Compounds

Abstract

A compound of formula (I) or (II): A1-(B1) x1-(D1) y1-(B1) x2-A1 (I) A1-(B2) x5-(D2) y2-(B3) x3-A2-(B3) x4-(D3) y3-(B2) x6-A1 (II) A2 is a divalent heteroaromatic electron accepting group; d1, D2 and D3 are independently at each occurrence an electron donating group; b1, B2 and B3 are independently in each occurrence a bridging group; x < 1-x > 6 are each independently 0, 1, 2 or 3; y1, y2, and y3 are each independently at least 1; and A1 is independently at each occurrence a group of formula (III) wherein J is C = O, C = S, S = O, SO2, NR11 or CR12R13, each Z1 is N and each Z2 is CR4, or each Z1 is CR4 and each Z2 is N, where each R4 is independently H or a substituent: # imgabs0 #

Description

Background Art

[0001] Embodiments of the present disclosure relate to electron accepting compounds, and more particularly to compounds suitable for use as electron accepting materials in photoresponsive devices.

[0002] Organic photodetectors may contain a photoactive layer of a blend of electron donating and electron accepting materials between the anode and cathode. Known electron accepting materials include fullerenes and non-fullerene acceptors (NFAs).

[0003] Yang et al., “End-capped group manipulation of indacenodithienothiophene-based non-fullerene small molecule acceptors for efficient organic solar cells” Nanoscale, 2020, 12, 17795-17804 discloses non-fullerene acceptor ITICs with a series of fused ring end groups for solar cells.

[0004] Wang et al., “Enhancement of intra- and inter-molecular π-conjugate deffects for anon-fullerene acceptor to achieve high-efficiency organic solar cells with an extended photoresponse range and optimized morphology”, Mater. Chem. Front., 2018, 2, 2006-2012 discloses an A–D–A type non-fullerene electron acceptor for solar cells, which has an electron-donating (D) core constructed by connecting a 2,5-difluorobenzene ring to two cyclopentadithiophene moieties and two electron-accepting (A) end groups of 2-(3-oxo-2,3-dihydro-1H-cyclopenta[b]naphthalene-1-ylidene)malononitrile.

[0005] Swick et al., "Fluorinatingπ-Extended Molecular Acceptors Yields Highly Connected Crystal Structures and Low Reorganization Energies for Efficient Solar Cells" discloses compounds ITN-F4 and ITzN-F4 for solar cells:

[0006]

[0007] Wu et al., “New Electron Acceptor with End-Extended Conjugation for High-Performance Polymer Solar Cells”, Energy Fuels 2021, 35, 23, 19061–19068 discloses compound IDTT8-N for solar cells:

[0008]

[0009] Li et al., "Systematic Merging of Nonfullerene Acceptorπ-Extension and Tetrafluorination Strategies Affords Polymer Solar Cells with>16% Efficiency" discloses nonfullerene acceptors BT-BIC, LIC, L4F and BO-L4F for solar cells:

[0010] Summary of the invention

[0011] The present disclosure provides a compound of formula (I) or (II):

[0012] A 1 –(B 1 )x 1 –(D 1 )y 1 –(B 1 )x 2 –A 1

[0013] (I)

[0014] A 1 –(B 2 )x 5 –(D 2 )y 2 –(B 3 )x 3 –A 2 –(B 3 )x 4 –(D 3 )y 3 –(B 2 )x 6 –A 1

[0015] (II)

[0016] in:

[0017] A 2 It is a divalent heteroaromatic electron-accepting group;

[0018] D 1 , D 2 and D 3 is independently at each occurrence an electron donating group;

[0019] B 1 , B 2 and B 3 is independently at each occurrence a bridging group;

[0020] x 1 -x 6 Each independently is 0, 1, 2 or 3;

[0021] y 1 -y 3 Each independently is at least 1;

[0022] A 1 is independently at each occurrence a group of formula (III):

[0023]

[0024] in:

[0025] Each R 1 are independently substituents;

[0026] R 2 is H or a substituent;

[0027] Each R 3 are independently H or a substituent;

[0028] J is C=O, S=O, SO 2 、C=S、NR 11 or CR 12 R 13 , where R 11 CN or COOR 40 And R 40 is H or a substituent, and R 12 and R 13 CN, CF, and 3 or COOR 40 ;as well as

[0029] Either each Z 1 is N and each Z 2 CR 4 , or each Z1 CR 4 And each Z 2 is N, where each R 4 is independently H or a substituent.

[0030] Optionally, each R 1 Independently selected from CN, CF 3 and COOR 40 , where R 40 At each occurrence, R is H or a substituent. 40 Preferably H or C 1-20 Hydrocarbyl group.

[0031] Optionally, each R 3 It is an electron withdrawing group.

[0032] Optionally, the electron withdrawing group is selected from Cl, F, CN, C 1-12 Fluoroalkyl and COOR 15 , where R 15 C 1-20 Hydrocarbyl group.

[0033] Optionally, each R 4 are independently selected from H or an electron withdrawing group.

[0034] The present disclosure provides a composition comprising an electron donating material and an electron accepting material, wherein the electron accepting material is a compound according to any one of the preceding claims.

[0035] The present disclosure provides an organic electronic device comprising an active layer, wherein the active layer comprises a compound or composition as described herein.

[0036] Optionally, the organic electronic device is an organic photoresponsive device comprising a bulk heterojunction layer disposed between an anode and a cathode, and wherein the bulk heterojunction layer comprises a composition as described herein.

[0037] Optionally, the organic electro-photoresponsive device is an organic photodetector.

[0038] The present disclosure provides a photosensor comprising a light source and an organic photodetector as described herein, wherein the photosensor is configured to detect light emitted from the light source.

[0039] Optionally, the light source emits light having a peak wavelength greater than 900 nm.

[0040] The present disclosure provides a formulation comprising a compound or composition as described herein dissolved or dispersed in one or more solvents.

[0041] The present disclosure provides a method of forming an organic electronic device as described herein, wherein the formation of the active layer comprises depositing a formulation as described herein onto a surface and evaporating the one or more solvents. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] The disclosed technology and accompanying drawings describe some implementations of the disclosed technology.

[0043] Figure 1 depicts an organic photoresponsive device according to some embodiments;

[0044] Figure 2 is a graph showing the relationship between wavelength and extinction coefficient for a toluene solution of compound example 1 and a toluene solution of comparative compound 1;

[0045] Figure 3 is a graph showing the relationship between wavelength and normalized absorption for the film of compound example 1 and the film of comparative compound 1;

[0046] Figure 4 is a graph of external quantum efficiency (EQE) versus wavelength for OPD device Example 1 in which the only acceptor is Compound Example 1 and for OPD device Example 2 in which the acceptors are Compound Example 1 and PCBM;

[0047] Figure 5 is a graph of the relationship between the external quantum efficiency (EQE) and wavelength for the OPD comparison device 2 containing the comparison compound 1 and PCBM; and

[0048] Figure 6 Dark currents at a reverse bias of -3 V are shown for an OPD device containing Compound Example 1 and for an OPD device containing Comparative Compound 1.

[0049] The accompanying drawings are not drawn to scale and have different viewpoints and perspectives. The accompanying drawings are some implementations and examples. In addition, for the purpose of discussing some embodiments of the disclosed technology, some components and / or operations may be divided into different blocks or combined into a single block. In addition, although the present technology can be subjected to various modifications and alternative forms, specific embodiments are shown by way of example in the accompanying drawings and are described in detail below. However, its purpose is not to limit the technology to the specific implementation described. On the contrary, the present technology is intended to cover all modifications, equivalents and alternatives that fall within the technical scope defined by the appended claims. DETAILED DESCRIPTION

[0050] Unless the context clearly requires otherwise, throughout the specification and claims, the words "comprise", "comprising", etc. should be interpreted as inclusive, rather than exclusive or exhaustive; that is, meaning "including but not limited to". In addition, when used in this application, the words "in this article", "above", "below" and words of similar meaning refer to the application as a whole rather than any particular part of the application. Where the context permits, the words in the detailed embodiments using the singular or plural may also include the plural or singular, respectively. The word "or" about a list of two or more items covers all the following interpretations of the word: any item in the list, all items in the list, and any combination of items in the list. When used in this application, a layer "above" another layer means that the layers can be in direct contact or there can be one or more intermediate layers. When used in this application, a layer "on another layer" means that the layers are in direct contact. Unless otherwise expressly stated, a reference to a specific atom includes any isotope of the atom.

[0051] The teachings of the technology provided herein can be applied to other systems, and need not be applied to the system described below. The elements and actions of the various examples described below can be combined to provide further implementations of the technology. Some alternative implementations of the technology can include not only the additional elements of those implementations mentioned below, but also fewer elements.

[0052] These and other changes can be made to the technology according to the detailed description below. Although this specification describes certain examples of the technology and describes the best mode contemplated, no matter how detailed the specification appears, the technology can be practiced in a variety of ways. As mentioned above, specific terms used when describing certain features or aspects of the technology should not be considered to imply that the terms are redefined herein to be limited to any specific characteristics, features, or aspects of the technology associated with the terms. In general, the terms used in the claims below should not be interpreted as limiting the technology to the specific examples disclosed in the specification unless the specific implementation section explicitly defines these terms. Therefore, the actual scope of the technology covers not only the disclosed examples, but also all equivalent ways of practicing or implementing the technology under the claims.

[0053] To reduce the number of claims, certain aspects of the technology are presented below in certain claim forms, but the applicant contemplates the various aspects of the technology in any number of claim forms.

[0054] In the following description, for the purpose of explanation, numerous specific details are set forth in order to provide a thorough understanding of the implementation of the disclosed technology. However, it is apparent to one skilled in the art that the embodiments of the disclosed technology can be practiced without some of these specific details.

[0055] Formula (I) and (II) are

[0056] A 1 –(B 1 )x 1 –(D 1 )y 1 –(B 1 )x 2 –A 1

[0057] (I)

[0058] A 1 –(B 2 )x 5 –(D 2 )y 2 –(B 3 )x 3 –A 2 –(B 3 )x 4 –(D 3 )y 3 –(B 2 )x 6 –A 1

[0059] (II)

[0060] A 1 It is a monovalent electron-accepting group.

[0061] A 2 It is a divalent heteroaromatic electron-accepting group.

[0062] D 1 , D 2 and D 3 is independently at each occurrence an electron donating group.

[0063] B 1 , B 2 and B 3 is independently at each occurrence a bridging group.

[0064] x 1 -x 6 Each independently is 0, 1, 2 or 3, preferably 0 or 1.

[0065] x 1 and x 2They are preferably the same, and are preferably both 0 or both 1.

[0066] x 3 and x 4 They are preferably the same, and are preferably both 0 or both 1, and more preferably both 0.

[0067] x 5 and x 6 They are preferably the same, and are preferably both 0 or both 1.

[0068] y 1 ,y 2 and 3 Each independently is at least 1, preferably 1, 2 or 3. 2 and 3 Preferably the same.

[0069] Electron acceptor group A 1 , A 2 and A 3 Each of the compounds of formula (I) has an electron-donating group D 1 , D 2 or D 3 The lowest unoccupied molecular orbital (LUMO) energy level of any of the LUMO deeper (i.e., away from vacuum), preferably at least 1 eV deep. The LUMO energy levels of electron accepting groups and electron donating groups can be determined by modeling the LUMO energy levels of these groups, wherein each bond to an adjacent group is replaced by a bond to a hydrogen atom. Gaussian09 software obtained using Gaussian (Gaussian) is used to model using Gaussian09 with B3LYP (functional) and LACVP * (basis set).

[0070] A 1 is independently at each occurrence a group of formula (III):

[0071]

[0072] Each R 1 Preferably, each R 1 Independently selected from CN; C 1-6 Fluoroalkyl, preferably CF 3 ; and COOR 40 , where R 40 Each occurrence is H or a substituent, preferably H or C 1-20 Hydrocarbyl group.

[0073] The C described in this paper 1-20 The hydrocarbyl group may be selected from phenyl which may be unsubstituted or substituted with one or more selected from C 1-12 Alkyl and linear, branched or cyclic C1-20 The alkyl group is substituted with a substituent.

[0074] R 2 is H or a substituent. Preferably, R 2 H, F, Cl, CN, NO 2 , C 1-16 Alkyl or C 1-16 Alkoxy, where C 1-16 Alkyl or C 1-16 One or more H atoms of the alkoxy group may be replaced by F.

[0075] Each R 3 are independently H or a substituent, preferably an electron withdrawing group. Preferred electron withdrawing groups are F, Cl, CN, C 1-12 Fluoroalkyl and COOR 15 , where R 15 C 1-20 Hydrocarbyl group.

[0076] J is C=O, C=S, S=O, SO 2 NR 11 or CR 12 R 13 , where R 11 , R 12 and R 13 As mentioned above, J is preferably C=O.

[0077] Either (i) each Z 1 is N and each Z 2 CR 4 , or (b) for each Z 1 CR 4 And each Z 2 is N, where each R 4 R is independently H or a substituent, preferably H or an electron-withdrawing group. 4 Preferably selected from 3 Electron withdrawing groups as described.

[0078] Preferably, the group of formula (III) has formula (IIIa):

[0079]

[0080] Exemplary groups of formula (III) include, but are not limited to:

[0081]

[0082] In some embodiments, the compound of formula (I) or (II) has an absorption peak greater than 900 nm, optionally greater than 1100 nm, optionally greater than 1250 nm. The absorption peak is suitably less than 1500 nm.

[0083] The present inventors unexpectedly discovered that a group A having formula (III) 1 The compound of formula (I) or (II) may have a low dark current.

[0084] Receptor unit A 2

[0085] A 2 Preferred are fused heteroaromatic groups comprising at least 2 fused rings, preferably at least 3 fused rings.

[0086] In some embodiments, formula (II) A 2 is a group of formula (VIII):

[0087]

[0088] in:

[0089] Ar 1 is an aromatic or heteroaromatic group; and

[0090] Y is O, S, NR 6 or R 7 -C=CR 7 , where R 7 is independently H or a substituent at each occurrence, wherein two substituents R 7 can be linked to form a single ring or multiple rings; and R 6 is H or a substituent.

[0091] In A 2 In the case of a group of formula (VIII), Ar 1 may be unsubstituted or substituted with one or more R 9 A monocyclic or polycyclic heteroaromatic group substituted by a group, wherein R 9 is independently at each occurrence a substituent.

[0092] Preferred R 9 The group is selected from

[0093] F;

[0094] CN;

[0095] NO 2 ;

[0096] C 1-20 Alkyl, in which one or more non-adjacent C atoms may be replaced by O, S, NR 17 Replace, where R17 C 1-12 Hydrocarbyl, COO or CO, and one or more H atoms of the alkyl may be replaced by F;

[0097] An aromatic or heteroaromatic group, preferably a phenyl group, which is unsubstituted or substituted with one or more substituents; and a group selected from the following:

[0098]

[0099] Where Z 40 , Z 41 , Z 42 and Z 43 Each independently is CR 13 or N, where R 13 Each occurrence is H or a substituent, preferably C 1-20 Hydrocarbyl group; Y 40 and Y 41 Each independently is O, S, NX 71 , where X 71 CN or COOR 40 ; or CX 60 X 61 , where X 60 and X 61 Independently for CN, CF 3 or COOR 40 ; W 40 and W 41 Each independently is O, S, NX 71 or CX 60 X 61 , where X 60 and X 61 Independently for CN, CF 3 or COOR 40 ; and, R 40 Each occurrence is H or a substituent, preferably H or C 1-20 Hydrocarbyl groups. Exemplary substituents R for aromatic or heteroaromatic groups 9 F, CN, NO 2 and C 1-12 Alkyl, in which one or more non-adjacent C atoms may be replaced by O, S, NR 7 , COO or CO, and one or more H atoms of the alkyl group may be replaced by F.

[0100] R as described anywhere herein 17 It can be, for example, C 1-12 Alkyl, unsubstituted phenyl; or phenyl, which is replaced by one or more C 1-6 Alkyl substitution.

[0101] If a C atom of an alkyl group as described anywhere herein is replaced by another atom or group, the replaced C atom may be a terminal C atom or a non-terminal C atom of the alkyl group.

[0102] A "non-terminal C atom" of an alkyl group as used anywhere herein means a C atom other than a C atom of a methyl group at the end of a normal alkyl chain or a C atom of a methyl group at the end of a branched alkyl chain.

[0103] If a terminal C atom of a group as described anywhere herein is replaced, the resulting group may be an anionic group comprising a countercation, for example an ammonium or metal countercation, preferably an ammonium or alkali metal cation.

[0104] A C atom of an alkyl substituent which is replaced by another atom or group as described anywhere herein is preferably a non-terminal C atom, and the resulting substituent group is preferably non-ionic.

[0105] Exemplary monocyclic heteroaromatic groups Ar 1 The preferred oxadiazoles are oxadiazoles, thiadiazoles, triazoles and 1,4-oxadiazoles which are unsubstituted or substituted by one or more substituents. Thiadiazoles are particularly preferred.

[0106] Exemplary polycyclic heteroaromatic groups Ar 1 A group of formula (V):

[0107]

[0108] X 1 and X 2 Each independently selected from N and CR 10 , where R 10 is H or a substituent, optionally H or a substituent R as described above 9 .

[0109] X 3 , X 4 , X 5 and X 6 Each independently selected from N and CR 10 , the condition is X 3 , X 4 , X 5 and X 6 At least one of them is CR 10 .

[0110] Z is selected from O, S, SO 2 NR 6 , PR 6 , C(R 10 ) 2 、Si(R 10 )2 C=O, C=S and C=C(R 5 ) 2 , where R 10 As mentioned above; R 6 is H or a substituent; R 5 Each time it occurs it is an electron withdrawing group.

[0111] Optionally, any NR described anywhere herein 6 or PR 6 Each R 6 Independently selected from H; C 1-20 Alkyl, in which one or more non-adjacent C atoms other than the C atom bonded to N or P may be replaced by O, S, NR 7 , COO or CO, and one or more H atoms of the alkyl group may be replaced by F. And phenyl, which is unsubstituted or substituted by one or more substituents, optionally one or more C 1-12 Alkyl groups are substituted, where one or more non-adjacent C atoms may be replaced by O, S, NR 7 , COO or CO, and one or more H atoms of the alkyl group may be replaced by F.

[0112] Preferably, each R 5 CN, COOR 40 ; or CX 60 X 61 , where X 60 and X 61 Independently for CN, CF 3 or COOR 40 , and R 40 Each occurrence is H or a substituent, preferably H or C 1-20 Hydrocarbyl group.

[0113] Formula (VIII) A 2 The group is preferably selected from the group consisting of the formulae (VIIIa) and (VIIIb):

[0114]

[0115] For the compound of formula (VIIIb), the two R 7 The groups may or may not be linked.

[0116] Preferably, when the two R 7 When the groups are not connected, each R 7 Independently selected from H; F; CN; NO 2 ; C 1-20 Alkyl, in which one or more non-adjacent C atoms may be replaced by O, S, NR 7 、CO、COO、NR6 , PR 6 or Si(R 10 ) 2 Substitution, where R 10 and R 6 As described above and one or more H atoms may be replaced by F. And aryl or heteroaryl, preferably phenyl, which is unsubstituted or substituted by one or more substituents. The substituents of aryl or heteroaryl may be selected from one or more of the following: F; CN; NO 2 ; and C 1-20 Alkyl, in which one or more non-adjacent C atoms may be replaced by O, S, NR 7 , CO or COO, and one or more H atoms of the alkyl group may be replaced by F.

[0117] Preferably, when the two R 7 When the group is attached, the group of formula (VIIIb) has the formula (VIIIb-1) or (VIIIb-2):

[0118]

[0119] Ar 2 is an aromatic or heteroaromatic group, preferably benzene, which is unsubstituted or substituted by one or more substituents. 2 may be unsubstituted or substituted with one or more substituents R as described above 2 replaced.

[0120] X is selected from O, S, SO 2 NR 6 , PR 6 , C(R 10 ) 2 、Si(R 10 ) 2 C=O, C=S and C=C(R 5 ) 2 , where R 10 , R 6 and R 5 As mentioned above.

[0121] Exemplary electron accepting groups of formula (VIII) include, but are not limited to:

[0122]

[0123]

[0124] Among them, Ak 1 C 1-20 Alkyl group.

[0125] A divalent electron accepting group other than formula (VIII) 2 Optionally selected from formula (IVa) to (IVj)

[0126]

[0127]

[0128] Y A1 It is O or S, preferably S.

[0129] R 23 At each occurrence is a substituent, optionally C 1-12 Alkyl, except for the one attached to Z 3 One or more non-adjacent C atoms other than the C atom of 6 , COO or CO, and one or more H atoms of the alkyl group may be replaced by F.

[0130] R 25 H; F; CN; NO independently at each occurrence 2 ; C 1-12 Alkyl, in which one or more non-adjacent C atoms may be replaced by O, S, NR 6 , COO or CO, and one or more H atoms of the alkyl group may be replaced by F. The aromatic group is optionally phenyl, which is unsubstituted or substituted by one or more selected from F and C 1-12 Alkyl is substituted with a substituent, wherein one or more non-adjacent C atoms may be substituted with O, S, NR 6 , COO or CO; or

[0131]

[0132] Where Z 40 , Z 41 , Z 42 and Z 43 Each independently is CR 13 or N, where R 13 Each occurrence is H or a substituent, preferably C 1-20 Hydrocarbyl groups;

[0133] Y 40 and Y 41 Each independently is O, S, NX 71 , where X 71 CN or COOR 40 ; or CX 60 X 61 , where X 60 and X 61 Independently for CN, CF 3 or COOR40 ;

[0134] W 40 and W 41 Each independently is O, S, NX 71 , where X 71 CN or COOR 40 ; or CX 60 X 61 , where X 60 and X 61 Independently for CN, CF 3 or COOR 40 ;as well as

[0135] R 40 At each occurrence, H or a substituent, preferably H or C 1-20 Hydrocarbyl group.

[0136] Z 3 N or P.

[0137] T 1 、T 2 and T 3 Each independently represents an aryl or heteroaryl ring, optionally benzene, which may be fused to one or more other rings. 1 、T 2 and T 3 The substituents (if present) are optionally selected from R 25 In a preferred embodiment, T 3 It is benzothiadiazole.

[0138] R 12 Each occurrence is a substituent, preferably C 1-20 Hydrocarbyl group.

[0139] Ar 5 is an arylene or heteroarylene group, optionally thiophene, fluorene or phenylene, which may be unsubstituted or substituted by one or more substituents, optionally one or more selected from R 25 substituted with non-H groups.

[0140] Bridge unit

[0141] Bridge unit B 1 , B 2 and B 3 Preferably each is selected from vinylene, arylene, heteroarylene, arylenevinylene and heteroarylenevinylene, wherein arylene and heteroarylene are monocyclic or bicyclic groups, each of which may be unsubstituted or substituted by one or more substituents.

[0142] Optionally, B1 , B 2 and B 3 Selected from units of formula (VIa)-(VIn):

[0143]

[0144] Where R 55 is H or a substituent; R 8 is independently H or a substituent at each occurrence, preferably H or a substituent selected from F; CN; NO 2 ; C 1-20 Alkyl, in which one or more non-adjacent C atoms may be replaced by O, S, NR 6 , COO or CO, and one or more H atoms of the alkyl group may be replaced by F. Phenyl, which is unsubstituted or substituted by one or more substituents; and -B(R 14 ) 2 , where R 14 At each occurrence is a substituent, optionally C 1-20 A hydrocarbon group. R of formula (VIa), (VIb) and (VIc) 8 The groups may be linked to form a bicyclic ring, for example thienopyrazine.

[0145] R 8 Preferably, hydrogen, C 1-20 Alkyl or C 1-19 Alkoxy.

[0146] Electron donating group D 1 , D 2 and D 3

[0147] The electron donating group is preferably a fused aromatic or heteroaromatic group, more preferably a fused heteroaromatic group containing three or more rings. Particularly preferred electron donating groups include fused thiophene or furan rings, optionally fused rings containing a thiophene or furan ring and one or more rings selected from benzene, cyclopentadiene, tetrahydropyran, tetrahydrothiopyran and piperidine rings, each of which is unsubstituted or substituted with one or more substituents.

[0148] Exemplary electron donating groups D 1 , D 2 and D 3 Includes groups of formula (VIIa)-(VIIp):

[0149]

[0150]

[0151] Among them, Y A O, S or NR independently at each occurrence 55 , Y A1O or S independently at each occurrence; X A C or Si; Z A O, CO, S, NR at each occurrence 55 or C(R 54 ) 2 ; R 51 , R 52 , R 54 and R 55 is independently H or a substituent at each occurrence; R 53 is independently a substituent at each occurrence; and Ar 4 is an optionally substituted monocyclic or condensed heteroaromatic group.

[0152] Optionally, R 51 and R 52 is independently selected at each occurrence from: H; F; C 1-20 Alkyl, in which one or more non-adjacent C atoms may be replaced by O, S, NR 7 , COO or CO, and one or more H atoms of the alkyl group may be replaced by F. As well as aromatic and heteroaromatic groups Ar 3 , which is unsubstituted or substituted with one or more substituents.

[0153] In some embodiments, Ar 3 It may be an aromatic group, such as phenyl.

[0154] Ar 4 Preferably, it is selected from the group consisting of optionally substituted oxadiazoles, thiadiazoles, triazoles and 1,4-diazines. 4 In the case of 1,4-diazines, the 1,4-diazines may be fused to other heterocyclic groups, groups optionally selected from optionally substituted oxadiazoles, thiadiazoles, triazoles, 1,4-diazines and succinimides.

[0155] Ar 3 The one or more substituents (if present) may be selected from C 1-12 Alkyl, in which one or more non-adjacent C atoms may be replaced by O, S, NR 7 , COO or CO, and one or more H atoms of the alkyl group may be replaced by F.

[0156] Preferably, each R 54 Selected from the group consisting of:

[0157] H;

[0158] F;

[0159] Straight chain, branched chain or cyclic C 1-20 Alkyl, in which one or more non-adjacent C atoms may be replaced by O, S, NR7 , CO or COO, where R 17 C 1-12 Hydrocarbon and the C 1-20 One or more H atoms of the alkyl group may be replaced by F; and

[0160] Formula (Ak)u–(Ar 7 )v, wherein Ak is C 1-20 Alkylene chains in which one or more non-adjacent C atoms may be replaced by O, S, NR 7 , CO or COO; u is 0 or 1; Ar 7 is independently at each occurrence an aromatic or heteroaromatic group that is unsubstituted or substituted with one or more substituents; and v is at least 1, optionally 1, 2 or 3.

[0161] Ar 7 The substituents (if present) are preferably selected from: F; Cl; NO 2 ; CN; and C 1-20 Alkyl, in which one or more non-adjacent C atoms may be replaced by O, S, NR 7 , CO or COO, and one or more H atoms of the alkyl group may be replaced by F. Preferably, Ar 7 It is phenyl.

[0162] Preferably, each R 51 For H.

[0163] Optionally, R 53 Select C at each occurrence 1-20 Alkyl, in which one or more non-adjacent C atoms may be replaced by O, S, NR 7 , COO or CO, and one or more H atoms of the alkyl group may be replaced by F; and phenyl, which is unsubstituted or substituted by one or more substituents, optionally one or more C 1-12 Alkyl groups are substituted, wherein one or more non-adjacent C atoms may be replaced by O, S, NR 7 , COO or CO, and one or more H atoms of the alkyl group may be replaced by F.

[0164] Preferably, R as described anywhere herein 55 H or C 1-30 Hydrocarbyl group.

[0165] In a preferred embodiment, D 1 , D 2 and D 3 Each is independently a group of formula (VIIa). Exemplary groups of formula (VIIa) include, but are not limited to:

[0166]

[0167] where Hc is independently C at each occurrence 1-20 Hydrocarbyl groups, such as C 1-20 Alkyl, unsubstituted aryl or substituted with one or more C 1-12 Alkyl substituted aryl group. The aryl group is preferably phenyl.

[0168] In some embodiments, y of formula (I) 1 is 1.

[0169] In some embodiments, y of formula (II) 2 and 3 Each is 1.

[0170] In some embodiments, y of formula (I) 1 Or y of formula (II) 2 and 3 At least one of D is greater than 1. In these embodiments, D 1 , D 2 or D 3 The chains of groups can be connected in any orientation. 1 is a group of formula (VIIa) and y 1 When it is 2, –[D 1 ] y1 -Can be selected from any of the following:

[0171]

[0172] Exemplary compounds of formula (I) include, but are not limited to:

[0173]

[0174]

[0175] Electron Donating Materials

[0176] The bulk heterojunction layer described herein comprises an electron donating material and a compound of formula (I) as described herein.

[0177] Exemplary donor materials are disclosed, for example, in WO 2013 / 051676, the contents of which are incorporated herein by reference.

[0178] The electron donating material may be a non-polymeric material or a polymeric material.

[0179] In a preferred embodiment, the electron donating material is an organic conjugated polymer, which may be a homopolymer or a copolymer, including alternating, random or block copolymers. The conjugated polymer is preferably a donor-acceptor polymer comprising alternating electron donating repeating units and electron accepting repeating units.

[0180] Preferred are non-crystalline or semi-crystalline conjugated organic polymers.

[0181] Further preferably, the electron donating polymer is a conjugated organic polymer having a low band gap, typically between 2.5 eV and 1.5 eV, preferably between 2.3 eV and 1.8 eV.

[0182] Optionally, the HOMO energy level of the electron donating polymer is no more than 5.5 eV from the vacuum energy level. Optionally, the HOMO energy level of the electron donating polymer is at least 4.1 eV from the vacuum energy level. As exemplary electron donating polymers, polymers selected from conjugated hydrocarbons or heterocyclic polymers can be mentioned, including polyacenes, polyanilines, polyazulenes, polybenzofurans, polyfluorenes, polyfurans, polyindenofluorenes, polyindoles, polyphenylenes, polypyrazolines, polypyrenes, polypyridazines, polypyridines, polytriarylamines, poly(phenylene vinylenes), poly(3-substituted thiophenes), poly(3,4-disubstituted thiophenes), polyselenophenes, poly(3-substituted selenophenes), poly(3,4-disubstituted thiophenes), polyselenophenes, poly(3-substituted selenophenes), poly(3,4-disubstituted thiophenes), polyselenophenes, poly(3-substituted selenophenes), poly(3,4-disubstituted thiophenes), polyselenophenes, poly(3,4-disubstituted thiophenes), polyselenophenes, poly(3,4-disubstituted thiophenes), polyselenophenes, poly(3,4-disubstituted thiophenes), polyselenophenes, poly(3,4-disubstituted thiophenes), polyselenophenes, polyselenophenes ... ,4-disubstituted selenophene), poly(bithiophene), poly(terthiophene), poly(diselenophene), poly(triselenophene), polythieno[2,3-b]thiophene, polythieno[3,2-b]thiophene, polybenzothiophene, polybenzo[1,2-b:4,5-b']dithiophene, polyisothianaphthene, poly(monosubstituted pyrrole), poly(3,4-disubstituted pyrrole), poly-1,3,4-oxadiazole, polyisothianaphthene, and their derivatives and copolymers.

[0183] Preferred examples of the donor polymer are copolymers of polyfluorene and polythiophene (each of which may be substituted), and polymers comprising benzothiadiazolyl and thiophene repeating units (each of which may be substituted).

[0184] Particularly preferred donor polymers comprise donor units (VIIa) provided as repeating units of the polymer, most preferably with electron accepting repeating units, such as divalent electron accepting units A as described herein provided as polymerized repeating units 1 .

[0185] Another particularly preferred donor polymer comprises repeating units of formula (X):

[0186]

[0187] Where R 18 and R 19 Each independently selected from: H; F; C 1-12An alkyl group in which one or more non-adjacent non-terminal C atoms may be replaced by O, S, COO or CO, and one or more H atoms of the alkyl group may be replaced by F; or an aromatic or heteroaromatic group Ar 6 , which is unsubstituted or substituted with one or more selected from F and C 1-12 The alkyl radical is substituted wherein one or more non-adjacent, non-terminal C atoms may be replaced by O, S, COO or CO.

[0188] The donor polymer is preferably a donor-acceptor (DA) copolymer comprising a donor repeat unit (eg a repeat unit of formula (VIIa) or (X)) and an acceptor repeat unit.

[0189] Organic Electronic Devices

[0190] The compound of formula (I) or (II) may be provided as an active layer of an organic electronic device. In a preferred embodiment, a bulk heterojunction layer of an organic photoresponsive device, more preferably an organic photodetector, comprises a composition as described herein.

[0191] The bulk heterojunction layer comprises or consists of an electron donating material as described herein and an electron accepting compound of formula (I) or formula (II).

[0192] In some embodiments, the bulk heterojunction layer contains two or more accepting materials and / or two or more electron accepting materials.

[0193] In some embodiments, the weight ratio of the electron donating material to the electron accepting material is from about 1:0.5 to about 1:2, preferably from about 1:1.1 to about 1:2.

[0194] Preferably, the electron donating material and the electron accepting material have a type II interface, i.e., the HOMO and LUMO energy levels of the electron donating material are shallower than the corresponding HOMO and LUMO energy levels of the electron accepting material. Preferably, the HOMO energy level of the compound of formula (I) or (II) is at least 0.05 eV deeper than the HOMO of the electron donating material, optionally at least 0.10 eV deeper.

[0195] Optionally, the gap between the HOMO energy level of the electron donating material and the LUMO energy level of the electron accepting compound of formula (I) or (II) is less than 1.4 eV.

[0196] Unless otherwise stated, the HOMO and LUMO levels of materials as described herein are measured by square wave voltammetry (SWV).

[0197] Figure 1An organic photoresponsive device according to some embodiments of the present disclosure is shown. The organic photoresponsive device includes a cathode 103, an anode 107, and a bulk heterojunction layer 105 disposed between the anode and the cathode. The organic photoresponsive device may be supported on a substrate 101, optionally a glass or plastic substrate.

[0198] Each of the anode and cathode may independently be a single conductive layer or may include multiple layers.

[0199] At least one of the anode and cathode is transparent so that light incident on the device can reach the bulk heterojunction layer. In some embodiments, both the anode and cathode are transparent. The transmittance of the transparent electrode can be selected according to the emission wavelength of the light source used with the organic photodetector.

[0200] Figure 1 An arrangement is shown in which the cathode is disposed between the substrate and the anode. In other embodiments, the anode may be disposed between the cathode and the substrate.

[0201] Organic photoresponsive devices may include Figure 1 In some embodiments, the work function modification layer is disposed between the bulk heterojunction layer and the anode, and / or between the bulk heterojunction layer and the cathode.

[0202] The area of ​​the OPD can be less than about 3 cm 2 , less than about 2cm 2 , less than about 1cm 2 , less than about 0.75cm 2 , less than about 0.5cm 2 or less than about 0.25 cm 2 Optionally, each OPD may be part of an OPD array, wherein each OPD is a PD having an area as described herein, optionally less than 1 mm 2 area, optionally at 0.5 μm 2 Up to 900μm 2 The pixels within the range of the array.

[0203] The substrate may be, but is not limited to, a glass or plastic substrate. The substrate may be an inorganic semiconductor. In some embodiments, the substrate may be silicon. For example, the substrate may be a silicon wafer. If, in use, incident light is to be projected through the substrate and the electrodes supported by the substrate, the substrate is transparent.

[0204] The bulk heterojunction layer contains a compound of formula (I) or (II) described herein and an electron donating compound. The bulk heterojunction layer may consist of these materials or may include one or more other materials, such as one or more other electron donating materials and / or one or more other electron accepting compounds.

[0205] Fullerene

[0206] In some embodiments, as described herein, the compound of formula (I) or (II) is the only electron-accepting material of a bulk heterojunction layer.

[0207] In some embodiments, the bulk heterojunction layer contains a compound of formula (I) or (II) and one or more additional electron accepting materials. Preferred additional electron accepting materials are fullerenes. The inventors unexpectedly discovered that the combination of a compound of formula (I) or (II) and fullerenes can enhance the external quantum efficiency of the OPD with little or no increase in dark current.

[0208] The weight ratio of the compound of formula (I) or (II): fullerene acceptor may be in the range of about 1:0.1 to 1:1, preferably in the range of about 1:0.1 to 1:0.5. The fullerene may be selected from, but not limited to, C 60 , C 70 , C 76 , C 78 and C 84 Fullerene or its derivatives, including but not limited to: PCBM type fullerene derivatives, including phenyl-C 61 -Methyl butyrate (C 60 PCBM); TCBM-type fullerene derivatives (e.g., tolyl-C 61 -Methyl butyrate (C 60 TCBM)); and ThCBM-type fullerene derivatives (e.g., thienyl-C 61 -Methyl butyrate (C 60 ThCBM).

[0209] The fullerene derivative may have formula (V):

[0210]

[0211] wherein A together with the CC group of the fullerene forms a monocyclic or condensed ring group, which may be unsubstituted or substituted by one or more substituents.

[0212] Exemplary fullerene derivatives include formula (Va), (Vb) and (Vc):

[0213]

[0214] Where R 20 -R32 Each is independently H or a substituent.

[0215] Substituent R 20 -R 32 is optionally and independently selected at each occurrence from the group consisting of: aryl or heteroaryl, optionally phenyl, which may be unsubstituted or substituted with one or more substituents; and C 1-20 Alkyl, in which one or more non-adjacent C atoms may be replaced by O, S, NR 7 , CO or COO, and one or more H atoms of the alkyl group may be replaced by F.

[0216] The substituents of the aryl or heteroaryl groups, if present, are optionally selected from C 1-12 Alkyl, in which one or more non-adjacent C atoms may be replaced by O, S, NR 7 , CO or COO, and one or more H atoms may be replaced by F.

[0217] Preparation

[0218] The bulk heterojunction layer may be formed by any process including but not limited to thermal evaporation and solution deposition methods.

[0219] Preferably, the bulk heterojunction layer is formed by depositing a formulation comprising an electron donating material, an electron accepting material, and any other components of the bulk heterojunction layer dissolved or dispersed in a solvent or a mixture of two or more solvents. The formulation can be deposited by any coating or printing method, including but not limited to spin coating, dip coating, roller coating, spray coating, doctor blade coating, wire rod coating, slot coating, inkjet printing, screen printing, gravure printing, and flexographic printing.

[0220] The one or more solvents of the formulation may optionally include a solvent selected from fluorine, chlorine, C 1-10 Alkyl and C 1-10 Benzene or naphthalene substituted with or consisting of one or more substituents of an alkoxy group, wherein two or more substituents may be linked to form a ring which may be unsubstituted or substituted with one or more C 1-6 Alkyl group-substituted, optionally toluene, xylene, trimethylbenzene, tetramethylbenzene, anisole, indan and alkyl-substituted derivatives thereof, and tetralin and alkyl-substituted derivatives thereof.

[0221] The formulation may include a mixture of two or more solvents, preferably a mixture of at least one benzene substituted with one or more substituents as described above and one or more additional solvents. The one or more additional solvents may be selected from esters, optionally alkyl or aryl esters of alkyl or aryl carboxylic acids, optionally benzoic acid C 1-10Alkyl esters, benzyl benzoate or dimethoxybenzene. In a preferred embodiment, a mixture of trimethylbenzene and benzyl benzoate is used as the solvent. In other preferred embodiments, a mixture of trimethylbenzene and dimethoxybenzene is used as the solvent.

[0222] In addition to the electron accepting material, the electron donating material and the one or more solvents, the formulation may also contain additional components. As examples of such components, adhesives, defoamers, degassing agents, viscosity enhancers, diluents, adjuvants, flow improvers, colorants, dyes or pigments, sensitizers, stabilizers, nanoparticles, surface active compounds, lubricants, wetting agents, dispersants and pH formulations may be mentioned.

[0223] application

[0224] The circuit may include an OPD connected to a voltage source for applying a reverse bias to the device and / or a device configured to measure photocurrent. The voltage applied to the photodetector may be variable. In some embodiments, the photodetector may be continuously biased when in use.

[0225] In some embodiments, the photodetector system includes a plurality of photodetectors as described herein, such as an image sensor of a camera.

[0226] In some embodiments, the sensor may include an OPD as described herein and a light source, wherein the OPD is configured to receive light emitted from the light source. In some embodiments, the light source has a peak wavelength of at least 900nm or at least 1000nm, optionally in the range of 900nm to 1500nm.

[0227] In some embodiments, the light from the light source may or may not be altered before reaching the OPD. For example, the light may be reflected, filtered, down-converted, or up-converted before reaching the OPD.

[0228] The organic photoresponsive device described herein may be an organic photovoltaic device or an organic photodetector. The organic photodetector as described herein may be used in a wide range of applications, including but not limited to detecting the presence and / or brightness of ambient light, and for sensors comprising an organic photodetector and a light source. The photodetector may be configured so that light emitted from a light source is incident on the photodetector, and changes in the wavelength and / or brightness of the light may be detected, such as due to absorption, reflection and / or emission of light by an object (e.g., a target material in a sample disposed in the light path between the light source and the organic photodetector). The sample may be a non-biological sample, such as a water sample, or a biological sample taken from a human or animal subject. The sensor may be, but is not limited to, a gas sensor, a biosensor, an X-ray imaging device, an image sensor such as a camera image sensor, a motion sensor (e.g., for security applications), a proximity sensor, or a fingerprint sensor. A 1D or 2D photosensor array may include a plurality of photodetectors as described herein in an image sensor. The photodetector may be configured to detect light emitted from a target analyte that emits light when illuminated by a light source, or in combination with a luminescent tag that emits light when illuminated by a light source. The photodetector may be configured to detect wavelengths of light emitted by the target analyte or a luminescent tag bound to the target analyte.

[0229] Examples

[0230] Example 1

[0231] The group of formula (III-1) can be formed according to the following reaction scheme:

[0232]

[0233] Step 1:

[0234] 1 (250 g, 1.06 mol) was dissolved in 2.5 L of dichloroethane. N-bromosuccinimide (754 g, 4.24 mol) was added to the reaction mixture in batches and heated at 75 ° C for 16 hours. Solid impurities were filtered out and washed with heptane. The filtrate was concentrated in vacuo to give 255 g of crude material. Product 2 was used in the next step without further purification.

[0235] Step 2:

[0236] 2 (99.9 g, 434 mmol) and 3 (55 g, 310 mmol) were dissolved in 1 L of ethanol. p-Toluenesulfonic acid (4.69 g, 24.7 mmol) was added to the reaction mixture and heated at 68°C for 3 hours. The reaction was then concentrated in vacuo to give 105 g of crude product, which was purified by column chromatography using dichloromethane to give 80 g of the desired product.

[0237] Step 3:

[0238] 4 (50 g, 134 mmol) was dissolved in 500 mL of methanol. Lithium hydroxide monohydride (12.9 g, 308 mmol) was added to the reaction mixture and stirred at room temperature for 16 hours. The reaction mixture was filtered and the resulting solid was stirred in dilute hydrochloric acid for 3 hours. The solid was filtered to obtain 30 g of the desired product 5.

[0239] Step 4:

[0240] 5 (30 g, 104 mmol) and acetic anhydride (600 mL) were combined in a flask. The reaction mixture was heated at 130° C. for 6 hours. Thereafter, it was cooled and concentrated under reduced pressure to give 30 g of crude product 6, which was used directly in the next step without further purification.

[0241] Step 5

[0242] Triethylamine (11.2 g, 111 mmol) was added to a stirred solution of 6 (30 g, 111 mmol) in acetic anhydride (240 mL). Tert-butyl acetoacetate (18.3 g, 116 mmol) was added dropwise thereto. The reaction mixture was stirred at room temperature for 16 hours, and then slowly poured into another flask containing 1.5 N hydrochloric acid (400 mL) and 400 mL ice water. It was then stirred at room temperature for 48 hours. The obtained solid was separated by filtration to obtain 15 g of the desired product 7 as a black solid, which was used in the next step without further purification.

[0243] Step 6

[0244] 7 (5 g, 18.7 mmol) was dissolved in pyridine (90 mL). Malononitrile (3.08 g, 46.7 mmol) was added thereto, and the mixture was stirred at room temperature for 2 hours. The reaction was concentrated under reduced pressure to give 9 g of crude material, which was purified by neutral alumina column chromatography using dichloromethane and 1% triethylamine in methanol. The resulting product was ground with hexane / dichloromethane and filtered to give 2.013 g of pure III-1 product (98.81% by HPLC) as a triethylamine salt.

[0245] Example 2

[0246] The group of formula (III-2) can be formed according to the following reaction scheme:

[0247]

[0248] Example 3

[0249] The group of formula (III-3) can be formed according to the following reaction scheme:

[0250]

[0251] Step 1

[0252] Same as III-1.

[0253] Step 2

[0254] 3 (150 g, 564 mmol) and 2 (181 g, 789 mmol) were dissolved in ethanol (2.5 L). p-Toluenesulfonic acid monohydrate (8.57 g, 45.1 mmol) was added to the reaction mixture and heated at 65 °C for 4 hours. Then, it was concentrated under vacuum to give 390 g of crude product 4, which was used in the next step without further purification.

[0255] Step 3

[0256] 4 (330 g, 717 mmol) was dissolved in 3 L of methanol. Lithium monohydride hydroxide (68.8 g, 1.64 mol) dissolved in 250 mL of water was added dropwise thereto. The obtained solid was filtered and stirred with 1.5 N HCl solution (2 L) for 3 hours. The precipitate was isolated by filtration, washed with 2 L of water and dried under vacuum to obtain 220 g of pure substance 5 as an off-white solid.

[0257] Step 4

[0258] 5 (150 g, 398 mmol) was dissolved in acetic anhydride (1.5 L, 14.6 mmol). The reaction mixture was heated at 130 °C for 16 h. After completion, the reaction mixture was concentrated under vacuum to afford 125 g of 6, which was used in the next step after further purification.

[0259] Step 5

[0260] 6 (50 g, 139 mmol) and acetic anhydride (50 g, 139 mmol) were mixed and cooled to 0 ° C. Triethylamine (20 mL, 0.197 mmol) was added, followed by tert-butyl acetoacetate (16.8 g, 145 mmol), and the reaction mixture was stirred at room temperature for 16 hours. Thereafter, the mixture was concentrated under reduced pressure and stirred with 1.5N hydrochloric acid (480 mL) and water (1920 mL) for 3 days. After completion, the mixture was filtered to give 35 g of the desired product 7. LCMS indicated a purity of 60%, and the material was then used in the next step.

[0261] Step 6

[0262] 7 (30 g, 84.2 mmol) was dissolved in toluene (1 L), and ethane-1,2-diol (104 g, 1.68 mol) and p-toluenesulfonic acid (3.19 g, 16.8 mmol) were added. The reaction mixture was heated to 135 ° C for 16 hours. During this period, water was frequently removed using a Dean-Stark apparatus. After completion, the mixture was cooled to room temperature and filtered through a celite bed, washed with ethyl acetate and then water, dried over sodium sulfate and concentrated in vacuo to give 38 g of crude product 8.

[0263] Step 7

[0264] Potassium hexacyanoferrate (III) (4.93 g, 13.4 mmol), 1-butylimidazole (2.91 g, 23.5 mmol) and cuprous (I) iodide (1.27 g, 6.71 mmol) were added to a solution of 8 (5 g, 11.2 mmol) in o-xylene (150 mL). The reaction mixture was heated at 148 ° C for 24 hours. Thereafter, potassium hexacyanoferrate (0.74 g), copper iodide (0.2 g) and 1-butylimidazole (0.46 mL) were added, and the mixture was further heated to 148 ° C for 24 hours. After completion, the mixture was cooled to room temperature and filtered through a celite pad, and the filtrate was washed with water and extracted with ethyl acetate. The organic phase was dried over sodium sulfate and concentrated in vacuo to obtain 7 g of crude intermediate. Further purification by column chromatography using ethyl acetate and hexane mixtures gave 3.5 g of the desired product 9 as a yellow solid.

[0265] Step 8

[0266] 9 (3 g, 8.92 mmol) was dissolved in trifluoroacetic acid (21 mL). The reaction mixture was heated at 40 °C for 3 hours. It was then concentrated in vacuo at 30 °C to give crude 10 with 50% of the desired product by LCMS, which was used as is in the next step.

[0267] Step 9

[0268] To a solution of malononitrile (0.304 g, 4.61 mmol) and sodium acetate (9.18 g, 112 mmol) in ethanol (120 mL) was added 10 (1.5 g, 5.13 mmol) dissolved in 250 mL of ethanol. The reaction mixture was stirred at room temperature for 3 hours and then concentrated in vacuo to give a crude product. The crude product was purified by column chromatography using a dichloromethane / methanol solvent system. The obtained product was suspended in ethyl acetate and stirred for 30 minutes, and filtered to give 0.5 g of a dark solid III-3 product (purity 88%).

[0269] Compound Example 1

[0270] Compound Example 1 can be formed according to the following reaction scheme:

[0271]

[0272] Compounds 2-4 were formed as shown in Table 1. Comparative compounds 2-4 are also shown.

[0273] Table 1

[0274]

[0275]

[0276]

[0277] Measurement method

[0278] The HOMO and LUMO energy levels were measured by square wave voltammetry (SWV).

[0279] In SWV, the current at the working electrode is measured while the potential between the working electrode and the reference electrode is swept linearly in time. The difference current between the forward and reverse pulses is plotted as a function of potential to produce a voltammogram. The measurement can be performed using a CHI 660D potentiostat.

[0280] The equipment for measuring HOMO or LUMO energy levels by SWV included a cell containing 0.1 M tert-butylammonium hexafluorophosphate in acetonitrile; a 3 mm diameter glassy carbon working electrode; a platinum counter electrode and a leak-free Ag / AgCl reference electrode.

[0281] Ferrocene was added directly to the existing cell at the end of the experiment for calculation purposes, where the oxidation and reduction potentials of ferrocene with respect to Ag / AgCl were determined using cyclic voltammetry (CV).

[0282] The sample was dissolved in toluene (3 mg / ml) and spun directly onto the glassy carbon working electrode at 3000 rpm.

[0283] LUMO = 4.8 - E Ferrocene (peak-to-peak average) - E Sample reduction (peak maximum).

[0284] HOMO = 4.8 - E ferrocene (average value between peaks) + E sample oxidation (peak maximum).

[0285] A typical SWV experiment was run at 15 Hz frequency; 25 mV amplitude and 0.004 V increment step size. For HOMO and LUMO data, results were calculated from 3 freshly spun film samples.

[0286] Absorption spectra were measured using a Cary 5000 UV-VIS-NIR spectrometer. Measurements were made from 175 nm to 3300 nm using an extended photometric range PbSmart NIR detector with variable slit width (down to 0.01 nm) to provide optimal control over data resolution.

[0287] Unless otherwise stated, absorbance values ​​are those of solutions. Absorption data is obtained by measuring the intensity of transmitted radiation through a sample of a solution. The absorption intensity is plotted against the incident wavelength to generate an absorption spectrum. A method for measuring absorption may include measuring a 15 mg / ml solution in a quartz cuvette and comparing it to a cuvette containing only solvent.

[0288] Unless otherwise stated, solution absorbance data presented herein were measured in toluene solutions.

[0289] Material Data

[0290] Referring to Table 2, the compound examples have longer peak absorption wavelengths than the corresponding comparative compounds.

[0291] Table 2

[0292] o-DCB: o-dichlorobenzene

[0293] TMB: 1,3,4-Trimethylbenzene

[0294] refer to Figure 2 , under the same absorption conditions, compound example 1 has a higher absorption intensity than comparative compound 1.

[0295] refer to Figure 3 And as shown in Table 1, the film of Compound Example 1 formed by spin coating from o-dichlorobenzene absorbs at about 1300 nm, which is about 150 nm longer than the film of Comparative Compound 1 formed by spin coating from toluene.

[0296] Device Example 1

[0297] A glass substrate coated with a 150 nm thick indium tin oxide (ITO) layer was coated with a 0.2% aqueous solution of polyethyleneimine (PEIE) to form a thin film of about 5 nm to modify the work function of ITO. A ca.500 nm thick bulk heterojunction layer of a mixture of donor polymer 1: compound example 1 (1:0.7 by weight) was deposited on the modified ITO layer by rod coating from a 10 mg / ml solution in o-dichlorobenzene / butyl benzoate solvent mixture (90:10 V / v). The MoO 3 ) and sputtering

[0298]

[0299] (ITO), MoO formed on the bulk heterojunction 3 Anode stack of (10nm) and ITO (50nm).

[0300]

[0301] Device Example 1A

[0302] A device was prepared as described in Device Example 1, except that the solution used to form the bulk heterojunction layer contained fullerene PCBM in addition to Donor Polymer 1 and Compound Example 1, and the weight ratio of Donor Polymer 1: Compound Example 1: PCBM was 1:0.7:0.3.

[0303] Comparison device 1

[0304] A device was prepared as described in Device Example 1A, except that Comparative Compound 1 was used instead of Compound Example 1.

[0305] refer to Figure 4 , the external quantum efficiency peaks at around 1300nm for device examples 1 and 1A. Including PCBM increases the EQE.

[0306] refer to Figure 5 , the EQE peak of comparison device 1 is around 900nm.

[0307] refer to Figure 6 , the dark current of device examples 1 and 2 at -3V reverse bias is much lower than that of comparative device 1.

[0308] Device Examples 2 to 4

[0309] The preparation method of device examples 2 to 4 is the same as that of device example 1A, except for the following:

[0310] - Compound Example 2 to 4 were used instead of Compound Example 1, respectively

[0311] -The solvents used to form the bulk heterojunction layer are shown in Table 3

[0312] - For Device Examples 2 and 4, the weight ratio of Donor Polymer 1: Compound Example: PCBM was 1:0.875:0.625. Comparative Devices 2 to 4 containing Comparative Compounds 2 to 4 were formed in the same manner as the corresponding Device Examples.

[0313] Table 3

[0314]

[0315] o-DCB: o-dichlorobenzene

[0316] BB: Butyl Benzoate

[0317] TMB: 1,3,4-Trimethylbenzene

[0318] DMOB: 1,2-dimethoxybenzene

[0319] 1-ClNp: 1-chloronaphthalene

[0320] simulation

[0321] The HOMO and LUMO energy levels of NFAs of formula (I) containing groups of formula (III) and comparative NFAs without groups of formula (III) were simulated. The results are listed in Table 4, where S1f corresponds to the oscillator strength (predicted absorption strength) of the transition from S1, and Eopt is the simulated optical gap.

[0322] NFAs containing electron-accepting end groups of formula (III) have smaller simulated band gaps and longer wavelength simulated optical gaps than NFAs containing relatively electron-accepting end groups.

[0323] Table 4

[0324]

[0325]

[0326]

[0327]

Claims

1. A compound of formula (I) or (II): A 1 –(B 1 )x 1 –(D 1 )y 1 –(B 1 )x 2 –A 1 (I) A 1 –(B 2 )x 5 –(D 2 )y 2 –(B 3 )x 3 –A 2 –(B 3 )x 4 –(D 3 )y 3 –(B 2 )x 6 –A 1 (II) in: A 2 It is a divalent heteroaromatic electron-accepting group; D 1 , D 2 and D 3 is independently at each occurrence an electron donating group; B 1 , B 2 and B 3 is independently at each occurrence a bridging group; x 1 -x 6 Each independently is 0, 1, 2 or 3; y 1 ,y 2 and 3 Each independently is at least 1; A 1 is independently at each occurrence a group of formula (III): in: Each R 1 are independently substituents; R 2 is H or a substituent; Each R 3 are independently H or a substituent; J is C=O, C=S, S=O, SO2, NR 11 or CR 12 R 13 , where R 11 CN or COOR 40 And R 40 is H or a substituent, and R 12 and R 13 Each independently is CN, CF3 or COOR 40 ;and Either each Z 1 is N and each Z 2 CR 4 , or each Z 1 CR 4 And each Z 2 is N, where each R 4 is independently H or a substituent.

2. The compound according to claim 1, wherein each Z 1 is N and each Z 2 CR 4 .

3. The compound according to claim 1, wherein each Z 2 is N and each Z 1 CR 4 .

4. A compound according to any one of the preceding claims, wherein each R 1 Independently selected from CN, CF3 and COOR 40 , where R 40 At each occurrence is H or a substituent.

5. A compound according to any one of the preceding claims, wherein each R 3 It is an electron withdrawing group.

6. The compound according to claim 5, wherein the electron withdrawing group is selected from Cl, F, CN, C 1-12 Fluoroalkyl and COOR 15 , where R 15 C 1-20 Hydrocarbyl group.

7. A compound according to any one of the preceding claims, wherein each R 4 are independently selected from H or an electron withdrawing group.

8. A composition comprising an electron donating material and an electron accepting material, wherein the electron accepting material is a compound according to any one of the preceding claims.

9. An organic electronic device comprising an active layer comprising a compound or composition according to any one of the preceding claims. 10 . The organic electronic device of claim 9 , wherein the organic electronic device is an organic photoresponsive device comprising a bulk heterojunction layer disposed between an anode and a cathode, and wherein the bulk heterojunction layer comprises the composition of claim 8 . The organic electronic device according to claim 10 , wherein the organic photoresponsive device is an organic photodetector. 12 . A photosensor comprising a light source and the organic photodetector according to claim 11 , wherein the organic photodetector is configured to detect light emitted from the light source.

13. The photosensor according to claim 12, wherein the light source emits light having a peak wavelength greater than 900 nm.

14. A formulation comprising a compound or composition according to any one of claims 1 to 8 dissolved or dispersed in one or more solvents.

15. A method of forming an organic electronic device according to any one of claims 9 to 11, wherein the formation of the active layer comprises depositing the formulation according to claim 14 onto a surface and evaporating the one or more solvents.

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