TW202448894A - Compound - Google Patents

Abstract

A compound of formula (I): wherein: X ¹is O, S, Se, NR ²or PR ²wherein R ²in each occurrence is H or a substituent; Y ¹is O, S or Se; Ar ¹in each occurrence is independently an unsubstituted or substituted monocyclic or polycyclic aryl or heteroaryl group or is absent; R ¹in each occurrence is independently a substituent; B ¹independently in each occurrence is a bridging group; f1 and f2 are each 1; g is at least 1; and A in each occurrence is independently a monovalent electron-accepting group.

Description

Compound

Compound

WO2022/129137 discloses a compound of the formula EAG-EDG-EAG, wherein EDG is a group of formula (II) and each EAG is independently an electron accepting group of formula (III):

WO2021/079140 discloses a composition comprising an electron acceptor material and an electron donor material, wherein the electron acceptor material is a compound of the formula EAG-EDG-EAG, wherein each EAG is an electron acceptor group and EDG is a group of the following formula:

The present disclosure provides compounds of formula (I): (I) wherein: X ¹ is O, S, Se, NR ² or PR ² , wherein R ² at each occurrence is H or a substituent; Y ¹ is O, S or Se; Ar ¹ at each occurrence is independently an unsubstituted or substituted monocyclic or polycyclic aromatic or heteroaromatic group or is absent; R ¹ at each occurrence is independently a substituent; B ¹ at each occurrence is independently a bridging group; f1 and f2 are each 1; g is at least 1; and A at each occurrence is independently a monovalent electron accepting group.

Optionally, at least one A is an electron accepting group of formula (II): (II) wherein: G is C=O, C=S, SO, SO ₂ , NR ³³ or C(R ³³ ) ₂ , wherein R ³³ is CN or COOR ⁴⁰ , wherein R ⁴⁰ is H or a substituent at each occurrence; R ³ is H or a substituent; Z is each independently CN, CF ₃ or COOR ⁴⁰ , wherein R ⁴⁰ is H or a substituent at each occurrence; and Ar ² is an unsubstituted or substituted monocyclic or polycyclic aromatic ring or heterocyclic aromatic ring.

According to the compound of technical solution 2, Ar ² is selected from: benzene substituted with at least one CN substituent; and unsubstituted or substituted monocyclic or polycyclic heteroaromatic groups.

Optionally, the group of formula (II) has formula (IIa): (IIa) wherein ^X7 - ^X10 are each independently ^CR12 or N, wherein ^R12 at each occurrence is H or a substituent selected from _C1-20 alkyl and electron withdrawing groups, with the proviso that when each of ^X7 - ^X10 is ^CR12 , at least one ^R12 is CN.

Optionally, the group of formula (II) has formula (IIb): (IIb) wherein Ar ³ is an unsubstituted or substituted monocyclic or polycyclic aromatic or heteroaromatic group.

Optionally, ^Ar2 is benzene substituted with at least one CN substituent.

Optionally, ^B1 is selected from unsubstituted or substituted furan; unsubstituted or substituted thiophene; or a fused analog thereof.

Optionally, ^B1 is a group of formula (III): (III) wherein Y ² is O, S or Se; and Ar ⁴ is an unsubstituted or substituted monocyclic or polycyclic aromatic or heteroaromatic group.

Optionally, the group of formula (III) is a group of formula (IIIa): (IIIa) wherein R ⁸ at each occurrence is H or a substituent.

Optionally, each Ar ¹ is absent.

The present disclosure provides a composition comprising a compound as described herein and an electron donating material.

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

The present disclosure provides an organic photoresponsive device, comprising an anode, a cathode, and a photoactive layer disposed between the anode and the cathode, wherein the photoactive layer comprises the composition as described herein.

The present disclosure provides a photo sensor comprising a light source and an organic photodetector as described herein, wherein the organic photodetector is configured to detect light emitted from the light source. Optionally, the light source emits light with a peak wavelength greater than 1000 nm.

Unless the context clearly requires otherwise, throughout the specification and claims, the words "comprise," "comprising," and the like are to be interpreted in an inclusive sense, and not in an exclusive or exhaustive sense; in other words, in the sense of "including, but not limited to." In addition, when used in this application, the words "herein," "above," "below," and words of similar import refer to this application as a whole and not to any particular part of this application. Where the context permits, words in the embodiments using the singular or plural may also include the plural or singular, respectively. The word "or" referring to a list of two or more items includes all of the following interpretations of the word: any one of the items in the list, all of the items in the list, and any combination of the items in the list. When used in this application, reference to a layer being "on" another layer means that the layers may be in direct contact or one or more intervening layers may be present. When used in this application, reference to a layer being "on" another layer means that the layers are in direct contact. Unless specifically stated otherwise, reference to a particular atom includes any isotope of that atom.

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

These and other variations can be made to the technology in light of the detailed description below. Although this specification describes certain examples of the technology, and describes the best mode contemplated, no matter how detailed this specification presents, the technology can be practiced in many ways. As mentioned above, when describing certain features or scopes of the technology, the use of specific terms should not be understood to imply that the term is redefined herein to be limited to any specific characteristics, features, or scope of the technology with which the term is associated. In general, unless such terms are expressly defined in the implementation section, the terms used in the following patent application scope should not be interpreted as limiting the technology to the specific examples disclosed in this specification. Therefore, the actual scope of the technology covers not only the examples disclosed, but also all equivalent ways of implementing or performing the technology according to the scope of the claims.

In order to reduce the number of patent claims, certain areas of the technology are presented below in the form of certain patent claims, but the applicant envisions various areas of the technology in multiple patent claim forms.

In the following description, for the purpose of explanation, numerous specific details are set forth in order to provide a thorough understanding of the implementation of the disclosed technology. However, it will be apparent to those skilled in the art that embodiments of the disclosed technology can be practiced without some of these specific details. Donor group D

The compound of formula (I) comprises an electron donating group D: (D) X ¹ is O, S, Se, NR ² or PR ² , wherein R ² is H or a substituent at each occurrence. Y ¹ is O, S or Se. Ar ¹ is independently unsubstituted or substituted monocyclic or polycyclic aryl or heteroaryl at each occurrence or absent. g is at least 1, preferably 1, 2 or 3. R ¹ is independently a substituent at each occurrence.

Preferably, R ¹ is independently selected at each occurrence from: C _1-20 alkyl, wherein one or more non-adjacent C atoms may be replaced by O, S, NR ¹⁷ , wherein R ¹⁷ is C _1-12 alkyl, COO or CO and one or more H atoms of the alkyl may be replaced by F; and aromatic or heteroaromatic groups, preferably C _6-20 aryl, more preferably phenyl, which is unsubstituted or substituted by one or more substituents.

Where present, substituents of the aromatic or heteroaromatic group R ¹ are preferably selected from substituents R ¹¹ , wherein R ¹¹ at each occurrence is independently selected from F, Cl, Br, CN, NO ₂ and C _1-20 alkyl, wherein one or more non-adjacent C atoms may be replaced by O, S, NR ¹⁷ , wherein R ¹⁷ is C _1-12 alkyl, COO or CO and one or more H atoms of the alkyl may be replaced by F.

Y ¹ is independently selected at each occurrence from F, Cl, Br, CN, NO ₂ and C _1-20 alkyl, wherein one or more non-adjacent C atoms may be replaced by O, S, COO, CO or NR ¹⁷ , wherein R ¹⁷ is C _1-12 alkyl, and wherein one or more H atoms of the alkyl may be replaced by F.

R ¹⁷ is optionally C _1-12 alkyl or phenyl, which is unsubstituted or substituted with one or more C _1-6 alkyl groups.

By "non-terminal C atom" of an alkyl group as used anywhere herein is meant a C atom other than the C atom of a methyl group at the terminal end of a normal alkyl chain or the C atom of a methyl group at the terminal end of a branched alkyl chain.

If a terminal C atom of a group described anywhere herein is replaced, the resulting group may be a cationic group comprising a counter cation, such as an ammonium or metal counter cation, preferably an ammonium or alkali metal cation.

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

^R2 is preferably H; _C1-12 alkyl, wherein one or more C atoms of the _C1-12 alkyl except the terminal C atom or the C atom bound to the N of ^NR2 may be replaced by O, S, CO or COO; or an aromatic or heteroaromatic group, preferably a _C6-12 aryl group, more preferably a phenyl group, which may be unsubstituted or substituted by one or more substituents.

Where present, substituents for the aromatic or heteroaromatic group R ² are preferably selected from R ¹¹ as described above.

More preferably, R ² is H or C _1-20 alkyl.

A C _1-20 alkyl group as described anywhere herein may be selected from C _1-20 alkyl groups; unsubstituted phenyl groups; and phenyl groups substituted with one or more C _1-12 alkyl groups.

Each of the electron accepting groups A of formula (I) has a lowest unoccupied molecular orbital (LUMO) energy level that is deeper (i.e., further from vacuum) than the donor group D of formula (I), preferably at least 1 eV deeper. The LUMO energy levels of the electron accepting groups A and the electron donating groups D can be determined by modeling the LUMO energy levels of these groups, wherein each bond to a neighboring group is replaced by a bond to a hydrogen atom. Modeling can be performed using Gaussian09 software obtained from Gaussian, using Gaussian09 with B3LYP (functional) and LACVP* (basis function set).

Preferably, the compound of formula (I) has a peak absorption wavelength greater than 1000 nm, optionally at least 1200 nm, preferably less than 1800 nm.

Each Ar ¹ may be present or absent independently. In embodiments where Ar ¹ is absent, the group D has the formula D-1: (D-1) wherein R ⁴ at each occurrence is independently H or a substituent, optionally H or a substituent R ¹¹ as described above. Preferably, each R ⁴ is H.

Optionally, only one Ar ¹ group is present.

Optionally, there are two Ar ¹ groups, in which case the Ar ¹ groups are the same or different. Preferably, Ar ¹ is independently selected at each occurrence from furan; thiophene; furanofuran; thienothiophene; and furanothiophene. Substituents for Ar ^1, if present, are optionally selected from substituents R ¹¹ as described above. Bridging unit

The bridging unit ^B1 is preferably selected from a vinyl group, an aryl group and a heteroaryl group. The aryl group and the heteroaryl group are preferably monocyclic or bicyclic groups, and each may be unsubstituted or substituted with one or more substituents.

Preferably, each B ¹ contains at least one arylene group or heteroarylene group, more preferably at least one heteroarylene group.

Exemplary monocyclic aromatic and heteroaromatic groups B ¹ are benzene, thiophene and furan, each of which may be unsubstituted or substituted with one or more substituents, optionally substituted with one or more substituents R ⁸ as described below.

Exemplary bicyclic groups ^B1 are selected from formula (III) and (IV): (III) (IV) wherein Ar ⁴ is an unsubstituted or substituted monocyclic aromatic or heteroaromatic group, preferably benzene; thiophene; furan; pyridine; or piperidine, each of which may be unsubstituted or substituted with one or more substituents, optionally substituted with one or more substituents R ⁸ as described below, and Y ² is O, S or Se.

The extended aryl group ^B1 is optionally selected from units of formula (VIa) to (VIo): (VIa) (VIb) (VIc) (VId) (VIe) (VIf) (VIg) (VIh) (VIi) (VIj) (VIk) (VIl) (VIm) (VIn) (VIo) wherein R ⁵⁵ is H or a substituent, optionally H or C _1-20 alkyl; and R ⁸ is independently H or a substituent at each occurrence, preferably H or a substituent selected from the following: F; CN; NO ₂ ; C _1-20 alkyl, wherein one or more non-adjacent C atoms may be replaced by O, S, NR ⁶ , COO or CO and one or more H atoms of the alkyl may be replaced by F; phenyl which is unsubstituted or substituted with one or more substituents; and -B(R ¹⁴ ) ₂ , wherein R ¹⁴ is a substituent at each occurrence, optionally C _1-20 alkyl.

Substituents for the phenyl group R ⁸ , if present, may be selected from the substituents R ¹¹ as described above.

^R6 is H or a substituent, preferably H or a _C1-20 alkyl group.

A C _1-20 alkyl group as described anywhere herein may be selected from C _1-20 alkyl groups; unsubstituted phenyl groups; and phenyl groups substituted with one or more C _1-12 alkyl groups.

The R ⁸ groups of formula (VIa), (VIb) and (VIc) may be linked to form a bicyclic ring, which may be substituted by one or more substituents, optionally substituted by one or more substituents selected from F; CN; NO ₂ ; C _1-20 alkyl, wherein one or more non-adjacent C atoms may be replaced by O, S, NR ⁶ , COO or CO and one or more H atoms of the alkyl may be replaced by F.

^R8 is preferably H, _C1-20 alkyl or _C1-19 alkoxy.

The R ⁸ groups in formula (VIa), (VIb) and (VIc) may be linked to form a bicyclic ring which may be substituted.

The monovalent receptor groups A can each be independently selected from any such units known to the skilled artisan.

The A groups in the compounds of formula (I) may be the same or different, preferably the same.

Exemplary monovalent acceptor groups include, but are not limited to, groups of formula (IXa)-(IXq): (IXa) (IXb) (IXc) (IXd) (IXe) (IXf) (IXg) (IXh) (IXi) (IXj) (IXk) (IXl) (IXm) (IXn) (IXo) (IXp) (IXq)

U is a 5- or 6-membered ring which is unsubstituted or substituted with one or more substituents and which may be fused to one or more other rings.

G is C=O, C=S, SO, SO ₂ , NR ³³ or C(R ³³ ) ₂ , wherein R ³³ is CN or COOR ⁴⁰ . G is preferably C=O or SO ₂ , more preferably C=O.

The N atom of formula (IXe) may be unsubstituted or substituted.

R ³ is H or a substituent, preferably H or a substituent selected from the group consisting of: C _1-12 alkyl, wherein one or more non-adjacent C atoms may be replaced by O, S, NR ⁶ , COO or CO and one or more H atoms of the alkyl may be replaced by F; and an aromatic group, optionally a phenyl group, which is unsubstituted or substituted with one or more substituents selected from F and C _1-12 alkyl, wherein one or more non-adjacent C atoms may be replaced by O, S, NR ⁶ , COO or CO.

Most preferably, ^R3 is H.

J is O or S, preferably O.

R ¹³ is a substituent at each occurrence, optionally C _1-12 alkyl, wherein one or more non-adjacent C atoms may be replaced by O, S, NR ⁶ , COO or CO and one or more H atoms of the alkyl may be replaced by F.

R ¹⁵ is independently H at each occurrence; F; C _1-12 alkyl, wherein one or more non-adjacent C atoms may be replaced by O, S, NR ⁶ , COO or CO and one or more H atoms of the alkyl may be replaced by F; an aromatic group, optionally phenyl, which is unsubstituted or substituted by one or more substituents selected from F and C _1-12 alkyl, wherein one or more non-adjacent C atoms may be replaced by O, S, NR ⁶ , COO or CO; or a group selected from the following: ; ; ; , .

R ¹⁶ is H or a substituent, preferably a substituent selected from the following: -(Ar ⁵ ) _w , wherein Ar ⁵ is independently unsubstituted or substituted aryl or heteroaryl at each occurrence, preferably thiophene, and w is 1, 2 or 3; ; ; ; , and C _1-12 alkyl, wherein one or more non-adjacent C atoms may be replaced by O, S, NR ⁶ , COO or CO and one or more H atoms of the alkyl may be replaced by F.

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

Substituents for ^Ar5 and ^Ar6 , where present, are optionally selected from _C1-12 alkyl groups, wherein one or more non-adjacent C atoms may be replaced by O, S, ^NR6 , COO or CO and one or more H atoms of the alkyl group may be replaced by F.

T ¹ , T ² and T ³ each independently represent an aryl or heteroaryl ring which may be fused to one or more other rings, optionally benzene. Substituents for T ¹ , T ² and T ³ , if present, are optionally selected from non-H groups of R ^25. In a preferred embodiment, T ³ is benzothiadiazole.

^Z1 is N or P.

Ar ⁸ is a fused heteroaromatic group which is unsubstituted or substituted with one or more substituents, optionally substituted with one or more non-H substituents R ³ , and which is bound to an aromatic C atom of B ¹ or B ² and to a boron substituent of B ¹ or B ² .

Preferred group A is a group having a non-aromatic carbon-carbon bond directly bonded to ^B1 .

Preferably at least one A, preferably two groups A are groups of formula (II): (II) wherein: G is as described above and is preferably C=O or SO ₂ , more preferably C=O; R ³ is as described above; Ar ² is an unsubstituted or substituted monocyclic or fused aromatic or heteroaromatic group, preferably benzene or a monocyclic or bicyclic heteroaromatic group having only C or N ring atoms, such as quinoxaline; and each Z is independently CN, CF ₃ or COOR ⁴⁰ , wherein R ⁴⁰ is H or a substituent at each occurrence, preferably H or a C _1-20 alkyl group. Preferably, each Z is the same. Preferably, each Z is CN.

Ar ² may be unsubstituted or substituted with one or more substituents. The substituents of Ar ² are preferably selected from the groups R ¹¹ described above.

Optionally, the group of formula (II) has formula (IIa): (IIa) ^X7 - ^X10 are each independently ^CR12 or N, wherein ^R12 at each occurrence is H or a substituent selected from _C1-20 alkyl and electron withdrawing groups. Preferably, the electron withdrawing group is F, Cl, Br or CN, more preferably F, Cl or CN; and most preferably CN.

The C _1-20 alkyl group R ¹² may be selected from C _1-20 alkyl groups; unsubstituted phenyl groups; and phenyl groups substituted by one or more C _1-12 alkyl groups.

In a particularly preferred embodiment, each of ^X7 - ^X10 is ^CR12 and each ^R12 is independently selected from H or an electron withdrawing group, preferably H, F or CN. According to this embodiment, ^R12 of ^X8 and ^X9 is an electron withdrawing group, preferably F or CN.

Optionally, the group of formula (II) has formula (IIb): (IIb) wherein Ar ³ is an unsubstituted or substituted monocyclic or polycyclic aromatic or heteroaromatic group. Preferably, Ar ³ is benzene which is unsubstituted or substituted with one or more substituents. The substituent of Ar ³ may be selected from R ¹¹ as described above, more preferably R ¹² as described above.

Exemplary groups of formula (IXd) include:

Exemplary groups of Formula (IXe) include:

Exemplary groups of formula (IXq) are: `

Exemplary groups of formula (IXg) are:

Exemplary groups of formula (IXj) are: wherein Ak is a C _1-12 alkylene chain, one or more C atoms of which may be replaced by O, S, NR ⁶ , CO or COO; An is an anion, optionally -SO ₃ ^- ; and each benzene ring is independently unsubstituted or substituted by one or more substituents selected from the substituents described with reference to R ³ .

Exemplary groups of formula (IXm) are:

Exemplary groups of formula (IXn) are:

The group of formula (IXo) is directly bonded to the bridging group ^B1 or ^B2 substituted by a group of formula -B( ^R14 ) ₂ , wherein ^R14 is a substituent at each occurrence, optionally a _C1-20 alkyl group; → is a bond to the boron atom -B( ^R14 ) ₂ ; and --- is a CC bond between the group of formula (IXo) and the bridging group.

Optionally, R ¹⁴ is selected from C _1-12 alkyl; unsubstituted phenyl; and phenyl substituted with one or more C _1-12 alkyl groups.

The group of formula (IXo), the group ^B1 or ^B2 and the B(R ¹⁴ ) ₂ substituent of ^B1 or ^B2 may be linked together to form a 5- or 6-membered ring.

The group of the formula (IXo) is selected from: Organic electronic devices

FIG1 shows an organic light responsive device, preferably an organic light detector, according to some embodiments of the present disclosure. The organic light responsive device comprises a cathode 103, an anode 107, and a bulk heterojunction layer 105 disposed between the anode and the cathode. The organic light responsive device can be supported on a substrate 101, optionally a glass or plastic substrate.

The bulk heterojunction layer comprises or consists of a compound of formula (I) and an electron-donating compound. The bulk heterojunction layer comprises one or more other materials, such as one or more other electron-donating materials and/or one or more other electron-accepting materials.

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

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

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

Each of the anode and the cathode may independently be a single conductive layer, or may include a plurality of layers.

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

Figure 1 illustrates a configuration in which the photoresponsive device comprises a bulk heterojunction photoactive layer 105. In other embodiments, the photoactive layer comprises an electron accepting sublayer comprising or consisting of a compound of formula (I) disposed between the anode and the cathode; and an electron donating sublayer comprising or consisting of one or more electron donating materials disposed between the anode and the electron accepting layer and in direct contact with the electron accepting layer.

Figure 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.

The organic photoresponsive device may include layers other than the anode, cathode, and photoactive layer. In some embodiments, the hole transport layer and/or the electron blocking layer are disposed between the anode and the photoactive layer. In some embodiments, the electron transport layer and/or the hole blocking layer are disposed between the cathode and the photoactive layer. In some embodiments, the work function modification layer is disposed between the photoactive layer and the anode and/or between the photoactive layer and the cathode.

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. When in use, if incident light is transmitted through the substrate and the electrode is supported by the substrate, then the substrate is transparent. Electron Supply Material

Exemplary electron donating materials for the photoactive layer as described herein are disclosed, for example, in WO 2013/051676, the contents of which are incorporated herein by reference.

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

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

Preferably, it is a non-crystalline or semi-crystalline conjugate organic polymer.

Also preferably, the electron donating polymer is a conjugated organic polymer having a band gap generally 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 energy level of no more than 5.5 eV from the vacuum energy level. Optionally, the electron donating polymer has a HOMO energy level of at least 4.1 eV from the vacuum energy level. As exemplary electron donating polymers, there can be mentioned polymers selected from conjugated hydrocarbons or heterocyclic polymers, including polyacene, polyaniline, polyazulene, polybenzofuran, polyfluorene, polyfuran, polyindole, polyphenylene, polypyrazoline, polypyrene, polytantalum, polypyrrolidone ... , polypyridine, polytriarylamine, poly(phenylene vinylene), poly(3-substituted thiophene), poly(3,4-bissubstituted thiophene), polyselenophene, poly(3-substituted selenophene), poly(3,4-bissubstituted selenophene), poly(dithiophene), poly(terthiophene), poly(diselenophene), poly(triselenophene), polythieno[2,3-b]thiophene, polythieno[3,2-b]thiophene, polybenzothiophene, polybenzo[1,2-b:4,5-b']dithiophene, polyisobenzothiophene, poly(monosubstituted pyrrole), poly(3,4-bissubstituted pyrrole), poly-1,3,4- Oxadiazole, polyisobenzothiophene, their derivatives and copolymers.

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

The donor polymer is preferably a donor-acceptor (DA) copolymer comprising a donor repeating unit and an acceptor repeating unit.

Preferred donor units are selected from thiophene, optionally substituted with one or more substituents R ¹¹ as described above; and repeating units of formula (X), (XI) and (XII): (X) wherein: ^YA at each occurrence is independently O, S or ^NR55 ; ^ZA at each occurrence is O, CO, S, ^NR55 or C( ^R54 ) ₂ ; and ^R51 , ^R54 and ^R55 at each occurrence are independently H or a substituent.

Optionally, R ⁵¹ is independently selected at each occurrence from H; F; C _1-20 alkyl, wherein one or more non-adjacent C atoms may be replaced by O, S, NR ² , COO or CO and one or more H atoms of the alkyl may be replaced by F; and aromatic or heteroaromatic groups Ar ³ which are unsubstituted or substituted by one or more substituents.

In some embodiments, Ar ³ may be an aromatic group, such as a phenyl group. If present, one or more substituents of Ar ³ may be selected from C _1-12 alkyl groups, wherein one or more non-adjacent C atoms may be replaced by O, S, NR ⁶ , COO or CO and one or more H atoms of the alkyl group may be replaced by F.

Preferably, each R ⁵¹ is H.

Preferably, each R ⁵⁴ is selected from the group consisting of: H; F; a linear, branched or cyclic C _1-20 alkyl group, wherein one or more non-adjacent C atoms may be replaced by O, S, NR ¹⁷ , CO or COO, wherein R ¹⁷ is a C _1-12 alkyl group and one or more H atoms of the C _1-20 alkyl group may be replaced by F; and a group of formula (Ak)u-(Ar ⁷ )v, wherein Ak is a C _1-20 alkyl chain, wherein one or more non-adjacent C atoms may be replaced by O, S, NR ⁶ , CO or COO; u is 0 or 1; Ar ⁷ is independently an aromatic or heteroaromatic group at each occurrence, which is unsubstituted or substituted by one or more substituents; and v is at least 1, and optionally 1, 2 or 3.

Substituents for Ar ⁷ , if present, are preferably selected from F; Cl; NO ₂ ; CN; and C _1-20 alkyl, wherein one or more non-adjacent C atoms may be replaced by O, S, NR ⁶ , CO or COO and one or more H atoms may be replaced by F. Preferably, Ar ⁷ is phenyl.

Preferably, R ⁵⁵ is H or C _1-20 alkyl. (XI) wherein R ¹⁸ and R ¹⁹ are each independently selected from H; F; C _1-12 alkyl, wherein one or more non-adjacent, non-terminal C atoms may be replaced by O, S, COO or CO and one or more H atoms of the alkyl may be replaced by F; or an aromatic or heteroaromatic group Ar ⁶ which is unsubstituted or substituted by one or more substituents selected from F and C _1-12 alkyl, wherein one or more non-adjacent, non-terminal C atoms may be replaced by O, S, COO or CO. (XII) wherein Y ³ is O, S or Se, preferably S; R ⁵ at each occurrence is H or a substituent, more preferably H or a substituent R ¹¹ as described above, most preferably H; and Q is C(R ²¹ ) ₂ or Si(R ²¹ ) ₂ , wherein R ²¹ at each occurrence is a substituent, preferably a substituent selected from the following: C _1-20 alkyl, wherein one or more non-adjacent C atoms may be replaced by O, S, NR ¹⁷ , wherein R ¹⁷ is C _1-12 alkyl, COO or CO and one or more H atoms of the alkyl may be replaced by F; and an aromatic or heteroaromatic group, preferably C _6-20 aryl, more preferably phenyl, which is unsubstituted or substituted by one or more substituents. Substituents for the aromatic or heteroaromatic group R ²¹ may be selected from those described above for R ¹¹ .

Preferred receptor units include benzothiadiazole optionally substituted with one or more substituents R ¹¹ ; and repeating units of formula (XIII): (XIII) wherein R ² is as described above; and Y ⁴ is O, S or Se, preferably S. Fullerene

In some embodiments, the compound of formula (I) is the sole electron-accepting material of an electron-accepting sublayer or bulk heterojunction layer as described herein.

In some embodiments, the electron accepting layer or bulk heterojunction layer contains a compound of formula (I) and one or more other electron accepting materials. Preferably, the other electron accepting material is fullerene. The weight ratio of the compound of formula (I): fullerene acceptor can be in the range of about 1:0.1-1:1, preferably in the range of about 1:0.1-1:0.5.

The fullerene may be selected from, but not limited to, C ₆₀ , C ₇₀ , C ₇₆ , C ₇₈ and C ₈₄ fullerenes or derivatives thereof, including, but not limited to, PCBM-type fullerene derivatives (including phenyl-C ₆₁ -butyric acid methyl ester (C ₆₀ PCBM)), TCBM-type fullerene derivatives (e.g., tolyl-C ₆₁ -butyric acid methyl ester (C ₆₀ TCBM)) and ThCBM-type fullerene derivatives (e.g., thienyl-C ₆₁ -butyric acid methyl ester (C ₆₀ ThCBM)).

The fullerene derivative may have formula (V): (V)

A and the C-C group of the fullerene together form a monocyclic or condensed ring group which may be unsubstituted or substituted with one or more substituents.

Exemplary fullerene derivatives include formula (Va), (Vb) and (Vc): (Va) (Vb) (Vc) wherein R ²⁰ to R ³² are each independently H or a substituent.

The substituents ^R20 - ^R32 are optionally and independently at each occurrence selected from the group consisting of aryl or heteroaryl, optionally phenyl, which may be unsubstituted or substituted with one or more substituents; and _C1-20 alkyl, wherein one or more non-adjacent C atoms may be replaced by O, S, ^NR6 , CO or COO and one or more H atoms may be replaced by F.

Substituents of the aryl or heteroaryl groups, when present, are optionally selected from C _1-12 alkyl groups, wherein one or more non-adjacent C atoms may be replaced by O, S, NR ⁶ , CO or COO and one or more H atoms may be replaced by F. Formulations

The photoactive layer can be formed by any process including but not limited to thermal evaporation and solution deposition.

Preferably, the electron acceptor layer or bulk heterojunction layer is formed by depositing a formulation dissolved or dispersed in a solvent or a mixture of two or more solvents, followed by evaporation of one or more solvents, the formulation comprising a compound of formula (I) and any other components of the layer, including one or more electron donating materials in the case of a bulk heterojunction layer. The formulation can 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 rod coating, slit coating, inkjet printing, screen printing, gravure printing and flexographic printing.

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 other solvents. The one or more other solvents may be selected from esters, optionally alkyl or aryl esters of alkyl or aryl carboxylic acids, optionally C _1-10 alkyl benzoate, benzyl benzoate or dimethoxybenzene. In a preferred embodiment, a mixture of trimethylbenzene and benzyl benzoate is used as a solvent. In other preferred embodiments, a mixture of trimethylbenzene and dimethoxybenzene is used as a solvent.

The formulation may contain other components in addition to the electron accepting material, the electron donating material and the one or more solvents. As examples of such components, there may be mentioned adhesives, defoamers, deaerators, viscosity enhancers, diluents, adjuvants, flow improvers, colorants, dyes or pigments, sensitizers, stabilizers, nanoparticles, surface active compounds, lubricants, wetting agents, dispersants and inhibitors.

The photoactive layer is formed on one of the anode and the cathode of the organic photoresponsive device and the other of the anode and the cathode is formed on the photoactive layer. Application

The circuit may include an OPD connected to one or more voltage sources for applying a reverse bias to the device; a device configured to measure the photocurrent; and an amplifier configured to amplify the output signal of the OPD. The voltage applied to the photodetector may be variable. In some embodiments, the photodetector may be continuously biased when in use.

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

In some embodiments, the sensor may include an OPD and a light source as described herein, wherein the OPD is configured to receive light emitted from the light source. In some embodiments, the light source has a peak wavelength of at least 1000 nm or at least 1200 nm, preferably in the range of 1000-1500 nm.

In some embodiments, the light from the light source may or may not be changed before it reaches the OPD. For example, the light may be reflected, filtered, down-converted, or up-converted before it reaches the OPD.

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

The detection surface area of an OPD as described herein can be selected based on the desired application. Optionally, an OPD as described herein has a detection surface area of less than about 3 ^cm2 , less than about 2 ^cm2 , less than about 1 ^cm2 , less than about 0.75 ^cm2 , less than about 0.5 ^cm2 , or less than about 0.25 ^cm2 . Optionally, each OPD can be part of an array of OPDs, wherein each OPD is a pixel of the array having an area as described herein, optionally less than 1 ^mm2 , optionally in the range of 0.5 ^{microns2-900 microns2} . Example Measurements

Unless otherwise stated, the HOMO and LUMO energy levels of materials as described herein were measured by square wave voltammetry (SWV).

In SWV, the current at the working electrode is measured as the potential between the working electrode and the reference electrode is swept linearly with time. The differential current between the forward pulse and the reverse pulse is plotted as a function of potential to obtain a voltammogram. The CHI 660D potentiostat can be used for measurement.

The apparatus used to measure the HOMO or LUMO energy level by SWV may include the following: 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.

At the end of the experiment, ferrocene was added directly to the existing cell for calculation purposes, where the potential for oxidation and reduction of ferrocene relative to Ag/AgCl was determined using cyclic voltammetry (CV).

The samples were dissolved in toluene (3 mg/ml) and centrifuged directly onto a glassy carbon working electrode at 3000 rpm. LUMO = 4.8-E ferrocene (peak-to-peak average) - E sample reduced (peak maximum). HOMO = 4.8-E ferrocene (peak-to-peak average) + E sample oxidized (peak maximum).

A typical SWV experiment was run at 15 Hz frequency; 25 mV amplitude and 0.004 V increment step. Results were calculated for both HOMO and LUMO data from three freshly centrifuged film samples.

Unless otherwise stated, absorption spectra were measured using a Cary 5000 UV-VIS-NIR spectrometer. For optimal control over data resolution, measurements were acquired from 175 nm to 3300 nm using a PbSmart NIR detector with variable slit width (down to 0.01 nm) for extended photometric range.

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

Unless otherwise stated, the solution absorption data provided herein were measured in toluene solution. Synthesis

Compounds of formula (I) having a donor group D-1 in which the Ar ¹ group is absent as described above can be prepared according to the following general scheme 1 and following the methods described in WO2021/079140 (the contents of which are incorporated herein by reference), wherein R' is a C _1-12 alkyl group: General Scheme 1

The donor group D wherein at least one Ar ¹ is present can be prepared according to General Scheme 2: General Scheme 2 General process 3

Compounds of formula (I) containing both heteroaromatic and vinylene bridges can be prepared according to General Scheme 4. General Scheme 4 Model data

The energy levels of the exemplary compounds were modeled using Gaussian09 software available from Gaussian using Gaussian09 with B3LYP (functional). The results are shown in Table 1, where S1f corresponds to the oscillator strength (predicted absorption strength) of the transition from S1. Table 1

Table 1 shows the effect of acceptor group A on the band gap for the case of ^X1 = O. Structure HOMO /eV LUMO /eV E _g /nm S1f λ _max / nm -5.22 -3.61 773 2.53 816 -5.60 -4.09 824 2.43 864 -5.45 -3.87 792 2.72 834 -5.39 -3.97 875 2.78 917 -5.68 -4.35 932 2.72 966 Table 2

Table 2 shows the effect of acceptor group A on the band gap for the case of ^X1 = S. Structure HOMO /eV LUMO /eV E _g /nm S1f λ _max / nm -5.31 -3.62 736 2.37 794 -5.68 -4.10 785 2.34 843 -5.52 -3.88 755 2.56 813 -5.47 -3.97 832 2.63 894 -5.76 -4.35 886 2.58 943 Table 3

Table 3 shows the effect of acceptor group A on the band gap for the case of X ¹ = Se. Structure HOMO /eV LUMO /eV E _g /nm S1f λ _max / nm -5.30 -3.61 733 2.28 795 -5.68 -4.09 782 2.24 845 -5.52 -3.87 751 2.45 815 -5.46 -3.97 829 2.54 895 -5.75 -4.35 883 2.48 946 Table 4

Table 4 shows the content of thienopyrrolidone Modeled band gap of bridge compounds. Structure HOMO /eV LUMO /eV E _g /nm S1f λ _max / nm -5.69 -4.26 866 2.26 923 -5.48 -4.10 903 2.46 961 -5.75 -4.42 932 2.51 987 -5.77 -4.26 821 2.09 898 -5.55 -4.10 855 2.32 934 -5.82 -4.42 884 2.36 961 -5.77 -4.25 816 2.00 899 -5.55 -4.09 850 2.24 934 -5.82 -4.41 878 2.27 962 Table 5

Table 5 shows the modeled band gaps of compounds with only one Ar ¹ group present. Structure HOMO /eV LUMO /eV E _g /nm S1f λ _max / nm -5.18 -3.58 775 2.67 828 -5.59 -4.05 828 2.60 880 -5.63 -4.30 936 2.84 984 -5.69 -4.36 929 2.81 993 Table 6

Table 6 shows the modeled band gaps of compounds with two Ar ¹ groups present. Structure HOMO /eV LUMO /eV E _g /nm S1f λ _max / nm -5.15 -3.55 777 2.55 845 -5.49 -4.00 835 2.43 903 -5.57 -4.25 944 2.55 1014 -5.65 -4.30 920 2.80 1003

101: substrate 103: cathode 107: anode 105: bulk heterojunction layer

The disclosed technology and the accompanying drawings describe some embodiments of the disclosed technology. FIG. 1 is a schematic diagram of an organic light responsive device according to some embodiments. The drawings are not drawn to scale and have various viewpoints and perspectives. The drawings are some embodiments and examples. In addition, for the purpose of discussing some embodiments of the disclosed technology, some components and/or operations may be separated into different blocks or combined into a single block. In addition, although the technology is suitable for various modifications and alternative forms, specific embodiments have been shown by way of example in the drawings and described in detail below. However, it is not desired to limit the technology to the specific embodiments described. Instead, it is desired that the technology cover all modifications, equivalents and alternatives that fall within the scope of the technology as defined in the attached application scope.

Claims (15)

A compound of formula (I), (I) wherein: X ¹ is O, S, Se, NR ² or PR ² , wherein R ² at each occurrence is H or a substituent; Y ¹ is O, S or Se; Ar ¹ at each occurrence is independently an unsubstituted or substituted monocyclic or polycyclic aromatic or heteroaromatic group or is absent; R ¹ at each occurrence is independently a substituent; B ¹ at each occurrence is independently a bridging group; f1 and f2 are each 1; g is at least 1; and A at each occurrence is independently a monovalent electron accepting group. The compound of claim 1, wherein at least one A is an electron accepting group of formula (II): (II) wherein: G is C=O, C=S, SO, SO ₂ , NR ³³ or C(R ³³ ) ₂ , wherein R ³³ is CN or COOR ⁴⁰ , wherein R ⁴⁰ is H or a substituent at each occurrence; R ³ is H or a substituent; Z is each independently CN, CF ₃ or COOR ⁴⁰ , wherein R ⁴⁰ is H or a substituent at each occurrence; and Ar ² is an unsubstituted or substituted monocyclic or polycyclic aromatic ring or heterocyclic aromatic ring. The compound of claim 2, wherein Ar ² is selected from: benzene substituted with at least one CN substituent; and an unsubstituted or substituted monocyclic or polycyclic heteroaromatic group. The compound of claim 3, wherein the group of formula (II) has formula (IIa): (IIa) wherein ^X7 - ^X10 are each independently ^CR12 or N, wherein ^R12 at each occurrence is H or a substituent selected from _C1-20 alkyl and electron withdrawing groups, with the proviso that when each of ^X7 - ^X10 is ^CR12 , at least one ^R12 is CN. The compound of claim 3, wherein the group of formula (II) has formula (IIb): (IIb) wherein Ar ³ is an unsubstituted or substituted monocyclic or polycyclic aromatic or heteroaromatic group. The compound of claim 3, wherein Ar ² is benzene substituted with at least one CN substituent. The compound of any one of claims 1 to 6, wherein B ¹ is selected from unsubstituted or substituted furan; unsubstituted or substituted thiophene; or a fused analog thereof. The compound of claim 7, wherein ^B1 is a group of formula (III): (III) wherein Y ² is O, S or Se; and Ar ⁴ is an unsubstituted or substituted monocyclic or polycyclic aromatic or heteroaromatic group. The compound of claim 8, wherein formula (III) is a group of formula (IIIa): (IIIa) wherein R ⁸ at each occurrence is H or a substituent. The compound of any one of claims 1 to 6, wherein each Ar ¹ is absent. A composition comprising the compound of any of the preceding claims and an electron donating material. A formulation comprising a compound or composition as claimed in any of the preceding claims dissolved or dispersed in one or more solvents. An organic photoresponsive device comprises an anode, a cathode, and a photoactive layer disposed between the anode and the cathode, wherein the photoactive layer comprises the composition of claim 12. A photo sensor comprises a light source and an organic photodetector as claimed in claim 13, wherein the organic photodetector is configured to detect light emitted from the light source. A photosensor as claimed in claim 14, wherein the light source emits light having a peak wavelength greater than 1000 nm.

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