AD-A'-DA type photoresponsive non-fullerene receptors for optoelectronic devices

Abstract

A compound of formula (I) 1 is a divalent heteroaromatic electron accepting group containing at least three fused aromatic rings or has a modeled LUMO greater than 2.70 eV from the vacuum level. 2 and A 3 are each independently a monovalent electron-accepting group. 1 and D. 2 is, independently at each occurrence, an electron donating group; D 1 and D. 2 At least one occurrence of at least one of is a fused heteroaromatic group containing at least four fused rings. 1 and B. 2 is independently at each occurrence a bridging group. 1 , x 2 , z 1 , and z 2 Each y is independently 0, 1, 2, or 3. 1 and y 2 is each independently at least 1. The compounds of formula (I) may be used as receptors in organic photodetectors. [Formula 1] TIFF2024533974000179.tif9150

Description

[Technical field]

[0001] [Background technology]

[0002] 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.

[0003] Electron-accepting non-fullerene compounds are known.

[0004] Korean Patent No. 20190117086 discloses an organic solar cell comprising a compound of the following formula: [ka]

[0005] In the formula, Pull1 is an electron-withdrawing group, k is 1 to 10, and L1 has the formula: [ka]

[0006] Kim et al., “Synthesis of ITIC Derivatives with Extended π-Conjugation as Non-Fullerene Acceptors for Organic Solar Cells,” ACS Appl. Mater. Interfaces 2019, 11, 50, 47121, discloses AD-A’-DA type molecular receptors for solar cells based on indacenodithienothiophene (IDTT) and thiophene-adjacent 2,1,3-benzothiadiazole.

[0007] Kim et al “Alkylated Indacenodithiophene-Based Non-fullerene Acceptors with Extended π-Conjugation for High-Performance Large-Area Organic Solar Cells” ACS Appl. Mater. Interfaces 2020,12,45,50638-50647 discloses AD-A'-DA type electron acceptors for organic solar cells based on alkylated indacenodithiophene (C8IDT), dicyanated thiophene-vicinate 2,1,3-benzothiadiazole (CNDTBT), and 2-(3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (INCN) or 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (FINCN).

[0008] Zhang et al., “Designing efficient AD-A1-DA-type non-fullerene acceptors with enhanced fill factor via noncovalently conformational locking,” Synthetic Metals Volume 278, August 2021, 116838, discloses AD-A1-DA-type non-fullerene acceptors (NFAs) PZ-dIDTC6 and PD-dIDTC6, which consist of indacenodithiophene (IDT) dimers bridged with weakly electron-withdrawing pyrazine (PZ) or pyridine (PD) units to improve the fill factor of non-fullerene organic solar cells.

[0009] Cai et al., “Effects of π-Bridge on Fused-Ring Electron Acceptor Dimers,” ACS Appl. Polym. Mater. 2021, 3, 1, 23-29, disclose photovoltaic cells containing non-fullerene acceptors (TTIDIC and BTIDIC) consisting of indacenodithiophene (IDT) dimers bridged with electron-rich thienothiophene (TT) or electron-accepting benzothiadiazole (BT).

[0010] Zhang et al., “A2-D-A1-D-A2-type small molecule acceptors incorporated with electron-deficient core for non-fullerene organic solar cells,” Solar Energy Volume 197, February 2020, Pages 511-518, discloses small molecule acceptors DFB-dIDT and BT-dIDT with 2,5-difluorobenzene (DFB) or benzothiadiazole (BT) (A1) as the electron-withdrawing core and indanone derivatives as the A2 units for organic solar cells.

[0011] Zhang et al, “Electron-Deficient and Quinoid Central Unit Engineering for Unfused Ring-Based A1-D-A2-D-A1-Type Acceptor Enables High Performance Nonfullerene Polymer Solar Cells with High V oc and PCE Simultaneously”, Small, DOI:10.1002 / smll.201907681, discloses non-fullerene small molecule receptors BO2FIDT-4Cl and BT2FIDT-4Cl with the same terminals (A1), indacenodithiophene units (D), and a fluorinated electron-deficient central unit of difluorobenzoxadiazole or difluorobenzothiadiazole (A2) for solar cells. Summary of the Invention

[0012] In some embodiments, the disclosure provides a compound of formula (I): [ka]

[0013] During the ceremony,

[0014] A 1 is a divalent heteroaromatic electron accepting group containing at least three fused aromatic rings, and / or A 1 is a divalent heteroaromatic electron accepting group with a modeled LUMO >2.70 eV from the vacuum level.

[0015] A 2 and A 3 are each independently a monovalent electron-accepting group,

[0016] D 1 and D. 2 is, independently at each occurrence, an electron donating group; D 1 and D. 2 at least one occurrence of at least one of is a fused heteroaromatic group containing at least four fused rings;

[0017] B 1 and B. 2 is independently at each occurrence a bridging group;

[0018] x 1 and x 2 are each independently 0, 1, 2, or 3;

[0019] y 1 and y 2 are each independently at least 1;

[0020] z 1 and z 2 are each independently 0, 1, 2, or 3. [Brief description of the drawings]

[0021] The disclosed technology and the accompanying drawings illustrate several implementations of the disclosed technology. [Figure 1] 1 illustrates an organic photoresponsive device according to some embodiments. [Diagram 2] 1 shows the absorption spectra of compound Example 1 according to an embodiment of the present disclosure and a comparative compound. [Diagram 3] 1 shows the absorption spectra of a solution and a film of compound Example 2 according to an embodiment of the present disclosure. [Figure 4] 1 shows the external quantum efficiency versus wavelength of an organic photodetector including compound Example 2. [Diagram 5] 1 shows the dark current (current density vs. voltage) of an organic photodetector including compound Example 2. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0022] 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 by way of example and are 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 that are within the scope of the technology as defined by the appended claims.

[0023] 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.

[0024] 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.

[0025] 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.

[0026] 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.

[0027] 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.

[0028] 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.

[0029] The bulk heterojunction layer comprises or consists of an electron donating material and an electron accepting compound of formula (I) as described herein.

[0030] In some embodiments, a bulk heterojunction layer contains two or more accepting materials and / or two or more electron accepting materials.

[0031] 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.

[0032] 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) 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.

[0033] Optionally, the gap between the HOMO level of the electron donating material and the LUMO level of the electron accepting compound of Formula (I) is less than 1.4 eV.

[0034] Unless otherwise stated, the HOMO and LUMO levels of the materials described herein are measured by square wave voltammetry (SWV).

[0035] 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.

[0036] 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.

[0037] 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.

[0038] The samples are dissolved in toluene (3 mg / ml) and spun at 3000 rpm directly onto a glassy carbon working electrode.

[0039] LUMO=4.8-E ferrocene (peak-to-peak average)-E reduced sample (peak maximum).

[0040] HOMO=4.8-E ferrocene (peak-to-peak average) + E oxidation of sample (peak maximum).

[0041] 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.

[0042] Preferably, the compound of formula (I) has an absorption peak above 1000 nm, more preferably above 1100 nm or 1200 nm, optionally in the range of 1000 to 1400 nm.

[0043] 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 300 nm to 2500 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.

[0044] Absorption data is obtained by measuring the intensity of radiation transmitted through a solution sample. The absorption intensity is plotted versus incident wavelength to generate an absorption spectrum. The absorption of the solution can be measured from a 0.015 mg / ml solution in a quartz cuvette and compared to a cuvette containing only the solvent.

[0045] In some embodiments, the electron accepting compound has the formula (I): [ka]

[0046] D 1 and D. 2 is, independently at each occurrence, an electron donating group. The compounds of formula (I) include a heteroaromatic group containing at least four fused rings, D 1 and D. 2 The compound includes at least one group selected from the group consisting of

[0047] In some embodiments, A 1 is a divalent heteroaromatic electron accepting group containing at least three fused aromatic rings.

[0048] In some embodiments, A 1 is a divalent heteroaromatic electron accepting group having a modeled LUMO level greater than 2.70 eV from the vacuum level, optionally at least 2.75 eV from the vacuum level.

[0049] A 2 and A 3 are each independently a monovalent electron-accepting group.

[0050] B 1 and B. 2 is independently at each occurrence a bridging group.

[0051] x 1 and x 2 are each independently 0, 1, 2, or 3, and preferably 0 or 1.

[0052] y 1 and y 2 are each independently at least 1, preferably 1, 2 or 3, and more preferably 1.

[0053] z 1 and z 2 are each independently 0, 1, 2, or 3, and preferably 0 or 1.

[0054] Electron-accepting group A 1 , A 2 , and A3 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).

[0055] Receptor unit A 1

[0056] A 1 can be a polycyclic heteroaromatic group which is unsubstituted or substituted with one or more substituents.

[0057] A in formula (I) 1 is the group of formula (II) [ka]

[0058] During the ceremony,

[0059] Ar 1 is a monocyclic or polycyclic aromatic or heteroaromatic group,

[0060] 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.

[0061] R in the formula 2is independently at each occurrence a substituent; R 2 Base.

[0062] Preferred R 2 The group is selected from:

[0063] F,

[0064] C.N.,

[0065] NO2,

[0066] 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;

[0067] Aromatic or heteroaromatic groups, preferably phenyl, which are unsubstituted or substituted with one or more substituents, and [ka]

[0068] or [ka]

[0069] A group selected from

[0070] 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 1~20 is a hydrocarbyl group, Y 40 and Y 41 are each independently O, S, or NX 71 (In the formula, X 71CN 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.

[0071] 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.

[0072] 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.

[0073] 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.

[0074] 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.

[0075] 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.

[0076] 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.

[0077] Exemplary polycyclic heteroaromatic groups Ar 1 is a group of formula (V): [ka]

[0078] 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.

[0079] 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:

[0080] Z is O, S, SO2, NR 4 , P.R. 4 , C(R3 )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.

[0081] Optionally, any NR described anywhere herein 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.

[0082] 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.

[0083] A in formula (II) 1 The radicals are preferably selected from radicals of formulae (IIa) and (IIb). [ka] [ka]

[0084] In the case of the compound of formula (IIb), two R 1 The groups may be bonded or unbonded.

[0085] Preferably, two R 1 When no groups are attached, 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).

[0086] Preferably, two R 1 When the group is attached, the group of formula (IIb) has the formula (IIb-1) or (IIb-2): [ka] [ka]

[0087] Ar 2 is an aromatic or heteroaromatic group, preferably benzene, which is unsubstituted or substituted with one or more substituents. 2may be unsubstituted as above or may contain one or more substituents R 2 may be substituted with.

[0088] 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.

[0089] Exemplary electron accepting groups of formula (II) include, but are not limited to, the following: [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0090] During the ceremony, Ak 1 is C 1~20 It is an alkyl group.

[0091] Another preferred acceptor unit is a thiophene, optionally a pyridine, a 1,4-diazine or a thiadiazole, fused to a 5- or 6-membered heteroaromatic ring containing at least one N atom. The aromatic carbon atoms of this acceptor unit may be unsubstituted or substituted with one or more substituents, optionally including non-H R as described below. 25 It may be substituted with one or more substituents selected from the group.

[0092] The divalent electron-accepting group other than the formula (II) is arbitrarily selected from the formulas (IVa) to (IVe), [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0093] 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.

[0094] R 25 are H, F, CN, NO2, 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), 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), optionally phenyl, or [ka]

[0095] Or [ka]

[0096] are independently selected from

[0097] 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,

[0098] 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 61are independently CN, CF3, or COOR 40 ) and

[0099] 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 COOR 40 ) and

[0100] R 40 is, at each occurrence, H or a substituent, preferably H or C 1-20 It is a hydrocarbyl group.

[0101] Z 1 is N or P.

[0102] 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:

[0103] Electron-accepting group A 2 , A 3

[0104] 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 the same.

[0105] Exemplary monovalent acceptor units include, but are not limited to, units of formulae (IIIa)-(IIIq): [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0106] 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.

[0107] The N atom in formula (IIIe) may be unsubstituted or substituted.

[0108] 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.

[0109] Preferably, R 10 is H.

[0110] J is O or S, preferably O.

[0111] 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.

[0112] R 15 are 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 1~12Alkyl (wherein one or more non-adjacent C atoms are O, S, NR 7 , COO, or CO; 2 , optionally phenyl, or [ka] [ka] [ka] [ka] [ka]

[0113] is a group selected from

[0114] R 16 is H or a substituent, preferably

[0115] -(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] [ka] [ka] [ka] [ka]

[0116] and

[0117] 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.

[0118] Ar 6 is a 5-membered heteroaromatic group, preferably thiophene or furan, which is unsubstituted or substituted with one or more substituents.

[0119] Ar 3 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.

[0120] T 1 , T 2 , and T 3 are each independently as defined above.

[0121] 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

[0122] Preferred group A 2 and A 3 D 1 Or D 2 , or B if present 2 is a group having a non-aromatic carbon-carbon bond directly bonded to

[0123] Preferably, A 2 and A3 At least one of, preferably A 2 and A 3 both of which have a group of formula (IIIa-1) [ka]

[0124] During the ceremony,

[0125] R 10 But as mentioned above,

[0126] each X 7 ~X 10 Independently, CR 12 or N, where R 12 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;

[0127] 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.

[0128] 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.

[0129] Exemplary groups of formula (IIId) include: [ka] [ka] [ka]

[0130] Exemplary groups of formula (IIIe) include: [ka] [ka]

[0131] Exemplary groups of formula (IIIq) are: [ka]

[0132] Exemplary groups of formula (IIIg) are: [ka]

[0133] Exemplary groups of formula (IIIj) are: [ka]

[0134] 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.

[0135] Exemplary groups of formula (IIIm) are: [ka] [ka]

[0136] Exemplary groups of formula (IIIn) are: [ka]

[0137] 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.

[0138] Optionally, R 14 is C 1~12 Alkyl, unsubstituted phenyl, and one or more C 1~12 phenyl substituted with an alkyl group.

[0139] 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.

[0140] Optionally, the group of formula (IIIo) is selected from: [ka] [ka] [ka]

[0141] Cross-linking unit

[0142] Cross-linking unit B 1 and B. 2 are preferably each selected from vinylene, arylene, heteroarylene, arylenevinylene, and heteroarylenevinylene, each of which may be unsubstituted or substituted with one or more substituents, where the arylene and heteroarylene groups are monocyclic or bicyclic groups.

[0143] Cross-linking unit B 1 and B. 2 is preferably a monocyclic or fused bicyclic arylene group or heteroarylene group, more preferably a monocyclic or fused bicyclic heteroarylene group.

[0144] x 1 and x 2 is at least 1, then each B 1 are preferably the same.

[0145] z 1 and z 2 is at least 1, then each B 2 are preferably the same.

[0146] Optionally, B 1 and B. 2 are independently selected from units of formulae (VIa) to (VIn), [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka] [ka]

[0147] In the formula, 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.

[0148] R 8 is preferably H, C 1~20 Alkyl, -COO-C 1~19Alkyl, C 1~19 Alkoxy or C 1~19 It is a thioalkyl.

[0149] Electron-donating group D 1 and D. 2

[0150] Electron-donating group D 1 and D. 2 is preferably a fused aromatic or heteroaromatic group, more preferably a fused heteroaromatic group containing three or more rings.

[0151] At least one D 1 and / or at least one D 2 Preferably, each D 1 and / or each D 2 Most preferably, D 1 and D. 2 Each occurrence contains at least four fused rings.

[0152] D 1 and D 2 and may be the same or different. Preferably, they are the same.

[0153] Particularly preferred electron donating groups include fused thiophene or furan rings, optionally fused rings comprising 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.

[0154] Exemplary Electron Donor Groups D Having at Least Four Fused Rings 1 and D. 2 Examples of the groups include the groups of the formulae (VIIa) to (VIIs): [ka] [ka]

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[0155] If present, the electron donating group D has only three fused rings 1 and D. 2 can be selected from the groups of formulae (VIIIa) to (VIIIe), [ka] [ka] [ka] [ka] [ka]

[0156] In the formula, Y A is independently at each occurrence O, S, or NR 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 R 55 is independently at each occurrence H or a substituent; R 53 is independently a substituent at each occurrence.

[0157] Optionally, R 51 and R 52 are independently H, F, C at 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.

[0158] In some embodiments, Ar 3 may be an aromatic group, for example phenyl.

[0159] 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.

[0160] Preferably, each R 54 is H, F, 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

[0161] 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.

[0162] 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.

[0163] Preferably R 54is C 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.

[0164] Preferably, each R 51 is H.

[0165] 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) substituted aryl or heteroaryl, preferably phenyl.

[0166] Preferably, R 55 is H or C 1~30 It is a hydrocarbyl group.

[0167] In some embodiments, y 1 and y 2 are each equal to 1.

[0168] 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 may be linked in any orientation.

[0169] Electron-donating materials

[0170] The bulk heterojunction layers described herein comprise an electron donating material and a compound of formula (I) described herein.

[0171] Exemplary donor materials are disclosed, for example, in WO2013051676, the contents of which are incorporated herein by reference.

[0172] The electron donating material can be a non-polymeric or polymeric material.

[0173] 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.

[0174] Preferred are amorphous or semi-crystalline conjugated organic polymers.

[0175] 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.

[0176] 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.

[0177] Particularly preferred donor polymers include a donor unit (VIIIa) 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.

[0178] Another particularly preferred donor polymer comprises donor repeat units and electron accepting repeat units, where the donor units are optionally substituted benzo[1,2-b:4,5-b']dithiophene units.

[0179] Optionally, the polymer comprises an electron donating benzo[1,2-b:4,5-b']dithiophene repeat unit of formula (X): [ka]

[0180] In the formula, R 17 and R 18 are each independently H, F, or C 1~20 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); 10 , is selected from.

[0181] Particularly preferred electron accepting repeat units of polymers comprising optionally substituted benzo[1,2-b:4,5-b']dithiophene unit donor units are repeat units of formula (XI): [ka]

[0182] In the formula, R 27 and R 28 are each independently selected from H or a substituent, more preferably an electron-withdrawing substituent, with R 27 and R 28 is an electron-withdrawing substituent. Exemplary electron-withdrawing substituents are F, CN, NO2, and COOR. 29 (In the formula, R 29is C 1~20 A hydrocarbyl group, optionally C 1~12 Alkyl or one or more C 1~12 phenyl optionally substituted with an alkyl group.

[0183] Additional Electron Accepting Materials

[0184] In some embodiments, the compound of formula (I) described herein is the only electron accepting material of the bulk heterojunction layer.

[0185] In some embodiments, the bulk heterojunction layer contains a compound of formula (I) 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.

[0186] 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.

[0187] 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 60TCBM), and ThCBM-type fullerene derivatives (e.g., thienyl-C 61 -Butyric acid methyl ester (C 60 Examples include ThCBM).

[0188] The fullerene derivative may have the formula (V): [ka]

[0189] 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.

[0190] Exemplary fullerene derivatives include those of formulae (Va), (Vb), and (Vc): [ka] [ka] [ka]

[0191] In the formula, R 20 ~R 32 are each independently H or a substituent.

[0192] 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.

[0193] 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.

[0194] compound

[0195] The bulk heterojunction layer may be formed by any process, including, but not limited to, thermal evaporation and solution deposition methods.

[0196] 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.

[0197] One or more solvents of the formulation are optionally chlorine, C 1~10 Alkyl and C 1~10 Alkoxy (wherein two or more substituents are linked together and 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.

[0198] 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.

[0199] 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.

[0200] Organic Electronic Devices

[0201] 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.

[0202] 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.

[0203] Each of the anode and cathode, independently, may be a single conductive layer or may include multiple layers.

[0204] 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.

[0205] 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.

[0206] 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.

[0207] 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

[0208] 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.

[0209] 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.

[0210] Purpose

[0211] 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.

[0212] In some embodiments, the photodetector system includes a plurality of photodetectors as described herein, for example, an image sensor of a camera.

[0213] In some embodiments, the 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, preferably at least 1000 nm, optionally in the range of 1000-1500 nm.

[0214] 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.

[0215] 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.

[0216] 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.

[0217] EXAMPLES

[0218] Compound Example 1

[0219] Compound Example 1 was prepared according to the following reaction scheme. [ka]

[0220] Compound 1 was developed by Zhang et al, “Electron-Deficient and Quinoid Central Unit Engineering for Unfused Ring-Based A1-D-A2-D-A1-Type Acceptor Enables High Performance Nonfullerene Polymer Solar Cells with High V oc and PCE Simultaneously” Small 2020, 16, 1907681.

[0221] compound 2

[0222] A solution of compound 1 (3.94 g, 1.97 mmol) in toluene (100 mL) was degassed for 45 min. Intermediate 1 (0.29 g, 0.82 mmol), Pd2(dba)3 (0.06 g, 0.07 mmol), and P(o-Tol)3 (0.08 g, 0.25 mmol) were added and the mixture was heated to 65° C. under nitrogen for 3.5 h and stirred at room temperature overnight. After this time, additional catalyst (60 mg) and ligand (75 mg) were added and the solution was heated to 100° C. for 1 h. An additional 90 mg of BisBT-diBr was added (50 mg) and the solution was heated at 100° C. for an additional 4.5 h. After this time, the mixture was cooled to room temperature and the solvent was removed under vacuum to give a red / brown solid. The crude residue was purified by column chromatography (heptane / dichloromethane and toluene / heptane) to give compound 2 (100 g) as a dark red / brown solid.

[0223] compound 3

[0224] Compound 2 (0.90 g, 0.45 mmol) was added to DMF (30 mL) under nitrogen and the mixture was gently heated until dissolved. The mixture was then cooled to approximately 2° C. in an ice bath. POCl3 (0.45 mL, 4.47 mmol) was added dropwise (maintaining temperature below 5° C.). Once the addition was complete, the mixture was stirred at room temperature for 15 min and then heated to 80° C. for 3.5 h. The reaction was then cooled to room temperature and quenched with saturated sodium acetate, followed by the addition of additional water. The mixture was extracted three times with toluene and the organic phases were combined and extracted with aqueous NaCl to remove any residual DMF. The crude residue was purified by column chromatography (toluene) to give compound 3 (0.99 g) as a red / brown solid.

[0225] Compound Example 1

[0226] Compound 3 (0.63 g, 0.30 mmol), intermediate 2 (0.39 g, 1.52 mmol) and p-toluenesulfonic acid (0.43 g, 2.28 mmol) were placed in a flask under nitrogen. Toluene (8 mL) and ethanol (16 mL) were added and the mixture was purged with nitrogen for 15 minutes. It was then heated to 65° C. overnight. After cooling to room temperature, it was filtered and washed twice with hot EtOH (25 mL), three times with hot MeOH (25 mL) and three times with pentane (25 mL) to give 0.66 g of a black solid. The crude solid was purified by column chromatography (dichloromethane / heptane), dissolved in dichloromethane (10 mL) and reprecipitated in pentane (100 mL) to give compound Example 1 (0.23 g) as a black solid.

[0227] 1H NMR(300MHz,THF-d8):δ 9.15(bs,2H), 9.01(d,3.93Hz,2H), 8.42(s,2H),8.12(s,2H), 8.05(bs,2H),7.88(s,2H), 7.38(d,8.11Hz,8H), 7.27(d, 7.73Hz,8H), 7.13(t,7.93Hz,16H), 2.58(t,7.01Hz,16H), 1.62-1.57(m,16H), 1.36-1.28(m,48H), 0.89-0.85(m,24H).

[0228] LCMS(APCI+ve):2513.45([M]+).

[0229] Compound Example 2

[0230] Compound Example 2 was prepared as described for Compound Example 1, except that Compound 4 was used instead of Compound 1, according to the following reaction scheme.

[0231] Compound 4 may be prepared as described in WO 2020 / 109825, the contents of which are incorporated herein by reference. [ka]

[0232] Absorption spectrum

[0233] The absorption spectrum of Compound Example 1 in o-dichlorobenzene solution is shown in Figure 2. It is overlaid with the absorption spectrum of Comparative Compound 1 shown below, which is based on Zhang et al., "Electron-Deficient and Quinoid Central Unit Engineering for Unfused Ring-Based A1-D-A2-D-A1-Type Acceptor Enables High Performance Nonfullerene Polymer Solar Cells with High V ocand PCE Simultaneously”, Small, DOI: 10.1002 / smll.201907681.

[0234] As shown in FIG. 2, the absorption peak of compound Example 1 is around 1000 nm, whereas the absorption peak of comparative compound 1 is around 700 nm. [ka]

[0235] Figure 3 shows the 1×10 -6 1 shows the absorption spectra of compound Example 2 in a toluene solution at M and in a film coated from the toluene solution. Compound Example 2 has a HOMO of −5.16 eV and a LUMO of −4.11 eV as measured by square wave voltammetry of a film of Compound Example 2.

[0236] Device Example 1

[0237] An organic photodetector was prepared having the following structure:

[0238] Cathode / donor:acceptor layer / anode

[0239] Glass-like substrates coated with an indium-tin oxide (ITO) layer were treated with polyethyleneimine (PEIE) to modify the working function of ITO.

[0240] A mixture of donor polymer 1 (donor, shown below), compound example 2 (non-fullerene acceptor) and PCBM (fullerene acceptor) in a donor:NFA:fullerene mass ratio of 1:0.875:0.625 was deposited on the modified ITO layer by bar coating from a 10 mg / ml solution in a 90:10 v / v solvent mixture of 1,2,4 trimethylbenzene:butylbenzoate. The film was dried at 80 °C to form a bulk heterojunction layer approximately 350-400 nm thick. An anode stack of MoO3 (10 nm) and ITO (50 nm) was formed on the bulk heterojunction by thermal evaporation (MoO3) and sputtering (ITO).

[0241] Donor Polymer 1 is a donor-acceptor polymer having donor repeat units of formula (VIIa) and acceptor repeat units, as shown below: Donor Polymer 1 may be prepared as described in WO 2013 / 051676, the contents of which are incorporated herein by reference. [ka]

[0242] Device Example 2

[0243] Device Example 2 was prepared as described for Device Example 1, except that Donor Polymer 2 was used instead of Donor Polymer 1. [ka]

[0244] The external quantum efficiency and dark current of device examples 1 and 2 are shown in Figures 4 and 5, respectively.

[0245] Modeling Example

[0246] All modeling described in these examples was carried out using Gaussian09 software available from Gaussian, using Gaussian09 with B3LYP (functional).

[0247] The HOMO and LUMO levels were modeled for individual donor and acceptor units, and the results are shown in Tables 1-3. Table 1 [Table 1-1] TIFF2024533974000127.tif80154 [Table 1-2] Table 2 [Table 2] Table 3 [Table 3-1] [Table 3-2]

[0248] Compounds with donor groups having three fused rings and more than three fused rings D were modeled and the results are shown in Table 4, where S1f corresponds to the oscillator strength of the transition from S1 (predicts the absorption intensity) and Eopt is the modeled optical gap.

[0249] As shown in Table 4, compounds containing donor groups with four or more fused rings have longer wavelength optical gaps than comparative compounds in which the donor groups have only three fused rings. Table 4 [Table 4-1] [Table 4-2] [Table 4-3]

Claims

1. A compound of formula (I), 【Chemical 1】 wherein, A １ is a divalent heteroaromatic electron-withdrawing group containing at least three condensed aromatic rings, A ２ and A ３ are each independently a monovalent electron-withdrawing group, D １ and D ２ is, independently at each occurrence, an electron-donating group, and at least one occurrence of at least one of D １ and D ２ is a condensed heteroaromatic group containing at least four condensed rings B １ and B ２ are each independently a crosslinking group upon each occurrence, 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 is, independently of each other, 0, 1, 2, or 3, a compound.

2. A compound of formula (I), 【Chemical 2】 wherein, A １ is a divalent heteroaromatic electron-accepting group having a modeled LUMO that exceeds 2.70 eV from the vacuum level, A ２ and A ３ are each independently a monovalent electron-withdrawing group, D １ and D ２ is, independently at each occurrence, an electron-donating group, and at least one occurrence of at least one of D １ and D ２ is a condensed heteroaromatic group containing at least four condensed rings B １ and B ２ is independently a crosslinking group each time it appears, x １ and x ２ each independently is 0, 1, 2, or 3, y １ and y ２ are each independently at least 1, z １ and z ２ is, independently of one another, 0, 1, 2, or 3, a compound.

3. A １ is a group of formula (II), [Chemical Formula 3] wherein, Ar １ is a monocyclic or polycyclic aromatic or heteroaromatic group, Y is O, S, NR ４ or R １ -C=C-R １ wherein, R １ is, in each occurrence, independently H or a substituent, 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 or 2.

4. A １ The compound according to claim 3, wherein A is a group of formula (IIa). 【Chemical Formula 4】

5. The compound according to claim 3, wherein the group of formula (II) has formula (IIb). 【Chemical Formula 5】

6. Two Rs １ The compound according to claim 5, wherein the two Rs are not bonded.

7. 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 and may be replaced, one or more H atoms may be replaced by F, C １～２０ alkyl, and may be unsubstituted or may be substituted with one or more substituents, and are independently selected from aryl or heteroaryl, wherein R ３ to R ４ are each independently H or a substituent, the compound according to claim 6.

8. Two Rs １ The compound according to claim 5, in which two Rs are bonded.

9. The compound of formula (IIb) has formula (IIb-1) or (IIb-2), [Chemical Formula 6] 【Chemical Formula 7】 wherein, 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 8.

10. Ar ２ The compound according to claim 9, wherein Ar is unsubstituted or benzene substituted with one or more substituents.

11. A １ The compound according to claim 2, wherein A is a thiophene condensed with a 5- or 6-membered heteroaromatic group containing at least one nitrogen ring atom.

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

13. 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, a compound according to claim 1 or 2.

14. D １ and D ２ are each independently selected from the units of formulas (VIIa) to (VIIp), 【Chemical 8】 【Chemical Formula 9】 【Chemical Formula 10】 【Chemical 11】 【Chemical 12】 【Chemical 13】 【Chemical 14】 【Chemical Formula 15】 【Chemical 16】 【Chemical 17】 【Chemical Formula 18】 【Chemical 19】 【Chemical 20】 【Chemical 21】 【Chemical 22】 【Chemical 23】 【Chemical Formula 24】 【Chemical 25】 【Chemical 26】 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 each independently H or a substituent, and R ５３ is independently a substituent each time it appears, the compound according to claim 1 or 2.

15. 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 is directly bonded to, the compound according to claim 1 or 2.

16. A ２ and A ３ each independently selected from the groups of formula (IIIa) to (IIIq), 【Chemical 27】 【Chemical 28】 【Chemical 29】 【Chemical Formula 30】 【Chemical 31】 【Chemical 32】 【Chemical 33】 【Chemical 34】 【Chemical 35】 【Chemical 36】 【Chemical 37】 【Chemical Formula 38】 【Chemical Formula 39】 【Chemical 40】 【Chemical Formula 41】 【Chemical 42】 【Chemical 43】 wherein, U is an unsubstituted or substituted 5- or 6-membered ring with one or more substituents and may be fused to one or more additional rings, R １０ is H or a substituent, J is O or S, 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 which may be fused to one or more further 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 or 2, which is a fused heteroaromatic group bonded to the aromatic C atom of B

17. A ２ and A ３ at least one of which is a group of formula (IIIa-1), 【Chemical 44】 wherein, Each X １ to X ４ is independently CR １２ or N, wherein R １２ is H at each occurrence or is a substituent selected from C １～２０ hydrocarbyl and an electron-withdrawing group, the compound according to claim 16.

18. The compound according to claim 1 or 2, wherein the compound has an absorption peak above 900 nm.

19. A composition comprising an electron-donating material and an electron-accepting material, wherein the electron-accepting material is the compound according to claim 1 or 2.

20. An organic electronic device comprising an active layer comprising the compound or composition according to claim 1 or 2.

21. The organic electronic device according to claim 20, wherein 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 19.

22. The organic electronic device according to claim 21, wherein the organic photo-responsive device is an organic photodetector.

23. A photosensor comprising a light source and the organic photodetector according to claim 22, wherein the photosensor is configured to detect light emitted from the light source.

24. The photosensor according to claim 23, wherein the light source emits light having a peak wavelength above 900 nm.

25. A formulation comprising the compound or composition according to claim 1 or 2 dissolved or dispersed in one or more solvents.

26. A method of forming the organic electronic device according to claim 20, wherein the formation of the active layer comprises deposition of the formulation according to claim 25 onto a surface and evaporation of the one or more solvents.

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