compound

Abstract

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) A 2 is a divalent heteroaromatic electron-accepting group, and D 1 , D 2 and D 3 is independently in each occurrence an electron donating group, B 1 , B 2 and B 3 is independently in each occurrence a bridging group, and x 1 ~x 6 are each independently 0, 1, 2 or 3; 1 , y 2 and y 3 are each independently at least 1, and A 1 is independently at each occurrence a group of formula (III), wherein J is C=O, C=S, S=O, SO, NR 11 or CR 12 R 13 and each Z 1 is N, and each Z 2 is CR 4 or each Z 1 is CR 4 and each Z 2 is N, where each R 4 are independently H or a substituent [Formula 1] TIFF2025537078000039.tif75170

Description

[Background technology]

[0001] FIELD OF THE DISCLOSURE 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 can contain a photoactive layer of a mixture of electron donating and electron accepting materials between an anode and a 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 a series of non-fullerene acceptors ITICs with fused ring end groups for solar cells.

[0004] Wang et al., "Enhancement of intra- and inter-molecular π-conjugated effects for a non-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 ADA-type non-fullerene electron acceptor for solar cells, which has an electron-donating (D) core constructed by linking a 2,5-difluorobenzene ring with two cyclopentadithiophene moieties and two electron-accepting (A) terminal groups of 2-(3-oxo-2,3-dihydro-1H-cyclopenta[b]naphthalen-1-ylidene)malononitrile.

[0005] Swick et al., "Fluorinating π-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. [ka]

[0006] 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. [ka]

[0007] Li et al., "Systematic Merging of Nonfullerene Acceptor π-Extension and Tetrafluorination Strategies Affords Polymer Solar Cells with >16% Efficiency," discloses nonfullerene acceptors BT-BIC, LIC, L4F, and BO-L4F for solar cells. [ka] Summary of the Invention

[0008] The present disclosure provides compounds of formula (I) or (II): A 1 -(B 1 )x1 -(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) During the ceremony, A 2 is a divalent heteroaromatic electron-accepting group, D 1 , D 2 and D 3 is independently in each occurrence an electron donating group; B 1 , B 2 and B 3 is independently in each occurrence a bridging group; x 1 ~x 6 are each independently 0, 1, 2 or 3; y 1 ~y 3 are each independently at least 1, A 1 is independently at each occurrence a group of formula (III), [ka] During the ceremony, 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, S=O, SO2, C=S, NR 11 or CR12 R 13 where R 11 CN or COOR 40 and R 40 is H or a substituent, and R 12 and R 13 are each independently CN, CF3 or COOR 40 and each Z 1 is N, and each Z 2 is CR 4 or each Z 1 is CR 4 and each Z 2 is N, where each R 4 are independently H or a substituent.

[0009] Optionally, each R 1 CN, CF3 and COOR 40 are independently selected from, where R 40 is H or a substituent at each occurrence. 40 is preferably H or C 1-20 It is a hydrocarbyl group.

[0010] Optionally, each R 3 is an electron-withdrawing group.

[0011] Optionally, the electron withdrawing group is Cl, F, CN, C 1-12 Fluoroalkyl and COOR 15 where R 15 is C 1-20 It is a hydrocarbyl group.

[0012] Optionally, each R 4 are independently selected from H or an electron withdrawing group.

[0013] 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.

[0014] The present disclosure provides organic electronic devices comprising an active layer comprising a compound or composition described herein.

[0015] Optionally, the organic electronic device is an organic photoresponsive device comprising a bulk heterojunction layer disposed between an anode and a cathode, the bulk heterojunction layer comprising a composition described herein.

[0016] Optionally, the organic photoresponsive device is an organic photodetector.

[0017] The present disclosure provides a light sensor including a light source and an organic photodetector as described herein, the light sensor configured to detect light emitted from the light source.

[0018] Optionally, the light source emits light having a peak wavelength greater than 900 nm.

[0019] The present disclosure provides formulations comprising a compound or composition described herein dissolved or dispersed in one or more solvents.

[0020] The present disclosure provides methods of forming the organic electronic devices described herein, wherein forming an active layer comprises depositing a formulation described herein onto a surface and evaporating one or more solvents.

[0021] The disclosed technology and the accompanying drawings illustrate several implementations of the disclosed technology. [Brief explanation of the drawings]

[0022] [Figure 1] 1 illustrates an organic photoresponsive device according to some embodiments. [Figure 2] 1 is a graph showing the wavelength versus extinction coefficient of a toluene solution of Compound Example 1 and a toluene solution of Comparative Compound 1. [Figure 3] 1 is a graph of normalized absorbance versus wavelength for a film of Compound Example 1 and a film of Comparative Compound 1. [Figure 4]1 is a graph of external quantum efficiency (EQE) versus wavelength for OPD Device Example 1, in which the acceptor is Compound Example 1 alone, and OPD Device Example 2, in which the acceptor is Compound Example 1 and PCBM. [Figure 5] 1 is a graph of external quantum efficiency (EQE) versus wavelength for OPD Comparative Device 2 containing Comparative Compound 1 and PCBM. [Figure 6] 1 shows the dark current at a reverse bias of −3 V of an OPD device containing Compound Example 1 and an OPD device containing Comparative Compound 1. DETAILED DESCRIPTION OF THE INVENTION

[0023] The drawings are not drawn to scale and have various perspectives and viewing angles. The drawings are of several implementations and examples. In addition, some components and / or operations may be separated into different blocks or combined into a single block for purposes of illustrating some of the embodiments of the disclosed technology. Furthermore, the technology is amenable to various modifications and alternative forms, and specific embodiments are shown by way of example in the drawings and described in detail below. However, the intention is not to limit the technology to the particular implementations described. On the contrary, the technology is intended to cover all modifications, equivalents, and alternatives falling within the scope of the technology as defined by the appended claims.

[0024] Unless the context clearly requires otherwise, throughout the specification and claims, words such as "comprise," "comprising," and the like, shall be construed in an inclusive sense, i.e., "including, but not limited to," as opposed to an exclusive or exhaustive sense. Furthermore, the words "herein," "above," "below," and words of similar import, when used in this application, refer to this application as a whole and not to particular portions of this application. Where the context permits, in the Detailed Description using the singular or plural, words may also include the plural or singular, respectively. The word "or" in connection with a list of two or more items encompasses all of the following interpretations of that word: any of the items in the list, all of the items in the list, and any combination of the items in the list. As used in this application, a reference to a layer "over" another layer means that the layers may be in direct contact or that there may be one or more intervening layers. As used in this application, a reference to a layer "on" another layer means that the layers are in direct contact. A reference to a particular atom includes any isotopes of that atom unless otherwise specified.

[0025] The teachings of the technology provided herein may be applied to other systems, not necessarily the systems described below. Elements and operations of various embodiments described below can be combined to provide further implementations of the technology. Some alternative implementations of the technology may include additional elements relative to those implementations described below, as well as fewer elements.

[0026] These and other changes can be made to the technology in light of the following detailed description. While this description describes particular examples of the technology and explains the best mode contemplated, no matter how detailed the description may appear, the technology can be practiced in many ways. As described above, a specific term used when describing a particular feature or aspect of the technology should not be construed as meaning that the term is redefined herein to be limited to any particular feature, characteristic, or aspect of the technology associated with that term. In general, the terms used in the following claims should not be construed as limiting the technology to the specific embodiments disclosed herein, unless such terms are otherwise expressly defined in the Detailed Description section. Thus, the actual scope of the technology encompasses not only the disclosed examples but also all equivalent ways of practicing or implementing the technology based on the claims.

[0027] In order to reduce the number of claims, certain aspects of the technology are presented below in particular claim forms, but applicant contemplates various aspects of the technology in any number of claim forms.

[0028] In the following description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of implementations of the disclosed technology. However, it will be apparent to one skilled in the art that embodiments of the disclosed technology may be practiced without some of these specific details.

[0029] Formulas (I) and (II) are as follows: 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 )x3 -A 2 -(B 3 )x 4 -(D 3 )y 3 -(B 2 )x 6 -A 1 (II)

[0030] A 1 is a monovalent electron-accepting group.

[0031] A 2 is a divalent heteroaromatic electron-accepting group.

[0032] D 1 , D 2 and D 3 is independently at each occurrence an electron donating group.

[0033] B 1 , B 2 and B 3 is independently at each occurrence a bridging group.

[0034] x 1 ~x 6 are each independently 0, 1, 2 or 3, preferably 0 or 1.

[0035] x 1 and x 2 are preferably the same, and preferably both 0 or both 1.

[0036] x 3 and x 4 are preferably the same, preferably both 0 or both 1, more preferably both 0.

[0037] x 5 and x 6 are preferably the same, and preferably both 0 or both 1.

[0038] y 1 , y 2 and y3 are each independently at least 1, preferably 1, 2, or 3. 2 and y 3 are preferably the same.

[0039] Electron-accepting group A 1 , A 2 and A 3 each of which is an electron donating group D of the compound of formula (I) 1 , D 2 or D 3 The electron-accepting and electron-donating groups have a lowest unoccupied molecular orbital (LUMO) level that is deeper (i.e., farther from vacuum) than the LUMO of either of the groups, preferably at least 1 eV deeper. The LUMO levels of the electron-accepting and electron-donating groups can be determined by modeling the LUMO levels of these groups where each bond to an adjacent group is replaced with a bond to a hydrogen atom. Modeling may be performed using Gaussian09 software available from Gaussian, using Gaussian09 with B3LYP (functional) and LACVP* (basis set).

[0040] A 1 is independently at each occurrence a group of formula (III), [ka]

[0041] Each R 1 are independently substituents. Preferably, each R 1 CN, C 1-6 Fluoroalkyl, preferably CF3, and COOR 40 (where R 40 is, at each occurrence, H or a substituent, preferably H or C 1-20 are independently selected from the group consisting of:

[0042] C as described herein 1-20 The hydrocarbyl group may be selected from phenyl, said phenyl being unsubstituted or C 1-12 Alkyl and straight-chain, branched or cyclic C 1-20It may be substituted with one or more substituents selected from alkyl.

[0043] R 2 is H or a substituent. Preferably, R 2 are H, F, Cl, CN, NO2, 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 may be replaced by F.

[0044] 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 is C 1-20 It is a hydrocarbyl group.

[0045] J is C=O, C=S, S=O, SO2, NR 11 or CR 12 R 13 where R 11 , R 12 and R 13 is as defined above. J is preferably C=O.

[0046] (i) Each Z 1 is N, and each Z 2 is CR 4 or (b) each Z 1 is CR 4 and each Z 2 is N, where each R 4 are independently H or a substituent, preferably H or an electron-withdrawing group. 4 is preferably R 3 The electron-withdrawing group is selected from those described for

[0047] Preferably, the group of formula (III) has the formula (IIIa): [ka]

[0048] Exemplary groups of formula (III) include, but are not limited to, the following: [ka]

[0049] In some embodiments, the compound of formula (I) or (II) has an absorption peak above 900 nm, optionally above 1100 nm, optionally above 1250 nm. The absorption peak is suitably below 1500 nm.

[0050] The inventors have surprisingly found that the group A of formula (III) 1 It has been found that compounds of formula (I) or (II) having the formula: may have low dark current.

[0051] Receptor unit A 2 A 2 is preferably a fused heteroaromatic group containing at least two fused rings, preferably at least three fused rings.

[0052] In some embodiments, A of formula (II) 2 is a group of formula (VIII): [ka] During the ceremony, Ar 1 is an aromatic or heteroaromatic group, and Y is O, S, NR 6 or R 7 -C=CR 7 where R 7 is independently in each occurrence H or a substituent, where two substituents R 7 may be linked to form a monocyclic or polycyclic ring, and R 6 is H or a substituent.

[0053] A 2is a group of formula (VIII), Ar 1 is unsubstituted or contains one or more R 9 group (where R 9 may be a monocyclic or polycyclic heteroaromatic group substituted with (which at each occurrence is independently a substituent).

[0054] Preferred R 9 The group is selected from F, CN, NO2, C 1-20 Alkyl (where one or more non-adjacent C atoms are O, S, NR 17 where R 17 is C 1~12 hydrocarbyl, COO or CO, and one or more H atoms of the alkyl may be replaced by F; an aromatic or heteroaromatic group, preferably phenyl, which may be unsubstituted or substituted with one or more substituents, and [ka] A group selected from In the formula, Z 40 , Z 41 , Z 42 , and Z 43 are each independently 13 or N and R 13 is, at each occurrence, H or a substituent, preferably C 1-20 is a hydrocarbyl group, and Y 40 and Y 41 are independently O, S, and NX 71 (where X 71 CN or COOR 40 ) or CX 60 X 61 (where X 60 and X 61 are independently CN, CF3 or COOR 40 ) and W 40 and W 41 are independently O, S, and NX 71 , or CX60 X 61 (where X 60 and X 61 are independently CN, CF3 or COOR 40 ) and R 40 is, at each occurrence, H or a substituent, preferably H or C 1-20 Aromatic or heteroaromatic group R is a hydrocarbyl group. 9 Exemplary substituents for are F, CN, NO, and C 1-12 alkyl, where one or more non-adjacent C atoms are O, S, NR 7 , COO or CO, and one or more H atoms of the alkyl may be replaced by F.

[0055] R as described elsewhere herein 17 For example, C 1-12 alkyl, unsubstituted phenyl, or one or more C 1-6 It may be a phenyl substituted with an alkyl group.

[0056] If a C atom of an alkyl group described anywhere in this specification is replaced with another atom or group, the replaced C atom may be a terminal C atom or a non-terminal C atom of the alkyl group.

[0057] The "non-terminal C atom" of an alkyl group as used anywhere in this specification means a C atom other than the C atom of the terminal methyl group of an n-alkyl chain or the C atom of the terminal methyl group of a branched alkyl chain.

[0058] When the terminal C atom of the groups 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.

[0059] A C-atom of an alkyl substituent that is replaced by another atom or group anywhere mentioned herein is preferably a non-terminal C-atom, and the resulting substituent is preferably non-ionic.

[0060] Exemplary monocyclic heteroaromatic groups Ar 1 are oxadiazoles, thiadiazoles, triazoles, and 1,4-diazines which are unsubstituted or substituted with one or more substituents. Thiadiazoles are particularly preferred.

[0061] Exemplary Polycyclic Heteroaromatic Groups Ar 1 is a group of formula (V): [ka]

[0062] X 1 and X 2 N and CR 10 are independently selected from 10 is H or a substituent, optionally H or the substituent R 9 is.

[0063] X 3 , X 4 , X 5 and X 6 is X 3 , X 4 , X 5 and X 6 At least one of the 10 N and CR, provided that 10 are each independently selected from

[0064] Z is O, S, SO2, NR 6 , PR 6 , C(R 10 )2, Si(R 10 )2C=O, C=S, and C=C(R 5 )2, where R 10 As mentioned above, R 6 is H or a substituent, and R 5 is an electron-withdrawing group in each occurrence.

[0065] Optionally, any NR described anywhere herein 6 or PR6 Each R 6 is H, C 1-20 Alkyl (wherein one or more non-adjacent C atoms other than the C atom bonded to N or P are O, S, NR 7 , COO or CO, and one or more H atoms of the alkyl may be replaced by F), and unsubstituted or one or more substituents, optionally one or more C 1-12 Phenyl substituted with alkyl groups, where one or more non-adjacent C atoms of the alkyl are O, S, NR 7 , COO, or CO, and one or more H atoms of the alkyl may be replaced by F).

[0066] Preferably, each R 5 CN, COOR 40 , or CX 60 X 61 (where X 60 and X 61 are independently CN, CF3 or COOR 40 and R 40 is, at each occurrence, H or a substituent, preferably H or C 1-20 is a hydrocarbyl group).

[0067] A in formula (VIII) 2 The group is preferably selected from groups of formula (VIIIa) and (VIIIb): [ka]

[0068] In the case of compounds of formula (VIIIb), two R 7 The groups may be bonded or unbonded.

[0069] Preferably, two R 7 When no groups are bonded, each R 7 are H, F, CN, NO2, C 1-20 Alkyl (where one or more non-adjacent C atoms are O, S, NR 7 , CO, COO, NR 6, PR 6 , or Si(R 10 )2, where R 10 and R 6 and aryl or heteroaryl, preferably phenyl, which may be unsubstituted or substituted with one or more substituents. Substituents for the aryl or heteroaryl groups are F, CN, NO, and C. 1-20 Alkyl (where one or more non-adjacent C atoms are O, S, NR 7 , CO, COO, and one or more H atoms may be replaced by F).

[0070] Preferably, two R 7 When the group is attached, the group of formula (VIIIb) has formula (VIIIb-1) or (VIIIb-2): [ka]

[0071] Ar 2 is an aromatic or heteroaromatic group, preferably benzene, which is unsubstituted or substituted with one or more substituents. 2 may be unsubstituted as above, or may contain one or more substituents R 2 may be substituted with.

[0072] X is O, S, SO2, NR 6 , PR 6 , C(R 10 )2, Si(R 10 )2C=O, C=S, and C=C(R 5 )2, where R 10 , R 6 and R 5 The above is as stated above.

[0073] Exemplary electron accepting groups of formula (VIII) include, but are not limited to: [ka] During the ceremony, Ak 1 is C 1~20 It is an alkyl group.

[0074] Divalent electron-accepting group A other than formula (VIII) 2 is arbitrarily selected from formulas (IVa) to (IVj): [ka]

[0075] Y A1 is O or S, preferably S.

[0076] R 23 represents, at each occurrence, a substituent, optionally C 1-12 Alkyl (where Z 3 At least one non-adjacent C atom other than the C atom bonded to is O, S, or NR 6 , COO, or CO, and one or more H atoms of the alkyl may be replaced by F).

[0077] R 25 are H, F, CN, NO2, and C independently at each occurrence. 1-12 Alkyl (where one or more non-adjacent C atoms are O, S, NR 6 , COO or CO, and one or more H atoms of the alkyl may be replaced by F), unsubstituted or F and C 1-12 Alkyl (where one or more non-adjacent C atoms are O, S, NR 6 an aromatic group substituted with one or more substituents selected from the group consisting of phenyl, COO, or CO; [ka] A group selected from In the formula, Z 40 , Z 41 , Z 42 , and Z 43 are each independently13 or N and R 13 is, at each occurrence, H or a substituent, preferably C 1-20 is a hydrocarbyl group, Y 40 and Y 41 are independently O, S, and NX 71 (where X 71 CN or COOR 40 ) or CX 60 X 61 (where X 60 and X 61 are independently CN, CF3 or COOR 40 ) and W 40 and W 41 are independently O, S, and NX 71 (where X 71 CN or COOR 40 ) or CX 60 X 61 (where X 60 and X 61 are independently CN, CF3 or COOR 40 ) and R 40 is, in each occurrence, H or a substituent, preferably H or C 1-20 It is a hydrocarbyl group.

[0078] Z 3 is N or P.

[0079] 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 further rings. 1 , T 2 , and T 3 The substituents, when present, are optionally R 25 In a preferred embodiment, the non-H group is selected from the group consisting of T 3 is a benzothiadiazole.

[0080] R at each occurrence 12is a substituent, preferably C 1-20 It is a hydrocarbyl group.

[0081] Ar 5 may be unsubstituted or may contain one or more substituents, optionally R 25 is an arylene or heteroarylene group, optionally substituted with one or more non-H groups selected from:

[0082] Crosslinking Unit Crosslinking unit B 1 , B 2 and B 3 are preferably each selected from vinylene, arylene, heteroarylene, arylenevinylene, and heteroarylenevinylene, each of which may be unsubstituted or substituted with one or more substituents, and wherein the arylene and heteroarylene groups are monocyclic or bicyclic groups.

[0083] Optionally, B 1 , B 2 and B 3 is selected from units of formulae (VIa) to (VIn): [ka] In the formula, R 55 is H or a substituent, and R 8 is independently at each occurrence H or a substituent, preferably H, or F, CN, NO, C 1-20 Alkyl (where one or more non-adjacent C atoms are O, S, NR 6 , COO or CO, and one or more H atoms of the alkyl may be replaced by F), phenyl which is unsubstituted or substituted with one or more substituents, and -B(R 14 )2(where R 14 represents, at each occurrence, a substituent, optionally C 1-20 R in formula (VIa), (VIb) and (VIc) is a substituent selected from the group consisting of aryl, ... 8The groups may be linked to form a bicyclic ring, for example a thienopyrazine.

[0084] R 8 is preferably H, C 1-20 Alkyl, or C 1-19 It is an alkoxy.

[0085] Electron-donating group D 1 , D 2 and D 3 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.

[0086] Exemplary Electron-Donating Groups D 1 , D 2 and D 3 contains groups of formulae (VIIa) to (VIIp): [ka] TIFF2025537078000019.tif114170, Y A represents independently at each occurrence O, S, or NR 55 and Y A1 is independently O or S in each occurrence, and X A is C or Si, and Z A is O, CO, S, NR at each occurrence. 55 or C(R 54 )2 and R 51 , R 52 , R 54 and R 55 is independently in each occurrence H or a substituent; R 53 is independently a substituent in each occurrence, and Ar 4is an optionally substituted monocyclic or fused heteroaromatic group.

[0087] Optionally, R 51 and R 52 H, F, C at each occurrence 1-20 Alkyl (where one or more non-adjacent C atoms are O, S, NR 7 , COO or CO, and one or more H atoms of the alkyl may be replaced by F), and an aromatic or heteroaromatic group Ar which is unsubstituted or substituted with one or more substituents. 3 are independently selected from

[0088] In some embodiments, Ar 3 may be an aromatic group, for example, phenyl.

[0089] Ar 4 is preferably selected from optionally substituted oxadiazoles, thiadiazoles, triazoles, and 1,4-diazines. 4 is a 1,4-diazine, the 1,4-diazine may be condensed with a further heterocyclic group, optionally a group selected from optionally substituted oxadiazole, thiadiazole, triazole, 1,4-diazine and succinimide.

[0090] Ar 3 When present, one or more of the substituents in 1-12 Alkyl (where one or more non-adjacent C atoms are O, S, NR 7 , COO or CO, and one or more H atoms of the alkyl may be replaced by F).

[0091] Preferably, each R 54 teeth, H, F, Linear, branched, or cyclic C 1-20 Alkyl (where one or more non-adjacent C atoms are O, S, NR 7 , CO or COO (wherein R17 is C 1-12 Hydrocarbyl, C 1-20 one or more H atoms of the alkyl may be replaced by F), and Formula (Ak)u-(Ar 7 )v group (where Ak is C 1-20 Alkylene chain (where one or more non-adjacent C atoms are O, S, NR 7 , may be replaced by CO or COO), u is 0 or 1, Ar 7 is independently selected at each occurrence from the group consisting of: an aromatic or heteroaromatic group that is unsubstituted or substituted with one or more substituents; and v is at least 1 and optionally 1, 2, or 3.

[0092] Ar 7 The substituents, when present, are F, Cl, NO, CN, and C 1-20 Alkyl (where one or more non-adjacent C atoms are O, S, NR 7 , optionally replaced by CO or COO, and one or more H atoms may be replaced by F). 7 is phenyl.

[0093] Preferably, each R 51 is H.

[0094] Optionally, R 53 At each occurrence, C 1-20 Alkyl (where one or more non-adjacent C atoms are O, S, NR 7 , COO or CO, and one or more H atoms of the alkyl may be replaced by F), and unsubstituted or with one or more substituents, optionally one or more C 1-12 Phenyl substituted with alkyl groups (wherein one or more non-adjacent C atoms are O, S, NR 7 , COO, or CO, and one or more H atoms of the alkyl may be replaced by F).

[0095] Preferably, R as described anywhere in this specification 55 is H or C 1-30 It is a hydrocarbyl group.

[0096] In a preferred embodiment, D 1 , D 2 and D 3 are each independently a group of formula (VIIa). Exemplary groups of formula (VIIa) include, but are not limited to: [ka] where Hc, independently at each occurrence, is C 1-20 Hydrocarbyl groups, such as C 1-20 alkyl, unsubstituted aryl, or one or more C 1-12 The aryl group is preferably phenyl.

[0097] In some embodiments, y in formula (I) 1 is 1.

[0098] In some embodiments, y in formula (II) 2 and y 3 are each 1.

[0099] In some embodiments, y in formula (I) 1 Or y in formula (II) 2 and y 3 At least one of D is greater than 1. 1 Base, D 2 Group or D 3 The chains of groups may each be attached in any orientation. For example, D 1 is a group of formula (VIIa), and y 1 If is 2, then -[D 1 ] y1 may be selected from any of the following: [ka]

[0100] Exemplary compounds of formula (I) include, but are not limited to, the following: [ka]

[0101] Electron-donating materials The bulk heterojunction layers described herein comprise an electron donating material and a compound of formula (I) described herein.

[0102] Exemplary donor materials are disclosed, for example, in WO2013 / 051676, the contents of which are incorporated herein by reference.

[0103] The electron donating material can be a non-polymeric or polymeric material.

[0104] In a preferred embodiment, the electron donating material is an organic conjugated polymer, which can be a homopolymer or a copolymer (including alternating, random, or block copolymers). The conjugated polymer is preferably a donor-acceptor polymer that comprises alternating electron donating and electron accepting repeat units.

[0105] Preferred are amorphous or semi-crystalline conjugated organic polymers.

[0106] More preferably, the electron donating polymer is a conjugated organic polymer with a low bandgap, typically between 2.5 eV and 1.5 eV, preferably between 2.3 eV and 1.8 eV.

[0107] Optionally, the electron donating polymer has a HOMO level 5.5 eV or less from the vacuum level. Optionally, the electron donating polymer has a HOMO level at least 4.1 eV from the vacuum level. Exemplary electron donating polymers include polyacenes, polyanilines, polyazulenes, polybenzofurans, polyfluorenes, polyfurans, polyindenofluorenes, polyindoles, polyphenylenes, polypyrazolines, polypyrenes, polypyridazines, polypyridines, polytriallylamines, poly(phenylene vinylenes), poly(3-substituted thiophenes), poly(3,4-disubstituted thiophenes), polyselenophenes, poly(3-substituted selenophenes), poly(3,4-disubstituted selenophenes), poly(bisthiophenes), poly(3- ... Mention may be made of polymers selected from conjugated hydrocarbon or heterocyclic polymers including poly(terthiophene), poly(bisselenophene), poly(terselenophene), 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, derivatives and copolymers thereof.

[0108] Preferred examples of the donor polymer are copolymers of polyfluorene and polythiophene, each of which may be substituted, and polymers containing benzothiadiazole-based and thiophene-based repeating units, each of which may be substituted.

[0109] Particularly preferred donor polymers include a donor unit (VIIa) provided as a repeat unit of the polymer, and most preferably an electron-accepting repeat unit, such as a divalent electron-accepting unit A as described herein, provided as a repeat unit of the polymer. 1 It has.

[0110] Another particularly preferred donor polymer comprises repeat units of formula (X): [ka] In the formula, R18 and R 19 are H, F, and C 1-12 alkyl (wherein 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 may be replaced by F), or unsubstituted or a mixture of F and C 1-12 an aromatic or heteroaromatic group Ar substituted with one or more substituents selected from alkyl (wherein one or more non-adjacent non-terminal C atoms may be replaced by O, S, COO or CO); 6 are each independently selected from

[0111] The donor polymer is preferably a donor-acceptor (DA) copolymer comprising donor repeat units, for example repeat units of formula (VIIa) or (X), and acceptor repeat units.

[0112] Organic Electronic Devices The compounds of formula (I) or (II) can be provided as an active layer in an organic electronic device. In a preferred embodiment, a bulk heterojunction layer of an organic photoresponsive device, more preferably an organic photodetector, comprises the composition described herein.

[0113] The bulk heterojunction layer comprises or consists of an electron donating material and an electron accepting compound of formula (I) or (II) described herein.

[0114] In some embodiments, the bulk heterojunction layer contains two or more acceptor materials and / or two or more electron-acceptor materials.

[0115] In some embodiments, the weight ratio of electron donor material(s) to electron acceptor material(s) is from about 1:0.5 to about 1:2, preferably from about 1:1.1 to about 1:2.

[0116] Preferably, the electron donor material has a type II interface with the electron acceptor material, i.e., the electron donor material has a HOMO and LUMO that are shallower than the corresponding HOMO and LUMO levels of the electron acceptor material. Preferably, the compound of formula (I) or (II) has a HOMO level that is at least 0.05 eV deeper, optionally at least 0.10 eV deeper, than the HOMO of the electron donor material.

[0117] Optionally, the gap between the HOMO level of the electron donating material and the LUMO level of the electron accepting compound of Formula (I) or (II) is less than 1.4 eV.

[0118] Unless otherwise specified, the HOMO and LUMO levels of the materials described herein are measured by square wave voltammetry (SWV).

[0119] 1 shows an organic photoresponsive device according to some embodiments of the present disclosure. The organic photoresponsive device comprises 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.

[0120] Each of the anode and cathode may independently be a single conductive layer or may include multiple layers.

[0121] At least one of the anode and cathode is transparent to allow light incident on the device to reach the bulk heterojunction layer. In some embodiments, both the anode and the cathode are transparent. The transmittance of the transparent electrode can be selected according to the emission wavelength of the light source for use with the organic photodetector.

[0122] 1 shows a configuration 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.

[0123] Organic photoresponsive devices may comprise layers other than the anode, cathode, and bulk heterojunction layer shown in Figure 1. In some embodiments, a hole transport layer is disposed between the anode and the bulk heterojunction layer. In some embodiments, an electron transport layer is disposed between the cathode and the bulk heterojunction layer. In some embodiments, a work function modifying layer is disposed between the bulk heterojunction layer and the anode and / or between the bulk heterojunction layer and the cathode.

[0124] The area of ​​the OPD is approximately 3 cm 2 Less than 2cm 2 Less than 1cm 2 Less than 0.75cm 2 Less than 0.5cm 2 Less than or about 0.25 cm 2 Optionally, each OPD may be part of an OPD array, and each OPD may have an area as described herein, optionally less than 1 mm 2 less than, optionally 0.5 microns 2 ~900 microns 2 are pixels of an array having an area in the range of

[0125] 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. A substrate is transparent if, in use, incident light is transmitted through the substrate and electrodes supported by the substrate.

[0126] The bulk heterojunction layer comprises a compound of Formula (I) or (II) described herein and an electron-accepting compound. The bulk heterojunction layer may consist of these materials or may comprise one or more additional materials, such as one or more additional electron-donating materials and / or one or more additional electron-accepting compounds.

[0127] fullerene In some embodiments, the compound of Formula (I) or (II) is the only electron-accepting material of the bulk heterojunction layer described herein.

[0128] In some embodiments, the bulk heterojunction layer comprises a compound of Formula (I) or (II) and one or more additional electron-accepting materials. A preferred additional electron-accepting material is a fullerene. The inventors have surprisingly discovered that the combination of a compound of Formula (I) or (II) and a fullerene can increase the external quantum efficiency of an OPD with little or no increase in dark current.

[0129] The weight ratio of the compound of formula (I) or (II) to the 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, but is not limited to, C 60 , C 70 , C 76 , C 78 and C 84 It may be selected from fullerenes or their derivatives, including but not limited to phenyl-C 61 -Butyric acid methyl ester (C 60 PCBM), TCBM-type fullerene derivatives (e.g., tolyl-C 61 -Butyric acid methyl ester (C 60 TCBM), and ThCBM-type fullerene derivatives (e.g., thienyl-C 61 -Butyric acid methyl ester (C 60 These include, but are not limited to, PCBM-type fullerene derivatives, including ThCBM.

[0130] The fullerene derivative may have the formula (V): [ka] wherein A together with the CC group of the fullerene forms a monocyclic or fused ring group which may be unsubstituted or substituted with one or more substituents.

[0131] Exemplary fullerene derivatives include those of formula (Va), (Vb), and (Vc): [ka] In the formula, R 20 ~R 32 are each independently H or a substituent.

[0132] Substituent R 20 ~R 32 optionally and independently, at each occurrence, represents aryl or heteroaryl, which may be unsubstituted or substituted with one or more substituents, optionally phenyl, and C 1-20 Alkyl (where one or more non-adjacent C atoms are O, S, NR 7 , CO or COO, and one or more H atoms may be replaced by F).

[0133] The aryl or heteroaryl substituents, when present, are optionally C 1-12 Alkyl (where one or more non-adjacent C atoms are O, S, NR 7 , CO or COO, and one or more H atoms may be replaced by F).

[0134] compound The bulk heterojunction layer can be formed by any process, including, but not limited to, thermal evaporation and solution deposition methods.

[0135] Preferably, the bulk heterojunction layer is formed by depositing a formulation comprising the electron donating material(s), the electron accepting material(s), 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 may be deposited by any coating or printing method, including, but not limited to, spin coating, dip coating, roll coating, spray coating, doctor blade coating, wire bar coating, slit coating, inkjet printing, screen printing, gravure printing, and flexographic printing.

[0136] One or more solvents of the formulation may optionally contain fluorine, chlorine, C 1-10 Alkyl and C 1-10 Alkoxy (wherein two or more substituents are linked together and are unsubstituted or one or more C 1-6 The alkyl group may form a ring which may be substituted with alkyl groups), optionally comprising benzene or naphthalene substituted with one or more substituents selected from toluene, xylene, trimethylbenzene, tetramethylbenzene, anisole, indane, and its alkyl-substituted derivatives, and tetralin and its alkyl-substituted derivatives.

[0137] The formulation may comprise a mixture of two or more solvents, preferably a mixture comprising at least one benzene substituted with one or more substituents as described above, and one or more further solvents, the one or more further solvents being esters, optionally alkyl, or aryl esters of alkyl or aryl carboxylic acids, optionally C 1-10 The solvent may be selected from alkyl benzoates, benzyl benzoate, or dimethoxybenzene. In a preferred embodiment, a mixture of trimethylbenzene and benzyl benzoate is used as the solvent. In another preferred embodiment, a mixture of trimethylbenzene and dimethoxybenzene is used as the solvent.

[0138] In addition to the electron-accepting material, the electron-donating material, and one or more solvents, the formulation may contain further components, such as adhesives, antifoaming agents, degassing agents, viscosity enhancers, diluents, adjuvants, flow improvers, colorants, dyes or pigments, sensitizers, stabilizers, nanoparticles, surface-active compounds, lubricants, wetting agents, dispersants, and inhibitors.

[0139] Purpose 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 the photocurrent. The voltage applied to the photodetector may be variable. In some embodiments, the photodetector may be continuously biased during use.

[0140] In some embodiments, the photodetector system includes multiple photodetectors described herein, for example, camera image sensors.

[0141] In some embodiments, a sensor may include an OPD described herein and a light source, where 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 900 nm or at least 1000 nm, optionally in the range of 900-1500 nm.

[0142] In some embodiments, the light from the light source may or may not be modified before reaching the OPD, for example, the light may be reflected, filtered, downconverted, or upconverted before reaching the OPD.

[0143] The organic photoresponsive devices described herein may be organic photovoltaic devices or organic photodetectors. The organic photodetectors described herein may be used in a wide range of applications, including, but not limited to, detecting the presence and / or intensity of ambient light, as well as in sensors comprising an organic photodetector and a light source. The photodetector may be configured such that light emitted from a light source is incident on the photodetector, and changes in the wavelength and / or intensity of the light can be detected, for example, due to absorption, reflection, and / or emission of light from a target material in an object, e.g., a sample, disposed in the optical path between the light source and the organic photodetector. The sample may be a non-biological sample, e.g., a water sample, or a biological sample collected from a human or animal subject. The sensor may be, but is not limited to, a gas sensor, a biosensor, an imaging sensor such as an X-ray imaging device or camera imaging sensor, a motion sensor (e.g., for use in security applications), a proximity sensor, or a fingerprint sensor. A 1D or 2D photo sensor array may comprise a plurality of the photodetectors described herein within an image sensor. The light detector may be configured to detect light emitted from a target analyte that emits light when illuminated by a light source or that is coupled to a light emitting tag that emits light when illuminated by a light source. The light detector may be configured to detect the wavelength of light emitted by the target analyte or its coupled light emitting tag. [Example]

[0144] Example 1 The group of formula (III-1) can be formed according to the following reaction scheme: [ka]

[0145] Step 1: 1 (250 g, 1.06 mol) was dissolved in 2.5 L of dichloroethane. N-Bromosuccinimide (754 g, 4.24 mol) was added portionwise to the reaction mixture, which was then heated at 75 °C for 16 h. The solid impurities were filtered and washed with heptane. The filtrate was concentrated in vacuo to give 255 g of crude material. The product 2 was used in the next step without further purification.

[0146] Step 2: 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, which was then heated at 68 °C for 3 h. 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.

[0147] Step 3: 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, which was then 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 give 30 g of the desired product 5.

[0148] Step 4: 5 (30 g, 104 mmol) and acetic anhydride (600 mL) were mixed in a flask. The reaction mixture was heated at 130° C. for 6 h. After this, 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.

[0149] Step 5 To a stirred solution of 6 (30 g, 111 mmol) in acetic anhydride (240 mL) was added triethylamine (11.2 g, 111 mmol). To this was added tert-butyl acetoacetate (18.3 g, 116 mmol). The reaction mixture was stirred at room temperature for 16 h and then slowly poured into a separate flask containing 1.5 N hydrochloric acid (400 mL) and 400 mL of ice water. This was then stirred at room temperature for 48 h. The resulting solid was isolated by filtration to give 15 g of the desired product 7 as a black solid, which was used in the next step without further purification.

[0150] Step 6 7 (5 g, 18.7 mmol) was dissolved in pyridine (90 ml). To this was added malononitrile (3.08 g, 46.7 mmol), 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 1% triethylamine in dichloromethane and methanol. The resulting product was triturated with hexane / dichloromethane and filtered to give 2.013 g of pure III-1 product (98.81% by HPLC) as the triethylamine salt.

[0151] Example 2 The group of formula (III-2) can be formed according to the following reaction scheme: [ka]

[0152] Example 3 The group of formula (III-3) can be formed according to the following reaction scheme: [ka]

[0153] Step 1 Same as III-1.

[0154] Step 2 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, which was heated at 65 °C for 4 h. It was then concentrated in vacuo to give 390 g of crude product 4, which was used in the next step without further purification.

[0155] Step 3 4 (330 g, 717 mmol) was dissolved in 3 L of methanol. To this was added lithium hydroxide monohydride (68.8 g, 1.64 mol) dissolved in 250 mL of water, dropwise. The resulting solid was filtered and stirred with 1.5 N HCl solution (2 L) for 3 h. The precipitate was isolated by filtration, washed with 2 L of water, and dried under vacuum to give 220 g of pure material 5 as an off-white solid.

[0156] Step 4 5 (150 g, 398 mmol) was placed in acetic anhydride (1.5 L, 14.6 mmol). The reaction mixture was heated at 130° C. for 16 h. Upon completion, the reaction mixture was concentrated in vacuo to give 125 g of 6, which was further purified and used in the next step.

[0157] Step 5 6 (50 g, 139 mmol) and acetic anhydride (50 g, 139 mmol) were combined 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 h. After this time, the mixture was concentrated under reduced pressure and stirred with 1.5 N hydrochloric acid (480 mL) and water (1920 mL) for 3 days. Upon completion, the mixture was filtered to give 35 g of the desired product 7. LCMS showed 60% purity, and this material was carried on to the next step.

[0158] Step 6 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 h, during which time water was removed frequently using a Dean-Stark apparatus. Upon completion, the mixture was cooled to room temperature, filtered through a bed of Celite, washed with ethyl acetate and then water, dried over sodium sulfate, and concentrated in vacuo to give 38 g of crude product 8.

[0159] Step 7 To a solution of 8 (5 g, 11.2 mmol) in o-xylene (150 mL) was added potassium hexacyanoferrate(III) (4.93 g, 13.4 mmol), 1-butylimidazole (2.91 g, 23.5 mmol), and copper(I) iodide (1.27 g, 6.71 mmol). The reaction mixture was heated at 148 °C for 24 h. After this time, 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 h. Upon completion, the mixture was cooled to room temperature, filtered through a pad of Celite, and the filtrate was washed with water and extracted with ethyl acetate. The organic phase was dried over sodium sulfate and concentrated under vacuum to give 7 g of the crude intermediate. This was further purified by column chromatography using a mixture of ethyl acetate and hexane to give 3.5 g of the desired product 9 as a yellow solid.

[0160] Step 8 9 (3 g, 8.92 mmol) was dissolved in trifluoroacetic acid (21 mL). The reaction mixture was heated at 40° C. for 3 h. It was then concentrated in vacuo at 30° C. to give crude material 10, which was 50% of the desired product by LCMS and used directly in the next step.

[0161] Step 9 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 dropwise 10 (1.5 g, 5.13 mmol) dissolved in 250 mL of ethanol. The reaction mixture was stirred at room temperature for 3 h and then concentrated in vacuo to give the crude product. The crude product was purified by column chromatography using a dichloromethane / methanol solvent system. The resulting product was suspended in ethyl acetate, stirred for 30 min, and filtered to give 0.5 g of product III-3 as a dark solid (88% purity).

[0162] Compound example 1 Compound example 1 can be formed according to the following reaction scheme: [ka]

[0163] Compounds 2-4 were formed as shown in Table 1. Comparative compounds 2-4 are also shown. [Table 1-1] [Table 1-2]

[0164] Measurement method The HOMO and LUMO levels were measured by square wave voltammetry (SWV).

[0165] In SWV, the potential between the working and reference electrodes is linearly swept over time while the current at the working electrode is measured. The difference in current between the forward and reverse pulses is plotted as a function of potential to produce a voltammogram. Measurements can be performed using a CHI 660D potentiostat.

[0166] The apparatus for measuring HOMO or LUMO energy levels by SWV includes a cell containing 0.1 M tertiary butylammonium hexafluorophosphate in acetonitrile, a 3 mm diameter glassy carbon working electrode, a platinum counter electrode, and a leak-tight Ag / AgCl reference electrode.

[0167] Ferrocene is added directly to the existing cell at the end of the experiment for calculation purposes, and the potential is determined using cyclic voltammetry (CV) for the oxidation and reduction of ferrocene versus Ag / AgCl.

[0168] The sample is dissolved in toluene (3 mg / ml) and spun at 3000 rpm directly onto a glassy carbon working electrode.

[0169] LUMO = 4.8 - E ferrocene (peak-to-peak average) - E reduced sample (peak maximum).

[0170] HOMO = 4.8 - E ferrocene (peak-to-peak average) + E oxidation of sample (peak maximum).

[0171] A typical SWV experiment is performed at a frequency of 15 Hz, an amplitude of 25 mV, and an incremental step of 0.004 V. Results are calculated from three freshly spun film samples for both HOMO and LUMO data.

[0172] Absorption spectra were measured using a Cary 5000 UV-VIS-NIR spectrometer from 175 nm to 3300 nm using a PbSmart NIR detector for an extended photometric range with variable slit widths (down to 0.01 nm) for optimal control of data resolution.

[0173] Unless otherwise stated, absorption values ​​are for solutions. Absorption data is obtained by measuring the intensity of radiation transmitted through a solution sample. The absorption intensity is plotted against the incident wavelength to generate an absorption spectrum. A method for measuring the absorption rate may involve measuring a 15 mg / ml solution in a quartz cuvette and comparing it to a cuvette containing only solvent.

[0174] Unless otherwise stated, the solution absorption data provided herein was measured in toluene solution.

[0175] Material Data Referring to Table 2, the example compounds have longer peak absorption wavelengths than the corresponding comparative compounds. [Table 2]

[0176] Referring to FIG. 2, Compound Example 1 has a higher absorption intensity than Comparative Compound 1 under the same absorption conditions.

[0177] Referring to FIG. 3, as shown in Table 1, a film of Compound Example 1 formed by spin coating from o-dichlorobenzene absorbs at about 1300 nm, which is about 150 nm longer than a film of Comparative Compound 1 formed by spin coating from toluene.

[0178] Device Example 1 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 5 nm-thick film that modified the work function of the ITO. A 500 nm-thick bulk heterojunction layer of a mixture of donor polymer 1 and compound example 1 (weight ratio 1:0.7) was deposited on the modified ITO layer by bar coating from a 10 mg / ml solution in a 90:10 v / v o-dichlorobenzene / butyl benzoate solvent mixture. An anode stack of MoO (10 nm) and ITO (50 nm) was formed on the bulk heterojunction by thermal evaporation (MoO) and sputtering (ITO). [ka]

[0179] Device Example 1A The device was prepared as described for 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 in a weight ratio of Donor Polymer 1:Compound Example 1:PCBM1:0.7:0.3.

[0180] Comparison Device 1 A device was prepared as described for Device Example 1A, except that Comparative Compound 1 was used instead of Compound Example 1.

[0181] 4, the external quantum efficiency of Device Examples 1 and 1A peaks at about 1300 nm. The inclusion of PCBM increases the EQE.

[0182] Referring to FIG. 5, the EQE of Comparative Device 1 peaks at about 900 nm.

[0183] Referring to FIG. 6, the dark currents of Device Examples 1 and 2 at a reverse bias of −3 V are much lower than that of Comparative Device 1.

[0184] Device examples 2-4 Device Examples 2-4 were prepared as described for Device Example 1A with the following exceptions: Compound examples 2 to 4 were used instead of compound example 1. The solvents used to form the bulk heterojunction layer are listed in Table 3. For device examples 2 and 4, the weight ratio of donor polymer 1: compound example: PCBM was 1:0.875:0.625

[0185] Comparative Devices 2-4, containing Comparative Compounds 2-4, were formed in the same manner as the corresponding device examples. [Table 3]

[0186] Modeling 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 modeled. The results are shown in Table 4, where S1f corresponds to the oscillator strength of the transition from S1 (predicting the absorption intensity) and Eopt is the modeled optical gap.

[0187] NFAs containing electron-accepting end groups of formula (III) have smaller modeled bandgaps and longer wavelength modeled optical gaps than NFAs containing comparable electron-accepting end groups. [Table 4-1] [Table 4-2] [Table 4-3]

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) During the ceremony, A ２ is a divalent heteroaromatic electron-accepting group, D １ , D ２ and D ３ is independently in each occurrence an electron donating group; B １ , B ２ and B ３ is independently in each occurrence a bridging group; x １ ~x ６ are each independently 0, 1, 2, or 3; y １ , y ２ and y ３ are each independently at least 1; A １ is independently at each occurrence a group of formula (III), 【Chemistry 1】 During the ceremony, 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, SO ２ , N.R. １１ or CR １２ R １３ where R １１ is CN or COOR ４０ and R ４０ is H or a substituent, and R １２ and R １３ are independently CN, CF ３ or COOR ４０ and Each Z １ is N, and each Z ２ is CR ４ or each Z １ is CR ４ and each Z ２ is N, where each R ４ are independently H or a substituent.

2. Each Z １ is N, and each Z ２ is CR ４ 2. The compound of claim 1, wherein:

3. Each Z ２ is N, and each Z １ is CR ４ 2. The compound of claim 1, wherein:

4. Each R １ CN, CF ３ and COOR ４０ where R ４０ 5. A compound according to any one of the preceding claims, wherein at each occurrence, is H or a substituent.

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

6. The electron-withdrawing group is Cl, F, CN, C １－１２ Fluoroalkyl and COOR １５ where R １５ is C １－２０ The compound of claim 5, which is a hydrocarbyl group.

7. Each R ４ is 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. 10. An organic electronic device comprising an active layer comprising a compound or composition according to any one of the preceding claims.

10. 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, the bulk heterojunction layer comprising the composition of claim 8.

11. The organic electronic device of claim 10 , wherein the organic photoresponsive device is an organic photodetector.

12. 12. A light sensor comprising: a light source; and the organic photodetector of claim 11, wherein the organic photodetector is configured to detect light emitted from the light source.

13. The optical sensor of 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. 12. A method for forming an organic electronic device according to any one of claims 9 to 11, wherein forming 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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