Photoresponsive asymmetric non-fullerene receptors of AD-A'-DA type for optoelectronic devices

Abstract

A compound of formula (I) 1 is an electron-accepting group, and D 1 and D. 2 is, independently at each occurrence, an electron donating group; A 1 , A 2 , and A 3 are each independently an electron-accepting group; B 1 and B. 2 is independently in each occurrence a bridging group; x 1 and x 2 are each independently 0, 1, 2, or 3; 1 and y 2 are each independently at least 1; z 1 and z 2 are each independently 0, 1, 2, or 3, and (i) to (iv): (i) (D 1 )y1 and (D 2 ) y2 is different, (ii) A 2 and A 3 (iii) (B 1 )x1 and (B 1 ) x2 is different, and (iv) (B 2 )z1 and (B 2 ) z2 is different from the other. The compound of formula (I) may be used as an electron acceptor in an organic photodetector. [Formula 1] TIFF2024532706000055.tif16149

Description

[Background technology]

[0001] Embodiments of the present disclosure relate to electron accepting compounds, and more particularly, but not exclusively, to compounds containing an electron accepting unit and an electron donating unit, which are suitable for use as electron accepting materials in photoresponsive devices.

[0002] Electron-accepting non-fullerene compounds are known.

[0003] US Patent Publication No. 20200328357 discloses asymmetric A-D'-D-D''-A non-fullerene acceptors with two different π-bridges containing alkylthienyl and alkoxythienyl units.

[0004] WO2020182174 discloses fluorescent compounds for bioimaging applications having donor-acceptor (DA) structures in which electron donating and electron withdrawing moieties are arranged alternately along a conjugated structure.

[0005] Zhang et al., “Non-Fullerene Acceptors with an Optical Response over 1000 nm toward Efficient Organic Solar Cells”, ACS Appl. Mater. Interfaces 2021, 13, 43, 51279-51288, disclose NFAs with π-bridging units and various end groups.

[0006] Kang et al, “Push-Pull Type Non-Fullerene Acceptors for Polymer Solar Cells: Effect of the Donor Core”, ACS Appl. Mater. Interfaces 2017, 9, 29, 24771-24777 disclose non-fullerene acceptors for solar cells.

[0007] Li et al., “Asymmetric AD-π-A-type nonfullerene small molecule acceptors for efficient organic solar cells” J. Mater. Chem. A, 2019, 7, 19348-19354 discloses an asymmetric nonfullerene small molecule receptor TTPT-T-2F with an AD-π-A structure. Summary of the Invention

[0008] The present disclosure provides a compound of formula (I): [ka]

[0009] A 1 is an electron accepting group.

[0010] D 1 and D. 2 is independently at each occurrence an electron donating group.

[0011] A 1 , A 2 , and A 3 are each independently an electron accepting group.

[0012] B 1 and B. 2 is independently at each occurrence a bridging group.

[0013] x 1 and x 2 are each independently 0, 1, 2, or 3.

[0014] y 1 and y 2 are each independently at least 1.

[0015] z 1 and z 2 are each independently 0, 1, 2, or 3.

[0016] At least one of (i) to (iv) applies.

[0017] (D 1 ) y1 and (D 2 ) y2 Different from

[0018] A 2 and A 3 Different from

[0019] (B 1 ) x1 and (B 1 ) x2 is different from, and

[0020] (B 2 ) z1 and (B 2 ) z2 is different.

[0021] The present disclosure provides a composition comprising an electron donor material and an electron accepting material, where the electron accepting material is a compound described herein.

[0022] The present disclosure provides an organic electronic device comprising an active layer comprising a compound or composition described herein.

[0023] The present disclosure provides a light sensor that includes a light source and an organic photodetector as described herein, where the light sensor is configured to detect light emitted from the light source.

[0024] The present disclosure provides formulations comprising a compound or composition described herein dissolved or dispersed in one or more solvents.

[0025] 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. [Brief description of the drawings]

[0026] The disclosed technology and the accompanying drawings illustrate several implementations of the disclosed technology. [Figure 1] FIG. 1 illustrates an organic photoresponsive device according to some embodiments. The drawings are not drawn to scale and have various perspectives and views. The drawings are some implementations and examples. In addition, some components and / or operations may be separated into different blocks or combined into a single block for the purpose of describing some of the embodiments of the technology of the present disclosure. Furthermore, the technology is applicable to various modifications and alternative forms, and specific embodiments are shown in the drawings as examples and described in detail below. However, the intention is not to limit the technology to the specific implementation forms described. On the contrary, the technology is intended to cover all modifications, equivalents, and alternatives within the scope of the technology as defined by the appended claims. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0027] Unless the context clearly requires otherwise, throughout the specification and claims, words such as "comprise", "comprising" and the like shall be interpreted in an inclusive sense, i.e., "including but not limited to", as opposed to an exclusive or exhaustive sense. Additionally, the words "herein", "on", "under" and words of similar meaning, when used in this application, refer to this application as a whole and not to any particular portion of this application. Where the context permits, words in the detailed description using the singular or plural 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, namely, 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.

[0028] The teachings of the technology provided herein may be applied to other systems, not necessarily the systems described below. Elements and operations of the various embodiments described below can be combined to provide further implementations of the technology. Some alternative implementations of the technology may include additional elements to those implementations described below, as well as fewer elements.

[0029] These and other changes may be made to the technology in light of the detailed description below. This description describes certain examples of the technology and describes the best possible methods, but no matter how detailed the description may appear, the technology may be implemented in many ways. As described above, a particular term used when describing a particular feature or aspect of the technology should not be interpreted 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 interpreted as limiting the technology to the particular 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.

[0030] In order to reduce the number of claims, certain aspects of the technology are presented below in certain claim forms, but applicants contemplate the various aspects of the technology in any number of claim forms.

[0031] In the following description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the implementation 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.

[0032] The compounds of formula (I) described herein may be provided in a bulk heterojunction layer of a photoresponsive device, preferably a photodetector, where the bulk heterojunction layer is disposed between an anode and a cathode.

[0033] The bulk heterojunction layer comprises or consists of an electron donating material and an electron accepting compound of formula (I) as described herein.

[0034] In some embodiments, a bulk heterojunction layer contains two or more accepting materials and / or two or more electron accepting materials.

[0035] In some embodiments, the weight ratio of electron donor material(s) to electron accepting material(s) is from about 1:0.5 to about 1:2, preferably from about 1:1.1 to about 1:2.

[0036] 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 (X) 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.

[0037] 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 (X) is less than 1.4 eV.

[0038] Unless otherwise stated, the HOMO and LUMO levels of the materials described herein are measured by square wave voltammetry (SWV).

[0039] In SWV, the potential between the working and reference electrodes is swept linearly in time while the current at the working electrode is measured. The difference current between the forward and reverse pulses is plotted as a function of potential to obtain a voltammogram. Measurements can be made using a CHI 660D potentiostat.

[0040] An apparatus for measuring HOMO or LUMO energy levels by SWV can include 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-free Ag / AgCl reference electrode.

[0041] Ferrocene is added directly to the existing cell at the end of the experiment for calculation purposes and the potentials are determined using cyclic voltammetry (CV) for the oxidation and reduction of ferrocene versus Ag / AgCl.

[0042] The samples are dissolved in toluene (3 mg / ml) and spun at 3000 rpm directly onto a glassy carbon working electrode.

[0043] LUMO=4.8-E ferrocene (peak-to-peak average)-E reduced sample (peak maximum).

[0044] HOMO=4.8-E ferrocene (peak-to-peak average) + E oxidation of the sample (peak maximum).

[0045] 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.

[0046] In some embodiments, the compound of formula (I) has an absorption peak above 900 nm, optionally above 1000 nm.

[0047] Unless otherwise stated, the absorption spectra of the materials described herein are measured using a Cary 5000 UV-VIS-NIR spectrometer. Measurements were performed from 175 nm to 3300 nm using a PbSmart NIR detector for extended photometric range with variable slit widths (down to 0.01 nm) for optimal control of data resolution.

[0048] Absorption data is obtained by measuring the intensity of radiation transmitted through a solution sample. The absorption intensity is plotted versus the incident wavelength to generate an absorption spectrum. A method for measuring the absorption rate may include measuring a 15 mg / ml solution in a quartz cuvette and comparing it to a cuvette containing only the solvent.

[0049] Unless otherwise stated, the absorption data provided herein was measured in toluene solution.

[0050] In some embodiments, the electron accepting compound has the formula (I): [ka]

[0051] D 1 and D. 2 is independently at each occurrence an electron donating group.

[0052] A 1 , A 2 , and A 3 are each independently an electron accepting group.

[0053] B 1 and B. 2 is independently at each occurrence a bridging group.

[0054] x 1 and x 2 are each independently 0, 1, 2, or 3, and preferably 0 or 1.

[0055] y 1 and y 2 are each independently at least 1, preferably 1, 2 or 3, and more preferably 1.

[0056] z 1 and z 2 are each independently 0, 1, 2, or 3, and preferably 0 or 1.

[0057] -(B 1 ) x1 -(D 1 ) y1 -(B 2 ) z1 -A 2 is -(B 1 ) x2 -(D 2 ) y2 -(B 2 ) z2 -A 3 Such compounds are hereinafter referred to as "asymmetric" compounds.

[0058] At least one of (i) to (iv) applies.

[0059] (i)(D 1 ) y1 and (D 2 ) y2 Different from

[0060] (ii)A 2 and A 3 Different from

[0061] (iii) (B 1 ) x1 and (B 1 ) x2 is different from, and

[0062] (iv)(B 2 ) z1 and (B 2 ) z2 is different.

[0063] In some preferred embodiments, D 1 and D 2 Unlike y 1 andy 2 is the same as or different from.

[0064] In some preferred embodiments, y 1 andy 2 Unlike D 1 and D 2 is the same as or different from.

[0065] (B 1 ) x1 and (B 1 ) x2 If different from x 1 and x 2 is the same, in this case (B 1 ) x1 B 1 But (B 1 ) x2 B 1 or x 1 and x 2 are different, preferably x 1 is 1 and x 2 is 0, in which case (B 1 ) x1 B 1 However, (B 1 ) x2 B 1 Preferably, x is different from 1 and x 2 are 0 respectively.

[0066] In some preferred embodiments, (B 2 ) z1 (B 2 ) z2 According to these embodiments, z 1 and z 2 is the same, in this case (B 2 ) z1 B 2 However, (B 2 ) z2 B 2 or z 1 and z 2 are different, preferably z 1 is 1 and z 2 is 0, in which case (B 2 ) z1 B 2 However, (B 2 ) z2 B 2 or is different from

[0067] Optionally, (B2 ) z1 B 2 is an optionally substituted monocyclic aromatic or heteroaromatic group, (B 2 ) z2 B 2 is a fused aromatic or heteroaromatic group.

[0068] D 1 and D 2 Difference from A 2 and A 3 Difference from B 1 Differences between groups, and B 2 The differences between the groups can in each case be differences in the ring structures and / or in the ring substituents.

[0069] In some embodiments, the -(B 1 ) x1 -(D 1 ) y1 -(B 2 ) z1 -A 2 And-(B 1 ) x2 -(D 2 ) y2 -(B 2 ) z2 -A 3 There is only one difference between

[0070] In some embodiments, the -(B 1 ) x1 -(D 1 ) y1 -(B 2 ) z1 -A 2 And-(B 1 ) x2 -(D 2 ) y2 -(B 2 ) z2 -A 3 In a preferred embodiment, the difference between y 1 andy 2 and are both 1, and D 1 and D 2 Unlike (B 2 ) z1 (B2 ) z2 is different.

[0071] Electron-accepting group A 1 , A 2 , and A 3 Each of the groups is an electron donating group D 1 Or D 2 The lowest unoccupied molecular orbital (LUMO) level 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).

[0072] In some embodiments, A of formula (I) 1 is a group of formula (II), [ka]

[0073] During the ceremony,

[0074] Ar 1 is an aromatic or heteroaromatic group,

[0075] Y is O, S, NR 4 or R 1 -C=CR 1 where R 1 is independently at each occurrence H or a substituent, and two substituents R 1 may be bonded to form a monocyclic or polycyclic ring, R 4 is H or a substituent.

[0076] Receptor unit A 1

[0077] Ar 1is a group of formula (II), Ar 1 is unsubstituted or contains one or more R 2 R may be a monocyclic or polycyclic heteroaromatic group substituted with a group, 2 is independently a substituent at each occurrence.

[0078] Preferred R 2 The group is selected from

[0079] F,

[0080] C.N.,

[0081] NO2,

[0082] C 1~20 Alkyl (wherein one or more non-adjacent C atoms are O, S, NR 7 may be replaced by R 7 is C 1~12 hydrocarbyl, COO, or CO, and one or more H atoms of the alkyl may be replaced by F;

[0083] Aromatic or heteroaromatic groups, preferably phenyl, which are unsubstituted or substituted with one or more substituents, and [ka]

[0084] or [ka]

[0085] A group selected from

[0086] In the formula, Z 40 , Z 41 , Z 42 , and Z 43 are each independently CR 13 or N and R 13 is H or a substituent at each occurrence, preferably C 1~20is a hydrocarbyl group, Y 40 and Y 41 are each independently O, S, or NX 71 (In the formula, X 71 CN or COOR 40 ) or CX 60 X 61 (In the formula, X 60 and X 61 are independently CN, CF3, or COOR 40 ) and W 40 and W 41 are each independently O, S, or NX 71 , or CX 60 X 61 (In the formula, X 60 and X 61 are independently CN, CF3, or COOR 40 ) and R 40 is H or a substituent at each occurrence, preferably H or C 1~20 A hydrocarbyl group. An aromatic or heteroaromatic group R 2 Exemplary substituents are F, CN, NO, and C. 1~12 Alkyl (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.

[0087] R as described anywhere in this specification 7 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.

[0088] If a C-atom of an alkyl group described anywhere in this specification 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.

[0089] 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 methyl group at the end of an n-alkyl chain or the C atom of the methyl group at the end of a branched alkyl chain.

[0090] When the terminal C atom of the groups described anywhere herein is replaced, the resulting group may be an anionic group comprising a countercation, e.g. an ammonium or metal countercation, preferably an ammonium or alkali metal cation.

[0091] A C-atom of an alkyl substituent which 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.

[0092] 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.

[0093] Exemplary polycyclic heteroaromatic groups Ar 1 is a group of formula (V), [ka]

[0094] X 1 and X 2 are each independently N and CR 3 where R 3 is H or a substituent, optionally H or the substituent R 2 It is.

[0095] X 3 , X 4 , X 5 , and X 6 are each independently N and CR 3 Selected from X 3 , X 4 , X 5 , and X 6 At least one of the following is CR 3 This is subject to the condition that:

[0096] Z is O, S, SO2, NR4 , P.R. 4 , C(R 3 )2, Si(R 3 )2C=O, C=S, and C=C(R 5 )2, where R 3 is as above, and R 4 is H or a substituent, R 5 is an electron-withdrawing group in each occurrence.

[0097] Optionally, any NR as described in any of the above. 4 Or PR 4 Each R 4 H and 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 may be unsubstituted or may have one or more substituents, optionally one or more C 1~12 Alkyl groups, in which 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 with F.

[0098] 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 H or a substituent, preferably H or C 1~20 It is a hydrocarbyl group.

[0099] A in formula (II) 1 The radicals are preferably selected from radicals of formulae (IIa) and (IIb). [ka]

[0100] In the case of the compound of formula (IIb), two R 1 The groups may be bonded or unbonded.

[0101] Preferably, two R 1 When no groups are bonded, each R 1 are H, F, CN, NO2, C 1~20 Alkyl (wherein one or more non-adjacent C atoms are O, S, NR 7 , CO, COO, N.R. 4 , P.R. 4 , or Si(R 3 )2, wherein R 3 and R 4 is as defined above, where one or more H atoms may be replaced by F, 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 (wherein 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).

[0102] Preferably, two R 1 When the group is attached, the group of formula (IIb) has the formula (IIb-1) or (IIb-2): [ka]

[0103] 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.

[0104] X is O, S, SO2, NR 4 , P.R. 4 , C(R 3 )2, Si(R 3 )2C=O, C=S, and C=C(R 5 )2, where R 3 , R 4 , and R 5 is as stated above.

[0105] Exemplary electron accepting groups of formula (II) include, but are not limited to, the following: [ka]

[0106] During the ceremony, Ak 1 is C 1~20 It is an alkyl group.

[0107] The divalent electron-accepting group other than the group represented by formula (II) is arbitrarily selected from the group represented by formulas (IVa) to (IVj). [ka]

[0108] R 23 represents, for each occurrence, a substituent, optionally C 1~12 Alkyl (where Z 1 At least one non-adjacent C atom other than the C atom bonded to is O, S, or NR 7 , COO, or CO, and one or more H atoms of the alkyl may be replaced by F.

[0109] R 25 are independently H, F, CN, NO2, and C at each occurrence. 1~12 Alkyl (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), unsubstituted or a combination of F and C 1~12Alkyl (wherein one or more non-adjacent C atoms are O, S, NR 7 , COO, or CO), optionally phenyl, or [ka]

[0110] or [ka]

[0111] A group selected from

[0112] 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,

[0113] Y 40 and Y 41 are each independently O, S, or 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

[0114] W 40 and W 41 are each independently O, S, or NX 71 (In the formula, X 71 CN or COOR 40 ) or CX 60 X 61 (In the formula, X 60 and X 61 are independently CN, CF3, or COOR40 ) and

[0115] R 40 is, at each occurrence, H or a substituent, preferably H or C 1~20 It is a hydrocarbyl group.

[0116] Z 1 is N or P.

[0117] 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 of, when present, optionally include, R 25 is selected from the non-H groups:

[0118] R at each occurrence 12 is a substituent, preferably C 1~20 It is a hydrocarbyl group.

[0119] 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:

[0120] Electron-accepting group A 2 , A 3

[0121] Monovalent acceptor group A 2 and A 3 may each be independently selected from any such unit known to one of skill in the art. 2 and A 3 may be the same or different, and are preferably different.

[0122] Exemplary monovalent acceptor units include, but are not limited to, units of formulae (IIIa)-(IIIq): [ka] TIFF2024532706000015.tif183170

[0123] U is a 5- or 6-membered ring that is unsubstituted or substituted with one or more substituents and may be fused to one or more additional rings.

[0124] The N atom in formula (IIIe) may be unsubstituted or substituted.

[0125] R 10 is H or a substituent, preferably C 1~12 Alkyl (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), and unsubstituted or a mixture of F and C 1~12 alkyl, and one or more non-adjacent C atoms are substituted with O, S, NR 7 , COO, or an aromatic group optionally substituted with CO, optionally a phenyl substituent.

[0126] Preferably, R 10 is H.

[0127] J is O or S, preferably O.

[0128] R 13 represents, for each occurrence, a substituent, optionally C 1~12 Alkyl (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.

[0129] R 15are H, F, and C independently at each occurrence. 1~12 Alkyl (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), unsubstituted or a combination of F and C 1~12 Alkyl (wherein one or more non-adjacent C atoms are O, S, NR 7 , COO, or CO; 2 , optionally phenyl, or [ka] is a group selected from

[0130] R 16 is H or a substituent, preferably

[0131] -(Ar 3 ) w (In the formula, Ar 3 is independently at each occurrence an unsubstituted or substituted aryl or heteroaryl group, preferably thiophene, and w is 1, 2, or 3; [ka]

[0132] and

[0133] C 1~12 Alkyl (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.

[0134] Ar 6 is a 5-membered heteroaromatic group, preferably thiophene or furan, which is unsubstituted or substituted with one or more substituents.

[0135] Ar3 and Ar 6 The substituents, when present, are optionally 1~12 Alkyl (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.

[0136] T 1 , T 2 , and T 3 are each independently as defined above.

[0137] Ar 8 is unsubstituted or has one or more substituents, optionally one or more non-H substituents R 10 and B 2 Aromatic C atoms and B 2 is a fused heteroaromatic group bonded to a boron substituent of

[0138] Preferred group A 2 and A 3 is D1 or D2, or B if present 2 is a group having a non-aromatic carbon-carbon bond directly bonded to

[0139] Preferably, A 2 and A 3 At least one of, preferably A 2 and A 3 both of which have a group of formula (IIIa-1) [ka]

[0140] During the ceremony,

[0141] R 10 But as mentioned above,

[0142] each X 7 ~X 10 Independently, CR 12 or N, where R12 is H for each occurrence or C 1~20 is a substituent selected from hydrocarbyl and electron-withdrawing groups. Preferably, the electron-withdrawing group is F, Cl, Br or CN, more preferably F, Cl or CN;

[0143] X 60 and X 61 are independently CN, CF3 or COOR 40 where R 40 is H or a substituent at each occurrence, preferably H or C 1~20 It is a hydrocarbyl group. Preferably, X 60 and X 61 are CNs, respectively.

[0144] C 1~20 Hydrocarbyl Group R 12 is C 1~20 Alkyl, unsubstituted phenyl, and one or more C 1~12 It may be selected from phenyl substituted with an alkyl group.

[0145] Exemplary groups of formula (IIId) include: [ka]

[0146] Exemplary groups of formula (IIIe) include: [ka]

[0147] Exemplary groups of formula (IIIq) are: [ka]

[0148] Exemplary groups of formula (IIIg) are: [ka]

[0149] Exemplary groups of formula (IIIj) are: [ka]

[0150] In the formula, Ak is C 1~12 Alkylene chain (one or more C atoms are O, S, NR 7 , CO, or COO), where An is an anion, optionally -SO3 - and each benzene ring is independently unsubstituted or R 10 and is substituted with one or more substituents selected from the substituents described for.

[0151] Exemplary groups of formula (IIIm) are: [ka]

[0152] Exemplary groups of formula (IIIn) are: [ka]

[0153] The group of formula (IIIo) is -B(R 14 ) 2-substituted bridging group B 2 where R 14 is a substituent in each occurrence, optionally C 1~20 is a hydrocarbyl group, and → is R 3 or R 6 Boron atom -B(R 14 )2, and --- is a bond to B 2 is a bond to.

[0154] Optionally, R 14 is C 1~12 Alkyl, unsubstituted phenyl, and one or more C 1~12 phenyl substituted with an alkyl group.

[0155] Group of formula (IIIo), B 2 Group, and B 2 B(R 14 ) The two substituents may be linked together to form a 5- or 6-membered ring.

[0156] Optionally, the group of formula (IIIo) is selected from: [ka]

[0157] Cross-linking unit

[0158] Cross-linking unit B 1 and B. 2 are preferably 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.

[0159] Optionally, B 1 and B. 2 is selected from the units of formulae (VIa) to (VIn), [ka]

[0160] In the formula, Y A is O, S, or NR 55 where R 55 is H or a substituent, R 8 is independently at each occurrence H or a substituent, preferably H, or F, CN, NO, C 1~20 Alkyl (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), phenyl which is unsubstituted or substituted with one or more substituents, and -B(R 14)2(where R 14 is a substituent in each occurrence, optionally C 1~20 R in formula (VIa), (VIb) and (VIc) is a substituent selected from the group consisting of aryl, aryl, aryl and aryl groups. 8 The groups may be linked to form a bicyclic ring, for example a thienopyrazine.

[0161] R 8 is preferably H, C 1~20 Alkyl or C 1~19 It is an alkoxy.

[0162] Electron-donating group D 1 and D. 2

[0163] 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 a fused thiophene or furan ring, optionally a fused ring 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.

[0164] Exemplary Electron Donating Groups D 1 and D. 2 Examples of the formula (VIIa) to (VIIp) include groups of the formula (VIIa) to (VIIp), [ka] TIFF2024532706000029.tif80161

[0165] In the formula, Y A is independently O, S, or NR at each occurrence 55 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 R55 is independently at each occurrence H or a substituent; R 53 is independently a substituent at each occurrence.

[0166] Optionally, R 51 and R 52 are independently assigned to H, F, and C in each occurrence. 1~20 Alkyl (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), and an aromatic or heteroaromatic group Ar which is unsubstituted or substituted by one or more substituents. 3 is selected from.

[0167] In some embodiments, Ar 3 may be an aromatic group, for example phenyl.

[0168] Ar 3 If present, one or more of the substituents in 1~12 Alkyl (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.

[0169] Preferably, each R 54 teeth,

[0170] H,

[0171] F,

[0172] Linear, branched, or cyclic C 1~20 Alkyl (wherein one or more non-adjacent C atoms are O, S, NR 7 , CO, or COO, where R 7 is C 1~12 Hydrocarbyl, C 1~20 one or more H atoms of the alkyl may be replaced by F, and

[0173] Formula (Ak)u-(Ar 7 ) v groups (where Ak is C 1~20 Alkylene chain (where one or more non-adjacent C atoms are O, S, NR 7 , 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.

[0174] Ar 7 The substituents, when present, are preferably F, Cl, NO, CN, and C 1~20 Alkyl (wherein 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. Preferably, Ar 7 is phenyl.

[0175] Preferably, each R 51 is H.

[0176] Optionally, R 53 independently for each occurrence, C 1~20 Alkyl (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), and may be unsubstituted or may have one or more substituents, optionally one or more C 1~12 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.

[0177] Preferably, R 55 is H or C 1~30 It is a hydrocarbyl group.

[0178] Preferably, D 1 and D. 2 are each independently a group of formula (VIIa). Exemplary groups of formula (VIIa) include, but are not limited to, [ka]

[0179] where Hc, independently at each occurrence, is 1~20 Hydrocarbyl groups, such as C 1~20 Alkyl, unsubstituted aryl, or one or more C 1~12 It is an aryl substituted with an alkyl group. The aryl group is preferably phenyl.

[0180] In some embodiments, y 1 and y 2 are each equal to 1.

[0181] In some embodiments, y 1 and y 2 At least one of D is greater than 1. 1 Group and / or D 2 Each chain of groups can be linked in any orientation. For example, D 1 is a group of formula (VIIa), y 1 If is 2, then -[D 1 ] y1 may be selected from any of the following: [ka]

[0182] Electron-donating materials

[0183] The bulk heterojunction layers described herein comprise an electron donating material and a compound of formula (I) or (X) described herein.

[0184] Exemplary donor materials are disclosed, for example, in WO2013051676, the contents of which are incorporated herein by reference.

[0185] The electron donating material can be a non-polymeric or polymeric material.

[0186] 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, which comprises alternating electron donating and electron accepting repeat units.

[0187] Preferred are amorphous or semi-crystalline conjugated organic polymers.

[0188] More preferably, the electron donating polymer is a conjugated organic polymer with a low band gap, typically between 2.5 eV and 1.5 eV, preferably between 2.3 eV and 1.8 eV. Optionally, the electron donating polymer has a HOMO level of 5.5 eV or less from the vacuum level. Optionally, the electron donating polymer has a HOMO level of 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, polytriarylamines, poly(phenylenevinylenes), poly(3-substituted thiophenes), poly(3,4-disubstituted thiophenes), polyselenophenes, poly(3-substituted selenophenes), poly(3,4-disubstituted selenophenes), poly(bisthiophenes), poly(phenylenevinylenes ... Mention may be made of polymers selected from conjugated hydrocarbons or heterocyclic polymers, including poly(terthiophenes), poly(bisselenophenes), poly(terselenophenes), polythieno[2,3-b]thiophenes, polythieno[3,2-b]thiophenes, polybenzothiophenes, polybenzo[1,2-b:4,5-b'dithiophenes, polyisothianaphthenes, poly(monosubstituted pyrroles), poly(3,4-disubstituted pyrroles), poly-1,3,4-oxadiazoles, polyisothianaphthenes, derivatives and copolymers thereof.

[0189] 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 repeat units, each of which may be substituted.

[0190] Particularly preferred donor polymers include a donor unit (VIIa) provided as a repeat unit of the polymer, and most preferably have an electron accepting repeat unit, such as a divalent electron accepting unit as described herein, provided as a repeat unit of the polymer.

[0191] Additional Electron Accepting Materials

[0192] In some embodiments, a compound of Formula (I) or (X) described herein is the only electron accepting material of a bulk heterojunction layer.

[0193] In some embodiments, the bulk heterojunction layer contains a compound of formula (I) or (X) and one or more additional electron accepting materials. The one or more additional electron accepting materials may be selected from non-fullerene acceptors and fullerenes.

[0194] Non-fullerene acceptors are described, for example, in Cheng et.al., “Next-generation organic photovoltaics based on non-fullerene acceptors”, Nature Photonics volume 12, pages 131-142 (2018), the contents of which are incorporated herein by reference, and include, but are not limited to, PDI, ITIC, ITIC, IEICO, and derivatives thereof, such as fluorinated derivatives thereof, such as ITIC-4F and IEICO-4F.

[0195] Exemplary fullerene electron accepting compounds include C 60 , C 70 , C 76 , C 78 , and C 84 Fullerenes or derivatives thereof, including but not limited to phenyl-C 61 -Butyric acid methyl ester (C 60 PCBM) containing PCBM-type fullerene derivatives, 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 Examples include ThCBM).

[0196] The fullerene derivative may have the formula (V): [ka]

[0197] 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.

[0198] Exemplary fullerene derivatives include those of formulae (Va), (Vb), and (Vc): [ka]

[0199] In the formula, R 20 ~R 32 are each independently H or a substituent.

[0200] Substituent R 20 ~R 32 optionally, and independently at each occurrence, aryl or heteroaryl, which may be unsubstituted or substituted with one or more substituents, optionally phenyl, and C 1~20 Alkyl (wherein 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.

[0201] The substituents of the aryl or heteroaryl, when present, are optionally 1~12 Alkyl (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.

[0202] compound

[0203] The bulk heterojunction layer may be formed by any process, including, but not limited to, thermal evaporation and solution deposition methods.

[0204] Preferably, the bulk heterojunction layer is formed by depositing a formulation including the electron donor material(s), the electron acceptor 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.

[0205] One or more solvents of the formulation are optionally chlorine, C 1~10 Alkyl and C 1~10 Alkoxy (two or more substituents may be linked, which may be unsubstituted or may have one or more C 1~6 The aryl group may form a ring optionally substituted with alkyl groups), optionally comprising or consisting of benzene 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.

[0206] 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 may be 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 benzoates, 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.

[0207] In addition to the electron-accepting material, the electron-donating material, and one or more solvents, the formulation may contain further components. Examples of such components include 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 inhibitors.

[0208] Organic Electronic Devices

[0209] The polymers or compositions described herein 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 the compositions described herein.

[0210] 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.

[0211] Each of the anode and cathode, independently, may be a single conductive layer or may include multiple layers.

[0212] 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 a light source for use with the organic photodetector.

[0213] 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.

[0214] 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.

[0215] 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 The pixels in the array have an area in the range

[0216] 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 the electrodes supported by the substrate.

[0217] The bulk heterojunction layer contains a polymer as described herein and an electron-accepting compound. The bulk heterojunction layer may consist of these materials or may include one or more additional materials, such as one or more additional electron-donating materials and / or one or more additional electron-accepting compounds.

[0218] Purpose

[0219] 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 in use.

[0220] In some embodiments, the photodetector system includes a plurality of photodetectors as described herein, for example, an image sensor of a camera.

[0221] In some embodiments, a sensor may include an OPD as 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 1000-1500 nm.

[0222] The present inventors have found that materials comprising an electron accepting unit of formula (I) may be used for the detection of light of longer wavelengths, particularly from 1300 to 1400 nm.

[0223] 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.

[0224] 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 brightness of ambient light, as well as in sensors that include organic photodetectors and light sources. The photodetectors may be configured such that light emitted from a light source is incident on the photodetector and changes in wavelength and / or brightness of the light may be detected, for example, due to absorption, reflection, and / or emission of light from a target material in an object, for example, a sample, disposed in the light path between the light source and the organic photodetector. The sample may be a non-biological sample, for example, 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 imaging sensor such as an x-ray imaging device, a camera imaging sensor, a motion sensor (e.g., for use in security applications), a proximity sensor, or a fingerprint sensor. A 1D or 2D photosensor array may comprise a plurality of the photodetectors described herein in 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 is coupled to a light emitting tag that emits light when illuminated by a light source. The light detector may be configured to detect a wavelength of light emitted by the target analyte or a light emitting tag coupled thereto. EXAMPLES

[0225] Compound Example 1

[0226] Compound Example 1 was prepared according to the following reaction scheme: [ka]

[0227] Modeling Data

[0228] All modeling described in these examples was carried out using Gaussian09 software available from Gaussian, using Gaussian09 with B3LYP (functional).

[0229] The HOMO and LUMO levels were modeled for individual donor and acceptor units, and the results are shown in Tables 2-4. Table 1 [Table 1] Table 2 [Table 2] Table 3 [Table 3-1] [Table 3-2]

[0230] Receptor unit A 1 preferably has a modeled LUMO at least 2.9 eV or at least 3.0 eV from the vacuum level.

[0231] The HOMO and LUMO levels were modeled for the asymmetric compound of formula (I) and a comparative symmetric compound. The results are shown in Tables 4-8, where S1f corresponds to the oscillator strength of the transition from S1 (predicts the absorption intensity) and Eopt is the modeled optical gap.

[0232] Table 4-D 1 and D 2 and different compounds. [Table 4] Table 5:z 1 is 1 and z 2 Compounds where is 0 [Table 5-1] [Table 5-2] Table 6: Various B 2 base [Table 6] Table 7:D 1 and D 2 Unlike z 1 is 1, and z 2 is 0 [Table 7] Table 8:D 1 and D2 are different, B 2 Different [Table 8]

Claims

1. A compound of formula (I), wherein 【Chemical 1】 In the formula,[[]]END]] A １ is an electron-withdrawing group, D １ and D ２ is, independently at each occurrence, an electron-donating group, A １ , A ２ , and A ３ are each independently an electron-withdrawing group, B １ and B ２ is, independently at each occurrence, a crosslinking group, x １ and x ２ are each independently 0, 1, 2, or 3, y １ and y ２ are each independently at least 1, z １ and z ２ are each independently 0, 1, 2, or 3, (i) to (iv)[[]]END]] (i) (D １ ) ｙ１ and (D ２ ) ｙ２ are different, (ii) A ２ and A ３ are different, (iii) (B １ ) ｘ１ and (B １ ) ｘ２ are different, and (iv) (B ２ ) ｚ１ and (B ２ ) ｚ２ wherein at least one of the compounds different from each other corresponds to the compound.

2. D １ and D ２ The compound according to claim 1, wherein they are different.

3. (B ２ ) ｚ１ and (B ２ ) ｚ２ which are different, the compound according to claim 1.

4. z １ and z ２ which are different, the compound according to claim 3.

5. z １ and z ２ are each 1, and (B ２ ). ｚ１ The B of ２ is the B of (B ２ ), ｚ２ which is different from the B of ２ the compound according to claim 3.

6. A １ is a group of formula (II), 【Chemical 2】 In the formula,[[]]END]] Ar １ is an aromatic group or a heteroaromatic group, Y is O, S, NR ４ or R １ -C=C-R １ wherein, R １ is independently H or a substituent at each occurrence, and two substituents R １ may combine to form a monocyclic ring or a polycyclic ring, and R ４ is H or a substituent, the compound according to claim 1.

7. The compound according to claim 6, wherein the group of formula (II) has formula (IIa). 【Chemical 3】

8. The compound according to claim 6, wherein the group of formula (II) has formula (IIb). 【Chemical Formula 4】

9. Two Rs １ The compound according to claim 8, wherein two Rs are not bonded.

10. Each R １ is H, F, CN, NO ２ , one or more non-adjacent C atoms are O, S, CO, COO, NR ４ , PR ４ , or Si(R ３ ) ２ may be replaced, and one or more H atoms may be replaced by F, a C １～２０ alkyl, and may be unsubstituted or may be substituted with one or more substituents, and is independently selected from aryl or heteroaryl, wherein R ３ and R ４ are each independently H or a substituent, the compound according to claim 9.

11. Two Rs １ The compound according to claim 8, in which two Rs are bonded.

12. The compound of formula (IIb) has formula (IIb-1) or (IIb-2), wherein 【Chemical Formula 5】 In the formula,[[]]END]] Ar ２ is an aromatic or heteroaromatic group that is unsubstituted or substituted with one or more substituents, X is O, S, SO ２ , NR ４ , PR ４ , C(R ３ ), ２ , Si(R ３ ), ２ C═O, C═S, and C═C(R ５ ), ２ selected from, where R ３ and R ４ are each independently selected from H and substituents at each occurrence, and R ５ is an electron-withdrawing group at each occurrence, the compound according to claim 11.

13. Ar ２ The compound according to claim 12, wherein Ar is unsubstituted or substituted benzene with one or more substituents.

14. x １ and x ２ wherein at least one of them is at least 1, and B １ is, each time it appears, independently selected from vinylene, arylene, heteroarylene, arylenevinylene and heteroarylenevinylene, each of which is unsubstituted or substituted with one or more substituents, the compound according to claim 1.

15. z １ and z ２ at least one of which is at least 1, and B ２ is, independently at each occurrence, vinylene, arylene, heteroarylene, arylenevinylene and heteroarylenevinylene, each of which is unsubstituted or substituted with one or more substituents, the compound according to claim 1.

16. D １ and D ２ are each independently selected from the units of formulas (VIIa) to (VIIp), 【Chemical Formula 6】 【Chem.】 wherein Y Ａ is independently O, S, or NR ５５ each time it appears, Z Ａ is O, S, NR ５５ , or C(R ５４ ), ２ each time it appears, R ５１ , R ５２ , R ５４ , and R ５５ are independently H or a substituent each time they appear, and R ５３ is independently a substituent each time it appears, the compound according to claim 1.

17. A ２ and A ３ at least one of which contains a non-aromatic carbon-carbon double bond, and the carbon atoms of the carbon-carbon double bond are D １ or D ２ to, or if present, B ２ The compound according to claim 1, which is directly bonded.

18. A ２ and A ３ are each independently selected from the groups of formulas (IIIa) to (IIIq), 【Chemical Formula 7】 [Chemical] In the formula,[[]]END]] U is an unsubstituted or substituted 5- or 6-membered ring which may be fused to one or more additional rings.[[]]END]] R １０ is H or a substituent, J is O or S.[[]]END]] R １３ is, in each occurrence, a substituent, R １５ is, each time it appears independently, H or a substituent, R １６ is a substituent, Ar ６ is a 5-membered heteroaromatic group that is unsubstituted or substituted with one or more substituents, T １ 、T ２ 、and T ３ each independently represents an aryl or heteroaryl ring that may be fused to one or more additional rings, and each of T １ 、T ２ 、and T ３ is independently unsubstituted or substituted with one or more substituents. Ar ８ is unsubstituted or substituted with one or more substituents and is a fused heteroaromatic group bonded to the aromatic C atom of B ２ and the boron substituent of B ２ The compound according to claim 1, which is a fused heteroaromatic group bonded to the aromatic C atom of B

19. A ２ and A ３ at least one of which is a group of formula (IIIa-1), [Chemical 8] In the formula,[[]]END]] Each X １ ~X ４ is, independently, CR １２ or N, wherein R １２ is, in each occurrence, H or a substituent selected from C １～２０ hydrocarbyl and an electron-withdrawing group, the compound according to claim 18.

20. The compound according to claim 1, wherein the compound has an absorption peak above 900 nm.[[]]END]]

21. A composition comprising an electron-donating material and an electron-accepting material, wherein the electron-accepting material is the compound of claim 1.[[]]END]]

22. An organic electronic device comprising an active layer comprising the compound or composition according to any one of claims 1 to 21.[[]]END]]

23. The organic electronic device is an organic photo-responsive device comprising a bulk heterojunction layer disposed between an anode and a cathode, and the bulk heterojunction layer comprises the composition according to claim 21, the organic electronic device according to claim 22.[[]]END]]

24. The organic photo-responsive device according to claim 23, wherein the organic photo-responsive device is an organic photodetector.[[]]END]]

25. An optical sensor comprising a light source and the organic photodetector according to claim 24, wherein the optical sensor is configured to detect light emitted from the light source.[[]]END]]

26. The optical sensor according to claim 25, wherein the light source emits light having a peak wavelength above 900 nm.[[]]END]]

27. A formulation comprising the compound or composition according to any one of claims 1 to 21 dissolved or dispersed in one or more solvents.[[]]END]]

28. A method of forming the organic electronic device according to claim 22, wherein the formation of the active layer comprises deposition of the formulation according to claim 27 onto a surface and evaporation of the one or more solvents.[[]]END]]

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