mg, 0.03 mmol) and the mixture is further degassed for 15 minutes. The mixture is stirred at 80°C for 17 hours, cooled to 23°C, and the solvent is removed under reduced pressure. The crude product is dissolved in 2-propanol (100 cm 3 ) to form a suspension and collect the solid by filtration. The crude product is purified using silica gel column chromatography (40-60 petroleum:dichloromethane; 8:2) to give intermediate 58 (545 mg, 88%) as a dark blue solid. 1H NMR (400MHz, CD2Cl2) 10.61(2H,s), 8.67(1H,s), 8.27(1H,s), 8.10(2H,d,J 7.6), 7.86(2H,dd,J 11.9, 7.7), 6.84(12H,d,J 12.0), 2.43(16H,m), 1.43-1.57(16H,m), 1.03-1.29(48H,m), 0.63-0.80(24H,m). Compound 109

[0709] [ka]

[0710] Anhydrous chloroform (48 cm 3 To a solution of intermediate 58 (120 mg, 0.07 mmol) in pyridine (0.2 cm 3 ) is added. The mixture is then degassed with nitrogen before adding 2-(5,6-difluoro-3-oxo-indan-1-ylidene)-malononitrile (66 mg, 0.29 mmol). The solution is then further degassed and stirred at 0° C. for 20 minutes and at 23° C. for 3 hours. The mixture is then diluted with ethanol (200 cm 3 ) to produce a heavy suspension. The solid was collected by filtration and diluted with methanol (50 cm 3 The crude product was washed with a 1:1 mixture of acetone:diethyl ether (200 cm 3 ) to form a suspension and stir for 30 minutes. The solid is collected by filtration to give compound 109 (110 mg, 73%) as a black solid. 1 H NMR (400MHz, CD2Cl2)9.60(2H,s), 9.31(2H,t,J 8.4), 8.84(1H,s), 8.57-8.65(2H,m), 8.45(1H,s), 8.04(2H,dd,J 12.0, 8.1), 7.78(2H,t,J 7.7), 6.93-7.03(12H,m), 2.51-2.63(16H,m), 1.57-1.66(16H,m), 1.23-1.36(48H,m), 0.79-0.90(24H,m). Example 110 compound 110

[0711] [ka]

[0712] Anhydrous chloroform (48 cm 3 To a solution of intermediate 58 (150 mg, 0.09 mmol) in pyridine (0.3 cm 3 The mixture is then degassed with nitrogen and then diluted with chloroform (10 cm 3 A solution of 3-(dicyanomethylidene)indan-1-one (69 mg, 0.36 mmol) in ethanol (500 cm) is then added. The solution is then further degassed and stirred at 23° C. for 4 h. The mixture is then diluted with ethanol (500 cm). 3 ) to produce a heavy suspension. The solids are collected by filtration and diluted with acetone (50 cm 3 ) to give compound 110 (98 mg, 54%) as a black solid. 1 H NMR (400MHz, CD2Cl2)9.57(2H,s), 9.33(2H,t,J 7.9), 8.82(1H,s), 8.76(2H,d,J 7.3), 8.44(1H,s), 8.01-8.07(2H,m), 7.99(2H,d,J 7.1), 7.78-7.90(4H,m), 6.98(12H,d,J 11.7), 2.48-2.62(16H,m), 1.50-1.65(24H,m), 1.20-1.41(48H,m), 0.78-0.92(24H,m). Example 111 Intermediate 59

[0713] [ka]

[0714] 3-Methoxy-thiophene (25.0 g, 219 mmol) and 2-ethyl-hexan-1-ol (51.4 cm 3 , 329 mmol) in anhydrous toluene (500 cm 3With stirring, 4-methylbenzenesulfonic acid hydrate (4.17 g, 21.9 mmol) is added and after 35 minutes at 23° C., the reaction is heated at reflux for 20 hours. The reaction is then cooled to 23° C. before being dissolved in additional toluene (50 cm 3 ) is added to the solution. 3 ) and salt water (250 cm 3 ), then dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product is purified by silica plug (40-60 petroleum) followed by column chromatography (40-60 petroleum) to give intermediate 59 (23.4 g, 50% yield) as a yellowish oil. 1 H NMR (400MHz, CDCl3) 7.18(1H,dd,J 5.3, 3.1), 6.77(1H,dd,J 5.3, 1.6), 6.24(1H,dd,J 3.2, 1.5), 3.84(2H,dd,J 5.8, 0.9), 1.72(1H,spt,J 6.1), 1.26-1.56(8H,m), 0.88-0.97(6H,m). Intermediate 60

[0715] [ka]

[0716] Anhydrous N,N-dimethylformamide (330 cm) was added at 0 °C. 3 To a solution of intermediate 59 (23.1 g, 109 mmol) in anhydrous N,N-dimethylformamide (110 cm 3 A solution of 1-bromo-pyrrolidine-2,5-dione (19.4 g, 109 mmol) in HCl (2000 cm3) was then added. The reaction mixture was then stirred at 23° C. for 41 h before being cooled to 100° C. with stirring over ice (2000 cm3). 3 Once dissolved, add half of the aqueous suspension to 40-60 ml of petroleum (300 cm 3 The aqueous layer is removed and the other half of the aqueous suspension is extracted. The aqueous layer is extracted with 40-60 ml of petroleum (200 cm 3 The organic extracts are then combined and washed with brine (2 x 200 cm 3), dried over magnesium sulfate, and filtered. Due to stability concerns, bulk samples are not concentrated under reduced pressure and are kept in solution until immediately prior to use. 1 H NMR indicates a quantitative yield of intermediate 60 as a yellow oil. H NMR (400 MHz, CDCl) 7.19 (1H, d, J 5.9), 6.75 (1H, d, J 5.9), 3.93 (2H, d, J 5.9), 1.71 (1H, sept, J 6.1), 1.24-1.60 (8H, m), 0.88-0.98 (6H, m). Intermediate 61

[0717] [ka]

[0718] Anhydrous tetrahydrofuran (180 cm 3 A suspension of 1-bromo-4-hexylbenzene (10.3 g, 42.5 mmol) in 1-bromo-4-hexylbenzene (50 cm) was treated with tert-butyllithium (50 cm) over 30 min. 3 , 85 mmol, 1.7 M in pentane) is added. The reaction is then warmed to -30 °C and then cooled back to -78 °C. Additional 1-bromo-4-hexylbenzene (1.00 g, 4.15 mmol) is then added to ensure the consumption of the remaining tert-butyllithium. Ethyl 2-[5-(3-ethoxycarbonyl-2-thienyl)thieno[3,2-b]thiophen-2-yl]thiophene-3-carboxylate (3.81 g, 8.50 mmol) is then added in one portion to the reaction mixture and the mixture is allowed to stir at 23 °C for 17 hours. The reaction is then diluted with diethyl ether (100 cm 3 ) and diluted with water (200 cm 3 The organic layer was washed with diethyl ether (100 cm 3 ) and diluted with water (200 cm 3 ) and salt water (100cm 3The organic layer is then dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product is then purified by column chromatography using a gradient solvent system (40-60 petroleum:dichloromethane; 1:0 to 2:3) to afford Intermediate 61 (5.61 g, 66% yield) as a pale yellow oil. 1 H NMR (400MHz, CDCl3)7.07-7.18(18H,m), 6.65(2H,s), 6.45(2H,d,J 5.4), 3.25(2H,s), 2.60(8H,t,J 7.7), 1.58-1.66(8H,m), 1.24-1.39(24H,m), 0.87-0.92(12H,m). Intermediate 62

[0719] [ka]

[0720] Anhydrous toluene (65 cm 3 To a degassed suspension of amberlyst 15 strong acid (10.8 g) in toluene (64 cm 3 A degassed solution of intermediate 61 (2.69 g, 2.68 mmol) in toluene (3 × 40 cm) is added and the reaction mixture is stirred at 23 °C for 15 min. The reaction mixture is then heated at 40 °C for 70 min and at 50 °C for an additional 45 min. The reaction is then diluted with toluene (3 × 40 cm). 3 ) and diethyl ether (5 × 50 cm 3 The mixture is then concentrated under reduced pressure and purified by column chromatography eluting with a gradient solvent system (40:60 petroleum:dichloromethane; 1:0 to 1:9) to give Intermediate 62 (540 mg, 21%) as a yellow solid. 1 H NMR (400MHz, CDCl3) 7.12-7.18(10H,m), 7.05-7.10(10H,m), 2.55(8H,t,J 7.8), 1.51-1.63(8H,m), 1.23-1.37(24H,m), 0.84-0.90(12H,m). Intermediate 63

[0721] [ka]

[0722] Anhydrous tetrahydrofuran (70 cm 3 A solution of intermediate 62 (1.15 g, 1.19 mmol) in HCl was cooled to −78° C. and then added n-butyllithium (1.4 cm 3 , 3.6 mmol, 2.5 M in hexane) is added via syringe. The mixture is then stirred at −78° C. for 1 hour before tributyltin chloride (1.1 cm 3 The mixture was stirred at 23° C. for 17 h and methanol (20 cm 3 ) was added and stirred for 6 hours, after which the reaction mixture was concentrated under reduced pressure. The crude product was extracted with methanol (3 × 10 cm 3 ), then anhydrous toluene (150 cm 3 The resulting mixture is then further degassed and heated at 80 °C with continued degassing for 19 hours. The reaction is then stirred at 23 °C for 4 days, after which it is concentrated under reduced pressure. The crude material is then partially purified by silica plug using a gradient solvent system (petroleum 40-60:dichloromethane; 1:0-2:3). The partially purified material is then diluted with methanol (6 × 10 cm). 3 ), and then triturated with anhydrous tetrahydrofuran (58 cm 3 ) and cooled to -78°C. To this mixture was added n-butyllithium (1.4 cm 3 , 3.5 mmol, 2.5 M in hexanes) is added dropwise and the reaction mixture is stirred for 1 hour. The reaction is then diluted with N,N-dimethylformamide (2.3 cm 3The reaction is quenched by the addition of diethyl ether (150 cm3), and after 1 h at -78 °C the reaction is allowed to stir at 23 °C for 15 h. 3 ) and diluted with salt water (20cm 3 ) and water (150 cm 3 The organic layer was then isolated and the aqueous layer was washed with diethyl ether (50 cm 3 The combined organic layers are then extracted with brine (20 cm 3 ) and water (100cm 3 ) and salt water (100cm 3 After further washing with HCl, they are dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The crude product is purified by column chromatography using a gradient solvent system (40–60 petroleum:dichloromethane; 1:0–2:3) followed by column chromatography using a gradient solvent system (80–100 petroleum:diethyl ether; 1:0–6:3) to give Intermediate 63 (285 mg, 17% yield over three steps) as a black solid. 1 H NMR (400MHz, CDCl3) 9.73(2H,s), 7.44(2H,s), 7.41(2H,s), 7.17(8H,d,J 8.2), 7.11(8H,d,J 8.2), 4.08(4H,d,J 5.1), 2.57(8H,t,J 7.8), 1.81(2H,spt,J 6.0), 1.43-1.66(16H,m), 1.22-1.40(32H,m), 0.82-1.00(24H,m). Compound 111

[0723] [ka]

[0724] Anhydrous chloroform (11 cm 3 To a solution of intermediate 63 (150 mg, 0.104 mmol) in pyridine (0.59 cm 3) is added and the solution is degassed for 25 minutes. The reaction mixture is then cooled to -20°C and 2-(5,6-difluoro-3-oxo-indan-1-ylidene)-malononitrile (95 mg, 0.41 mmol) is added. The reaction mixture is then degassed for an additional 15 minutes and warmed to 23°C over 3 hours. The cooling bath is then removed and the reaction is stirred at 23°C for an additional 2 hours before the reaction is ... 3 ), while washing with stirred methanol (200 cm 3 After 30 min, the precipitate was collected by filtration and added to methanol (3 × 10 cm 3 ) to give compound 45 (132 mg, 68% yield) as a black solid. 1 H NMR (400MHz, CDCl3)8.67(2H,s), 8.52(2H,dd,J 10.2, 6.5), 7.67(2H,s), 7.61-7.66(2H,m), 7.51(2H,s), 7.16-7.21(8H,m), 7.11-7.16(8H,m), 4.15(4H,d,J 5.4), 2.60(8H,t,J 7.7), 1.86(2H,spt,J 6.1), 1.50-1.69(16H,m), 1.25-1.43(32H,m), 1.01(6H,t,J 7.5), 0.92-0.97(6H,m), 0.85-0.92(12H,m). Example 112 compound 112 Intermediate 64

[0725] [ka]

[0726] -78 °C in anhydrous tetrahydrofuran (20 cm 3 A solution of 1-bromo-4-hexyloxy-benzene (1.43 g, 5.57 mmol) in 1-bromo-4-hexyloxy-benzene (6.55 cm) was treated with tert-butyllithium (6.55 cm) over 5 min. 3, 11.1 mmol, 1.7 M in pentane) is added. The reaction mixture is then stirred for 45 minutes. Intermediate 10 (550 mg, 0.93 mmol) is added in one portion, the cooling is removed and the reaction mixture is stirred at 23° C. for 17 hours. Water (50 cm 3 ) and diethyl ether (50 cm 3 The organic phase is diluted with water (2 × 30 cm 3 ), dried over magnesium sulfate, filtered, and concentrated under reduced pressure. The resulting solid was extracted with 40-60 petroleum (10 cm 3 ), stirred in a 2×10 cm 3 ) to give Intermediate 64 (1.13 g, 76%) as a pale green solid. 1 H NMR (400MHz, CDCl3)7.11-7.22(8H,m), 6.85(2H,d,J 3.4), 6.75-6.82(7H,m), 6.49(2H,d,J 3.4), 3.94(8H,t,J 6.6), 3.34(2H,s), 1.67-1.84(8H,m), 1.39-1.52(8H,m), 1.25-1.38(16H,m), 0.86-0.95(12H,m), 0.22(s, 18H). Intermediate 65

[0727] [ka]

[0728] Toluene (34 cm) at 75 °C 3 A solution of intermediate 64 (850 mg, 0.70 mmol) in toluene (500 ml) is degassed with a stream of nitrogen for 20 minutes. Amberlyst 15 strong acid (4.0 g) is added and the reaction mixture is degassed for an additional 10 minutes and stirred for 17 hours. The reaction is cooled to 23°C, filtered, and the solid is extracted with toluene (50 cm). 3 The combined organic phases are concentrated under reduced pressure. The intermediate material is extracted with chloroform (17 cm 3), N,N-dimethylformamide (819 mg, 11.2 mmol) is added and the solution is cooled to 0° C. Phosphoryl chloride (1.61 g, 10.5 mmol) is added over 10 minutes, the cooling is removed and the reaction is stirred at 65° C. for 17 hours. An aqueous solution of sodium acetate (100 cm 3 , 6M) is added and the biphasic solution is stirred at 65° C. for 2 h. The mixture is diluted with dichloromethane (15 cm 3 ) and the combined organic phase was extracted with water (2 × 20 cm 3 ), dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The solid was extracted with 40-60 petroleum (10 cm 3 ) and collected by filtration to give Intermediate 65 (763 mg, 63%) as an orange solid. 1 H NMR (400MHz, CD2Cl2)9.80(2H,s), 7.69(2H,s), 7.00-7.28(8H,m), 6.60-6.91(8H,m), 3.91(8H,t,J 6.6), 1.61-1.85(8H,m), 1.38-1.51(8H,m), 1.32(16H,m), 0.82-0.98(12H,m). compound 112

[0729] [ka]

[0730] Intermediate 65 (200 mg, 0.18 mmol) and 2-(3-oxo-indan-1-ylidene)-malononitrile (250 mg, 1.28 mmol) were dissolved in chloroform (5 cm 3 ) and bubble nitrogen through the suspension for 20 minutes. 3 379 mmol) is added and nitrogen is passed through the solution for an additional 20 minutes. The solution is stirred for 17 hours. Methanol (35 cm 3 ) was added, the solid was collected by filtration and added to methanol (3 × 10 cm 3 The solid is washed with acetone (5 cm 3 ), filtered, and added to acetone (3 × 2 cm 3The material is purified on silica gel eluting with a gradient solvent system (40-60 petroleum:dichloromethane; 11:9 to 2:3) to give compound 66 (66 mg, 25%) as a blue solid. 1 H NMR(400MHz, CDCl3)8.86(2H,s), 8.68(2H,d,J 7.4), 7.86-7.95(2H,m), 7.70-7.78(4H,m), 7.68(2H,s), 7.14(8H,d,J 8.7), 6.84(8H,d,J 8.5), 3.92(8H,t,J 6.5), 1.75(8H,m), 1.39-1.47(8H,m), 1.27-1.35(16H,m), 0.88(12H,m). Example 113 compound 113

[0731] [ka]

[0732] Intermediate 65 (200 mg, 0.18 mmol) and 2-(5-methyl-3-oxo-indan-1-ylidene)-malononitrile (268 mg, 1.28 mmol) were dissolved in chloroform (5 cm 3 ) and bubble nitrogen through the suspension for 20 minutes. 3 , 12.9 mmol) is added and nitrogen is passed through the solution for an additional 20 minutes. The solution is stirred for 17 hours. Methanol (35 cm 3 ) was added, the solid was collected by filtration and added to methanol (3 × 10 cm 3 The solid is washed with acetone (5 cm 3 ), filtered, and added to acetone (3 × 2 cm 3 The material is purified on silica gel eluting with a gradient solvent system (40-60 petroleum:dichloromethane; 11:9 to 2:3) to give compound 113 (69 mg, 26%) as a blue solid. 1H NMR (400MHz, CD2Cl2) 8.82-8.88(2H,m), 8.48-8.59(2H,m), 7.55-7.86(6H,m), 7.16-7.25(8H,m), 6.82-6.91(8H,m), 3.95(8H,t,J 6.6), 2.55-2.59(6H,m), 1.71-1.83(8H,m), 1.42-1.52(8H,m), 1.31-1.40(16H,m), 0.88-0.95(12H,m). Example 114 Intermediate 66

[0733] [ka]

[0734] -78 °C in anhydrous tetrahydrofuran (20 cm 3 A solution of 1-bromo-4-((S)-2-methyl-butoxy)-benzene (1.21 g, 4.98 mmol) in 1-bromo-4-((S)-2-methyl-butoxy)-benzene (1.21 g, 4.98 mmol) was treated with tert-butyllithium (5.9 cm) over 5 min. 3 , 10.0 mmol, 1.7 M in pentane) is added and the reaction mixture is stirred for 1 hour. Intermediate 10 (531 mg, 0.90 mmol) is added in one portion, the cooling is removed and the reaction mixture is stirred for 65 hours. Water (25 cm 3 ) was added and the mixture was stirred for 20 min and then ether (25 cm 3 The organic portion is extracted with water (2 × 15 cm 3 ), dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and evaporated to dryness. 3 The solid was collected by filtration and diluted with 40-60 petroleum (10 cm 3 ), filtered, and then added to 40-60 petroleum (2 x 10 cm 3 ) to give Intermediate 66 (785 mg, 68%) as a white solid. 1H NMR (400MHz, CD2Cl2)7.15-7.23(m,8H), 6.92(4H,dd,J 3.4, 1.94), 6.83(8H,dd,J 8.8, 2.1), 6.56(2H,dd,J 3.5, 1.9), 3.70-3.91(8H,m), 3.33(2H,d,J 2.0), 1.82-1.95(4H,m), 1.48-1.67(4H,m), 1.22-1.38(4H,m), 1.00-1.07(12H,m), 0.87-1.00(12H,m), 0.24-0.30(18H,m). Intermediate 67

[0735] [ka]

[0736] Intermediate 66 (785 mg, 0.68 mmol) and toluene (31 cm) were added at 75 °C. 3 To the degassed mixture of 1,000 ml of Amberlyst 15 strong acid (3.20 g) is added and the mixture is further degassed for 10 minutes. The reaction mixture is then stirred for 17 hours. The suspension is filtered and diluted with toluene (50 cm 3 ) and the solvent is removed under reduced pressure. The solid is washed with chloroform (15.7 cm 3 ) and N,N-dimethylformamide (793 mg, 10.9 mmol) is added. The solution is cooled to 0°C and phosphorus oxychloride (1.56 g, 10.2 mmol) is added over 10 minutes. The cooling is removed and the reaction is heated at 65°C for 17 hours. Aqueous sodium acetate (50 cm 3 , 10 M) is added and the mixture is stirred for 3 h. The solution is diluted with chloroform (15 cm 3 The combined organic phases are extracted with water (2 x 20 cm 3 ), dried over anhydrous magnesium sulfate, filtered, and the solvent removed under reduced pressure. The crude product is purified by flash chromatography eluting with a gradient solvent system (40-60 petroleum:dichloromethane; 2:3-4:1) to give Intermediate 67 (260 mg, 37%) as an orange solid. 1H NMR (400MHz, CD2Cl2)9.83(2H,d,J 0.9), 7.72(2H,s), 7.17(8H,d,J 8.6), 6.85(8H,d,J 8.7), 3.68-3.85(8H), 1.79-1.91(4H,m), 1.49-1.61(4H,m), 1.21-1.34(4H,m), 1.01(12H,d,J 6.7), 0.95(12H,t,J 7.5). compound 114

[0737] [ka]

[0738] Intermediate 67 (108 mg, 0.10 mmol), 2-(5-methyl-3-oxo-indan-1-ylidene)-malononitrile (152 mg, 0.73 mmol) and chloroform (2.7 cm 3 ), pyridine (0.59 cm 3 , 7.3 mmol) is added and the mixture is degassed for another 10 min. The reaction mixture is stirred for 5 h and methanol (30 cm 3 The solid is collected by filtration and diluted with methanol (2 × 10 cm 3 The crude product is purified by flash chromatography eluting with a gradient solvent system (40-60 petroleum:dichloromethane; 9:11 to 1:3) to give compound 114 (75 mg, 51%) as a blue solid. 1 H NMR (400MHz, CDCl3) 8.75(2H,s), 8.37-8.51(2H,s), 7.41-7.75(6H,s), 7.04-7.12(8H,s), 6.74-6.82(8H,m), 3.58-3.77(8H,m), 2.44-2.50(6H,m), 1.70-1.82(4H,m), 1.39-1.55(4H,m), 1.09-1.23(4H,m), 0.92(12H,d,J 6.7), 0.85(12H,t,J 7.5). Example 115 compound 115

[0739] [ka]

[0740] Chloroform (10cm 3 ) and pyridine (0.75 cm 3 A solution of intermediate 67 (135 mg, 0.130 mmol) in HCl is degassed with nitrogen for 10 min. 2-(3-oxo-indan-1-ylidene)-malononitrile (180 mg, 0.91 mmol) is added in one portion and the reaction mixture is stirred at 23° C. for 150 min. Methanol (15 cm 3 ) was added and the resulting precipitate was collected by filtration and diluted with methanol (3 × 10 cm 3 The solid is filtered through a pad of silica (40-60 petroleum:dichloromethane; 2:3). Concentration under reduced pressure is followed by refluxing acetone (20 cm 3 ), then in a 3:1 mixture of acetone:chloroform (40 cm 3 ) to give compound 115 (144 mg, 79%) as a dark blue powder. 1 H NMR (400MHz, CDCl3) 8.84(2H,s), 8.61-8.67(2H,m), 7.84-7.90(2H,m), 7.63-7.72(6H, m), 7.13-7.21(8H,m), 6.83-6.90(8H,m), 3.81(4H,m), 3.72(4H,m), 1.78-1.92(4H,m, J 6.6), 1.56(4H,m), 1.26(4H,m), 1.00(12H,d,J 6.7), 0.94(12H,t,J 7.5). Example 116 compound 116

[0741] [ka]

[0742] Anhydrous chloroform (40 cm 3 ) and pyridine (0.83 cm 3 A degassed solution of 10 mmol of anhydrous chloroform (8 cm) was added over 10 min.3 A degassed solution of 2-(5,6-difluoro-3-oxo-indan-1-ylidene)-malononitrile (135 mg, 0.587 mmol) in 2-propanol (300 cm ) is then added. The resulting solution is then degassed for an additional 30 min, warmed to 23° C., and stirred for 4 h. The reaction mixture is then diluted with 2-propanol (300 cm ). 3 ) and stirred for 1 hour. The resulting solid was collected by filtration and diluted with 2-propanol (100 cm 3 ) and ethanol (100 cm 3 The solid is then washed with dichloromethane (50 cm 3 ), and then suspended in methanol (500 cm 3 The solid was collected by filtration and poured into methanol (100 cm 3 ) and ice-cold acetone (100 cm 3 ) to give compound 116 (108 mg, 41%) as a dark blue solid. 1 H NMR (400MHz, CDCl3) 8.77(2H,s), 8.45(2H,dd,J 9.9, 6.5), 7.52-7.66(4H,m), 6.88(4H,s), 6.72(8H,d,J 1.5), 2.34-2.52(16H,m), 1.38-1.48(16H,m), 1.19(48H,d,J 2.0), 0.67-0.88(24H,m). Example 117 Intermediate 68

[0743] [ka]

[0744] Anhydrous tetrahydrofuran (100 cm 3 A solution of 1-bromo-3,5-dihexyl-benzene (5.21 g, 16.0 mmol) in 1,2-dichloro-3,5-dihexyl-benzene (1.21 g, 16.0 mmol) was treated with n-butyllithium (6.4 cm) over 30 min. 3 , 16 mmol, 2.5 M in hexane) is added dropwise. The reaction mixture is then stirred for 2 hours. Intermediate 24 (2.80 g, 3.21 mmol) is then added and the reaction mixture is warmed to 23° C. and stirred for 17 hours. Water (100 cm3 ) is added and the mixture is stirred for a further 1 h. 3 ) was added, and the organic layer was diluted with water (2 × 50 cm 3 ), dried over anhydrous magnesium sulfate, filtered, and the solvent removed under reduced pressure. The crude product is purified by column chromatography using a gradient solvent system (40-60 petroleum:dichloromethane; 19:1 to 1:4) to give Intermediate 68 (3.54 g, 63%) as a pale yellow oil. 1 H NMR (400MHz, CD2Cl2) 7.23(2H,s), 6.86-7.01(12H,m), 6.51(2H,s), 3.41(2H, s), 2.42-2.61(16H,m), 1.49-1.61(16H,m), 1.22-1.45(54H,m), 1.15(36H,d,J 7.3), 0.78-0.95(24H,m). Intermediate 69

[0745] [ka]

[0746] Anhydrous diethyl ether (100 cm 3 To a degassed suspension of amberlyst 15 strong acid (12 g) in toluene is added intermediate 68 (2.95 g, 1.67 mmol), followed by degassing for an additional 30 min. The resulting suspension is warmed to 23 °C and stirred for 1 h. The reaction mixture is filtered through a thin plug of Celite and diluted with diethyl ether (200 cm 3 The crude product was then purified by column chromatography (40-60 petroleum) and then washed thoroughly with anhydrous tetrahydrofuran (50 cm 3 ) and cooled to 0°C. The mixture was added with a solution of tetrabutylammonium fluoride (3.34 cm 3 , 3.34 mmol, 1 M in tetrahydrofuran) is added and the resulting mixture is stirred at 23° C. for 30 min. The solvent is then removed under reduced pressure and the residue is extracted with methanol (200 cm 3) and stirred for 30 minutes. The solid is collected by filtration to give Intermediate 69 (2.02 g, 85%) as a dark orange solid. 1 H NMR (400MHz, CDCl3) 7.13-7.21(4H,m), 6.71-6.84(12H,m), 2.33-2.49(16H,m), 1.38-1.48(16H,m), 1.08-1.22(48H,m), 0.70-0.80(24H,m). Intermediate 70

[0747] [ka]

[0748] Anhydrous tetrahydrofuran (25 cm 3 To a solution of intermediate 69 (600 mg, 0.42 mmol) in n-butyllithium (0.68 cm) was added over 10 min. 3 , 1.7 mmol, 2.5 M in hexanes) is added dropwise. The mixture is then stirred at −78° C. for 1 h before being diluted with anhydrous N,N-dimethylformamide (0.17 cm 3 , 2.5 mmol) is added. The cooling is then removed and the reaction mixture is stirred at 23° C. for 2 hours. Water (50 cm 3 ) was added and the mixture was stirred for 30 min. The organics were washed with diethyl ether (3 × 50 cm 3 ), combined, dried over anhydrous magnesium sulfate, filtered, and the solvent removed under reduced pressure. The crude product is purified by column chromatography using a gradient solvent system (40-60 petroleum:dichloromethane; 1:0 to 4:1) to give Intermediate 70 (450 mg, 72%) as a dark red sticky solid. 1 H NMR (400MHz, CDCl3)9.79(2H,s), 7.85(2H,s), 6.83(4H,s), 6.71(8H,d,J 1.0), 2.41(16H,t,J 7.6), 1.39-1.50(16H,m), 1.15(48H,br.s), 0.70-0.80(24H,m). compound 117

[0749] [ka]

[0750] Anhydrous chloroform (40 cm 3 ) and pyridine (1.15 cm 3 ) was added to a degassed solution of anhydrous chloroform (8 cm) for 10 min. 3 A degassed solution of 2-(5,6-difluoro-3-oxo-indan-1-ylidene)-malononitrile (187 mg, 0.814 mmol) in 2-(5,6-difluoro-3-oxo-indan-1-ylidene)-malononitrile (187 mg, 0.814 mmol) is then added. The reaction mixture is then degassed for an additional 30 min, warmed to 23° C. and stirred for 5 h. The reaction mixture is then diluted with methanol (300 cm 3 ) and stirred for 65 h. The solid was collected by filtration and diluted with ethanol (100 cm 3 ) and methanol (100 cm 3 ) to give compound 117 (62 mg, 16%) as a dark green solid. 1 H NMR (400MHz, CD2Cl2) 8.90(2H,s), 8.55(2H,dd,J 10.1, 6.5), 8.19(2H,s), 7.67(2H,t,J 7.5), 6.85-7.10(12H,m), 2.56(16H,t,J 7.6), 1.46-1.67(16H,m), 1.13-1.45(48H,m), 0.70-0.93(24H,m). Usage Example A The current-voltage characteristics are shown for a solar cell at 100mW.cm -2 Measurements are taken using a Keithley 2400 SMU illuminated by a Newport Solar Simulator with white light. The solar simulator is equipped with an AM1.5G filter. Illumination is calibrated using a Si photodiode. All device fabrication and characterization is performed in a dry nitrogen atmosphere.

[0751] The power conversion efficiency is calculated using the following formula:

[0752]

number

[0753] where FF is

[0754]

number

[0755] is defined as: OPV device properties are obtained for compositions containing Polymer 1 shown below and an acceptor that is either a compound of Formula I or a prior art compound, coated from organic solution. Details of the solution composition are shown in Table 1.

[0756] [ka]

[0757] P3HT is supplied by Merck KGaA.

[0758] [ka]

[0759] Polymer 1 (x=y=1) and its preparation are disclosed in WO 2011 / 131280 A1.

[0760] [ka]

[0761] Polymer 2 (x=y=1) and its preparation are disclosed in WO 2014 / 202184 A1.

[0762] [ka]

[0763] Polymer 3 (x=5; y=1) and its preparation are disclosed in US Pat. No. 8,455,606 B2. PCBM-C60 and Lisicon® PV-A630 are fullerene derivatives supplied by Merck KGaA. A1: Inverted bulk heterojunction organic photovoltaic devices Organic photovoltaic (OPV) devices are fabricated on prepatterned ITO-glass substrates (13 Ω / square) purchased from LUMTEC Corporation. The substrates are cleaned using common solvents (acetone, isopropanol, and deionized water) in an ultrasonic bath. A layer of commercially available aluminum zinc oxide (AlZnO, Nanograde) is applied as a uniform coating by doctor blade at 40 °C. The AlZnO film is then annealed at 100 °C for 10 min in air. The active material solution (i.e., polymer + acceptor) is prepared in a volume of 25 mg cm. -3 The solution is prepared to a concentration of 1000 ppm to completely dissolve the solute. Thin films are blade-coated in an air atmosphere to achieve an active layer thickness of 50-800 nm as measured using a profilometer. A short drying period is then performed to ensure the removal of residual solvent.

[0764] Typically, the blade-coated film is dried on a hot plate for 2 minutes at 70°C. The device is then transferred to an air atmosphere. On top of the active layer, 0.1 mL of poly(styrene sulfonic acid)-doped conductive polymer poly(ethylenedioxythiophene) [PEDOT:PSS Clevios HTL Solar SCA 434 (Heraeus)] is applied and uniformly coated by a doctor blade at 70°C. A Ag (100 nm) cathode is then thermally evaporated through a...

Claims

1. In the compounds of formula I, 【Chemistry 1】 in which the individual radicals, independently of one another, on each occurrence, identically or differently, have the following meanings: Ar ２，３ are selected from the following formulas and their mirror images: 【Chemistry 1-1】 Ar ４，５ each is an arylene or heteroarylene having 5 to 20 ring atoms, monocyclic or polycyclic, unsubstituted or substituted by one or more identical or different groups L, -CY 1 ═CY 2 -, or -C≡C-; Y １ and Y ２ is H, F, Cl, or CN; W １ and W. ２ is S, O, or Se; V １ is CR ５ or N, U １ is CR １ R ２ and U ２ is CR ３ R ４ and Each of R1 to R4 is H, F, Cl or linear, branched or cyclic alkyl having 1 to 30 C atoms (wherein one or more CH ２ The groups may be -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR such that O and / or S atoms are not directly bonded to each other. ０ --, --SiR ０ R ００ -, -CF ２ -, -CR ０ =CR ００ -, -CY １ = C.Y. ２ - or -C≡C-, one or more H atoms are optionally replaced by F, Cl, Br, I or CN, and one or more CH ２ or CH ３ R is an aryl, heteroaryl, arylalkyl, heteroarylalkyl, aryloxy or heteroaryloxy ring system, each of which has 5 to 20 ring atoms, is monocyclic or polycyclic, and is unsubstituted or substituted with one or more identical or different groups L; １ and R ２ and / or R ３ and R ４ The pair may also form, together with the C atom to which they are attached, a spiro group having 5 to 20 ring atoms, which is mono- or polycyclic and unsubstituted or substituted by one or more identical or different groups L, Each of R 5-7 is H, F, Cl or a linear, branched or cyclic alkyl having 1 to 30 C atoms (wherein one or more CH 2 groups are optionally replaced by -O-, -S-, -C(═O)-, -C(═S)-, -C(═O)-O-, -O-C(═O)-, -NR 0 -, -SiR 0 R 00 -, -CF 2 -, -CR 0 ═CR 00 -, -CY 1 ═CY 2 - or -C≡C- such that the O and / or S atoms are not directly bonded to each other, one or more H atoms are optionally replaced by F, Cl, Br, I or CN, and one or more CH 2 or CH 3 groups are optionally substituted with cationic or anionic groups, or aryl, heteroaryl, arylalkyl, heteroarylalkyl, aryloxy or heteroaryloxy, wherein each of the above cyclic groups has 5 to 20 ring atoms, is monocyclic or polycyclic, and is unsubstituted or substituted with one or more identical or different groups L; R Ｔ１ and R Ｔ２ Each of the following formulas is used: 【Chemistry 2-1】 【Chemistry 2-2】 in which each radical, independently of one another, has the same or different meanings at each occurrence: R ａ and R ｂ each is aryl or heteroaryl each having 4 to 30 ring atoms and which is unsubstituted or substituted by one or more groups L or one of the meanings given for L, L is F, Cl, -NO ２ , -CN, -NC, -NCO, -NCS, -OCN, -SCN, R ０ , OR ０ , S.R. ０ , -C(=O)X ０ , -C(=O)R ０ , -C(=O)-OR ０ , -OC(=O)-R ０ , -NH ２ , -NHR ０ , -NR ０ R ００ , -C(=O)NHR ０ , -C(=O)NR ０ R ００ , -SO ３ R ０ , -SO ２ R ０ , -OH, -NO ２ , -CF ３ , -SF ５ or substituted silyl, or carbyl or hydrocarbyl having 1 to 30 C atoms, R ０ and R ００ each of is H or optionally fluorinated linear or branched alkyl having 1 to 20 C atoms, X ０ is a halogen, a and b are 0, 1, 2 or 3; m is 1, 2 or 3; L' is one of the meanings of H or L, r is 0, 1, 2, 3 or 4; s is 0, 1, 2, 3, 4 or 5; t is 0, 1, 2 or 3; u is 0, 1 or 2; compound.

2. Ar in Formula I ４～５ However, the following equations and their mirror images 【Chemistry 3】 in which each radical, independently of one another, has the same or different meanings at each occurrence: W １ and W. ２ is S, O, or Se; W ３ is N.R. ０ , S, O or Se; V １ is CR ５ or N, V ２ is CR ６ or N, R 5 to 7 have the meanings according to claim 1 , R8 is H, F, Cl, CN or linear, branched or cyclic alkyl having 1 to 30 C atoms (wherein one or more CH ２ The groups may be -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR such that O and / or S atoms are not directly bonded to each other. ０ --, --SiR ０ R ００ -, -CF ２ -, -CR ０ =CR ００ -, -CY １ = C.Y. ２ - or -C≡C-, one or more H atoms are optionally replaced by F, Cl, Br, I or CN, and one or more CH ２ or CH ３ the radicals are optionally substituted with cationic or anionic groups, or aryl, heteroaryl, arylalkyl, heteroarylalkyl, aryloxy or heteroaryloxy, each of the above cyclic radicals having from 5 to 20 ring atoms, being monocyclic or polycyclic and being unsubstituted or substituted with one or more identical or different radicals L as defined in claim 1; Y 1 and Y 2 have the meanings according to claim 1 , R 0 and R 00 have the meanings according to claim 1 .

2. The compound of claim 1 having the formula:

3. Ar in Formula I ２ and Ar ３ However, the following equations and their mirror images 【Chemistry 4】 wherein R ５～７ 3. The compound according to claim 1 or 2, wherein:

4. Ar in Formula I ４ and Ar ５ However, the following equations and their mirror images 【Chemistry 5】 wherein X is selected from the group consisting of １～４ each of which is H, F, Cl or a linear, branched or cyclic alkyl having 1 to 30 C atoms (wherein one or more CH ２ The groups may be -O-, -S-, -C(=O)-, -C(=S)-, -C(=O)-O-, -O-C(=O)-, -NR such that O and / or S atoms are not directly bonded to each other. ０ --, --SiR ０ R ００ -, -CF ２ -, -CR ０ =CR ００ -, -CY １ = C.Y. ２ - or -C≡C-, one or more H atoms are optionally replaced by F, Cl, Br, I or CN, and one or more CH ２ or CH ３ the radicals are optionally substituted with cationic or anionic groups, or aryl, heteroaryl, arylalkyl, heteroarylalkyl, aryloxy or heteroaryloxy, each of the above cyclic radicals having from 5 to 20 ring atoms, being monocyclic or polycyclic and being unsubstituted or substituted with one or more identical or different radicals L as defined in claim 1; Y 1 and Y 2 have the meanings according to claim 1 , R 0 and R 00 have the meanings given in claim 1 The compound according to any one of claims 1 to 3.

5. R Ｔ１ and R Ｔ２ A compound according to any one of claims 1 to 4, wherein both represent electron withdrawing groups.

6. R Ｔ１ and R Ｔ２ But the following formula 【Chemistry 6】 wherein L, L′, R ａ 6. Compounds according to any one of claims 1 to 5, in which r has the meaning given in claim 1.

7. The following formula: 【Chemistry 7-1】 【Chemistry 7-2】 【Chemistry 7-3】 【Chemistry 7-4】 wherein R １ , R ２ , R ３ , R ４ , R Ｔ１ , R Ｔ２ , Ar ４ , Ar ５ 7. Compounds according to any one of claims 1 to 6, in which a and b have the meanings indicated in claims 1 to 6.

8. R １～４ is selected from optionally fluorinated or arylated or heteroarylated alkyl or alkoxy having 1 to 16 C atoms, said aryl or heteroaryl being monocyclic or polycyclic, having 4 to 30 ring atoms and being unsubstituted or substituted with one or more groups L as defined in claim 1.

9. 9. A composition comprising one or more compounds according to any one of claims 1 to 8, further comprising one or more compounds having one or more of semiconducting, hole or electron transporting, hole or electron blocking, conductive, photoconductive, photoactive or luminescent properties, and / or a binder.

10. 10. The composition of claim 9, wherein the composition comprises one or more n-type semiconductors, at least one of which is a compound according to any one of claims 1 to 8, and the composition further comprises one or more p-type semiconductors.

11. 11. The composition of claim 9 or 10, comprising one or more p-type semiconductors selected from conjugated polymers.

12. The conjugated polymer has the formula: 【Chemistry 8-1】 【Chemistry 8-2】 【Chemistry 8-3】 【Chemistry 8-4】 【Chemistry 8-5】 【Chemistry 8-6】 【Chemistry 8-7】 【Chemistry 8-8】 【Chemistry 8-9】 【Chemistry 8-10】 【Chemistry 8-11】 【Chemistry 8-12】 【Chemistry 8-13】 【Chemistry 8-14】 wherein R １１～１９ denote, independently of one another, H or one of the meanings of L defined in claim 1; X １ , X ２ , X ３ and X ４ 12. The composition of claim 11, wherein: represents H, F or Cl; x and y are each, independently of one another, greater than 0 and less than 1, where x+y=1 and n is an integer greater than 1.

13. The conjugated polymer has the formula: R ３１ - Lock - R ３２ PT where "chain" denotes a polymer chain selected from formulas P1 to P53; R ３１ and R ３２ But, H, C １～２０ Alkyl or optionally substituted C ６～１２ Aryl or C ２～１０ 13. The composition of claim 11 or 12, exhibiting an end-capping group selected from heteroaryl.

14. The composition according to any one of claims 9 to 13, comprising one or more n-type semiconductors selected from fullerenes or fullerene derivatives.

15. A bulk heterojunction (BHJ) formed from the composition of any one of claims 9 to 14.

16. Use of a compound according to any one of claims 1 to 8, or a composition according to any one of claims 9 to 14, in an electronic or optoelectronic device, or a component of such a device, or an assembly comprising such a device.

17. A formulation comprising one or more compounds according to any one of claims 1 to 8 or a composition according to any one of claims 9 to 14, further comprising one or more solvents selected from organic solvents.

18. 15. An electronic device comprising a compound according to any one of claims 1 to 8 or a composition according to any one of claims 9 to 14, the electronic device being selected from an organic field effect transistor (OFET), an organic thin film transistor (OTFT), a Schottky diode, a thermoelectric device, or an LC window.

19. An optoelectronic device comprising a compound according to any one of claims 1 to 8, or a composition according to any one of claims 9 to 14, and selected from an organic light emitting diode (OLED), an organic light emitting transistor (OLET), an organic light emitting electrochemical cell (OLEC), an organic photovoltaic device (OPV), an organic photodetector (OPD), an organic solar cell, a dye sensitized solar cell (DSSC), a perovskite solar cell (PSC), an organic photoelectrochemical cell (OPEC), a laser diode, a photoconductor, or a photodetector.

20. A component comprising a compound according to any one of claims 1 to 8 or a composition according to any one of claims 9 to 14, the component being selected from a charge injection layer, a charge transport layer, an intermediate layer, a planarizing layer, an antistatic film, a polymer electrolyte membrane (PEM), a conductive substrate, or a conductive pattern.

21. An assembly comprising a compound according to any one of claims 1 to 8, or a composition according to any one of claims 9 to 14, selected from an integrated circuit (IC), a radio frequency identification (RFID) tag, a security mark, a security device, a flat panel display, a backlight for a flat panel display, an electrophotographic device, an electrophotographic recording device, an organic memory device, a sensor device, a biosensor, or a biochip.

Images