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WO2025186103A1 - Composé - Google Patents

Composé

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Publication number
WO2025186103A1
WO2025186103A1 PCT/EP2025/055387 EP2025055387W WO2025186103A1 WO 2025186103 A1 WO2025186103 A1 WO 2025186103A1 EP 2025055387 W EP2025055387 W EP 2025055387W WO 2025186103 A1 WO2025186103 A1 WO 2025186103A1
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WO
WIPO (PCT)
Prior art keywords
group
formula
independently
substituent
occurrence
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/EP2025/055387
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English (en)
Other versions
WO2025186103A8 (fr
Inventor
Michal MACIEJCZYK
Nir YAACOBI-GROSS
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cambridge Display Technology Ltd
Sumitomo Chemical Co Ltd
Original Assignee
Cambridge Display Technology Ltd
Sumitomo Chemical Co Ltd
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Priority claimed from GB2403418.3A external-priority patent/GB2639045A/en
Application filed by Cambridge Display Technology Ltd, Sumitomo Chemical Co Ltd filed Critical Cambridge Display Technology Ltd
Publication of WO2025186103A1 publication Critical patent/WO2025186103A1/fr
Publication of WO2025186103A8 publication Critical patent/WO2025186103A8/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/16—Electron transporting layers
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
    • C07D495/14—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/22—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D519/00—Heterocyclic compounds containing more than one system of two or more relevant hetero rings condensed among themselves or condensed with a common carbocyclic ring system not provided for in groups C07D453/00 or C07D455/00
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene

Definitions

  • Embodiments of the present disclosure relate to electron-accepting compounds and more specifically compounds suitable for use as an electron-accepting material in a photoresponsive device.
  • An organic photodetector may contain a photactive layer of a blend of an electron-donating material and an electron-accepting material between an anode and a cathode.
  • Known electron-accepting materials include fullerenes and non-fullerene acceptors (NFAs).
  • CN109776566 discloses a polysubstituted benzocyclopentadione derivative-based A-D-A conjugated molecule.
  • WO 2023/012366 discloses ADA'DA type non-fullerene acceptors.
  • a 1 is a divalent heteroaromatic electron-accepting group
  • a 2 and A 3 independently in each occurrence is the same or different and is a monovalent electron-accepting group
  • D 1 , D 2 and D 3 independently in each occurrence is the same or different and is an electrondonating group
  • B 1 , B 2 , and B 3 independently in each occurrence is the same or different and is a bridging group; x 1 and x 2 are each independently the same or different and are each 0, 1, 2 or 3; x 3 and x 4 are each independently the same or different and are each 0, 1, 2 or 3; y 1 , y 2 and y 3 are each independently the same or different and are each at least 1; z 1 and z 2 are each independently the same or different and are each 0, 1, 2 or 3; and wherein at least one occurrence of D 1 of formula (I) or at least one occurrence of at least one of D 2 and D 3 of formula (II) is a group of formula (III) (HI) wherein:
  • X 1 and X 2 are each independently selected from is O, S and NR 1 wherein R 1 is H or a substituent, with the proviso that at least one of X 1 and X 2 is NR 1 ;
  • Y is O or S
  • Ar 1 is a monocyclic, bicyclic or tricyclic aromatic or heteroaromatic group or is absent;
  • Ar 2 is a monocyclic or bicyclic or tricyclic aromatic or heteroaromatic group or is absent;
  • R 1 is H or a substituent
  • R 2 in each occurrence is independently a substituent.
  • X 1 is selected from O and S and X 2 is NR 1 .
  • X 2 is selected from O and S and X 1 is NR 1
  • Ar 1 is not present and the group of formula (III) has formula (III-A):
  • Ar 2 is not present and the group of formula (III) has formula (III-B): wherein R 4 is H or a substituent.
  • R 4 is H or a substituent.
  • neither Ar 1 nor Ar 2 is present and the group of formula (III) has formula (III- C):
  • Ar 1 and / or Ar 2 is a group of formula (IV):
  • At least one of A 2 and A 3 comprises a non-aromatic carbon-carbon double bond and a carbon atom of the carbon-carbon double bond is bound directly to D 1 , D 2 or D 3 , or if present, to B 1 or B 2 .
  • a 2 and A 3 are each independently selected from groups of formulae (IXa)-(IXr):
  • 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 further rings;
  • R 10 is H or a substituent
  • R 13 in each occurrence is a substituent
  • R 15 in each occurrence is independently H or a substituent
  • R 16 is a substituent
  • Ar 6 is a 5-membered heteroaromatic group which is unsubstituted or substituted with one or more substituents;
  • T 1 , T 2 and T 3 each independently represent an aryl or a 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 a fused heteroaromatic group which is unsubstituted or substituted with one or more substituents 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 ; and R 24 is H or a halogen.
  • At least one of A 2 and A 3 is a group of formula (IXa-2) and (IXa-3):
  • each X 7 -X 10 is independently CR 12 or N wherein R 12 in each occurrence is H or a substituent selected from C1-20 hydrocarbyl and an electron withdrawing group; and R 15 is H or a substituent.
  • the electron withdrawing group is F, Cl or CN.
  • a C1-20 hydrocarbyl group as described anywhere herein is preferably selected from C1-20 alkyl; unsubstituted phenyl; and phenyl substituted with one or more C1-12 alkyl groups.
  • the present disclosure provides a composition comprising an electron-donating material and an electron-accepting material wherein the electron accepting material is a compound of formula (I) or (II).
  • the present disclosure provides an organic electronic device comprising an active layer comprising a compound of formula (I) or (II).
  • the active layer may comprise a composition as described herein.
  • the organic electronic device is an organic photoresponsive device comprising a photoactive layer comprising the compound of formula (I) or (II) or the composition as described herein disposed between the anode and cathode.
  • the photoactive layer is a bulk heterojunction layer comprising a composition as described herein.
  • the organic photoresponsive device is an organic photodetector.
  • the present disclosure provides a photosensor comprising a light source and an organic photodetector as described herein wherein the photosensor is configured to detect light emitted from the light source.
  • the light source emits light having a peak wavelength of greater than 900 nm.
  • the present disclosure provides a formulation comprising a compound of formula (I) or (ii) or a composition as described herein dissolved or dispersed in one or more solvents.
  • the present disclosure provides a method of forming an organic electronic device as described herein wherein formation of the active layer comprises deposition of a formulation as described herein onto a surface and evaporation of the one or more solvents.
  • Figure 1 is a schematic illustration of an organic photoresponsive device according to some embodiments
  • Figure 2 is solution absorption spectra of Compound Examples 1 and 2 in 1,2,4- trimethylbenzene solution
  • Figure 3A is film absorption spectra of Compound Examples 1 and 2 formed by casting 1,2,4-trimethylbenzene solutions of the compounds
  • Figure 3B is film absorption spectra of Compound Examples 1 and 2 formed by casting 1,2-dichlorobenzene solutions of the compounds;
  • Figure 4A is a solution absorption spectrum of Compound Example 3 in 1,2,4- trimethylbenzene solution
  • Figure 4B is a film absorption spectrum of Compound Example 3 formed by casting a 1,2,4- trimethylbenzene solution of the compound;
  • Figure 5 is a plot of current density vs. voltage for an organic photodetector containing Compound Example 1;
  • Figure 6 is a plot of external quantum efficiency vs. wavelength for the organic photodetector of Figure 5;
  • Figure 7 shows plots of external quantum efficiency vs. wavelength for an organic photodetector containing Compound Example 1 and for an organic photodetector containing Compound Example 2;
  • Figure 8 shows plots of current density vs. voltage for the organic photodetectors of Figure 7;
  • Figure 9 is a plot of external quantum efficiency vs. wavelength for an organic photodetector containing Compound Example 3.
  • Figure 10 is a plot of current density vs. voltage for the organic photodetector of Figure 9.
  • references to a layer "over” another layer when used in this application means that the layers may be in direct contact or one or more intervening layers may be present. References to a layer “on” another layer when used in this application means that the layers are in direct contact. References to a specific atom include any isotope of that atom unless specifically stated otherwise.
  • FIG. 1 illustrates an organic photoresponsive device, preferably an organic photodetector, 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.
  • the bulk heterojunction layer comprises a non-fullerene acceptor (NFA) of formula (I) or a NFA of formula (II) and an electron-donating material:
  • NFA non-fullerene acceptor
  • a 1 is a divalent heteroaromatic electron-accepting group
  • a 2 and A 3 independently in each occurrence is a monovalent electron-accepting group
  • D 1 , D 2 and D 3 independently in each occurrence is an electron-donating group
  • B 1 , B 2 , and B 3 independently in each occurrence is a bridging group; x 1 and x 2 are each independently 0, 1, 2 or 3; x 3 and x 4 are each independently 0, 1, 2 or 3; y 1 , y 2 and y 3 are each independently at least 1; z 1 and z 2 are each independently 0, 1, 2 or 3.
  • Each of the electron-accepting groups A 1 and A 2 has a lowest unoccupied molecular orbital (LUMO) level that is deeper (i.e., further from vacuum) than the LUMO of any of the electron-donating groups D 1 , D 2 or D 3 , preferably at least 1 eV deeper.
  • the LUMO levels of electron-accepting groups and electron-donating groups may be as determined by modelling the LUMO level of these groups, in which each bond to adjacent group is replaced with a bond to a hydrogen atom. Modelling may be performed using Gaussian09 software available from Gaussian using Gaussian09 with B3LYP (functional) and LACVP* (Basis set).
  • At least one D 1 is a group of formula (III).
  • At least one occurrence of at least one of D 2 and D 3 is a group of Formula (III).
  • the bulk heterojunction layer may consist of the NFA of formula (I) or (II) and the electrondonating compound or it may comprise one or more further materials, for example one or more further electron-donating materials and I or one or more further electron-accepting materials.
  • the weight of the electron-donating material(s) to the electronaccepting material(s) is from about 1:0.5 to about 1:2, preferably about 1 : 1.1 to about 1:2.
  • the electron-donating material has a type II interface with the compound of formula (I) or (II), i.e., the electron-donating material has a shallower HOMO and LUMO than the corresponding HOMO and LUMO levels the compound of formula (I) or (II).
  • the compound of formula (I) or (II) has a HOMO level that is at least 0.05 eV deeper, optionally at least 0.10 eV deeper, than the HOMO of the electron-donating material.
  • the gap between the HOMO level of the electron-donating material and the LUMO level of the compound of formula (I) or (II) is less than 1.4 eV.
  • compounds of formula (I) and (II) have a peak absorption wavelength as measured in solution of greater than 900 nm, or greater than 1000 nm, optionally less than 1500 nm or 1400 nm.
  • Each of the anode and cathode may independently be a single conductive layer or may comprise a plurality of layers.
  • At least one of the anode and cathode is transparent so that light incident on the device may reach the bulk heterojunction layer.
  • both of the anode and cathode are transparent.
  • the transmittance of a transparent electrode may be selected according to an emission wavelength of a light source for use with the organic photodetector.
  • Figure 1 illustrates an arrangement in which the photoresponsive device comprises a bulk heterojunction photoactive layer 105.
  • the photoactive layer comprises an electron-accepting sub-layer comprising or consisting of a compound of formula (I) or (II) described herein disposed between the anode and cathode; and an electron-donating sub-layer 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 illustrates an arrangement in which the cathode is disposed between the substrate and the anode.
  • the anode may be disposed between the cathode and the substrate.
  • the organic photoresponsive device may comprise layers other than the anode, cathode and the photoactive layer.
  • a hole-transporting layer and I or an electron-blocking layer is disposed between the anode and the photoactive layer.
  • an electron-transporting layer and / or a hole-blocking layer is disposed between the cathode and the photoactive layer.
  • a 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, without limitation, a glass or plastic substrate.
  • the substrate can be an inorganic semiconductor.
  • the substrate may be silicon.
  • the substrate can be a wafer of silicon.
  • the substrate is transparent if, in use, incident light is to be transmitted through the substrate and the electrode supported by the substrate.
  • At least one occurrence of D 1 of formula (I) or at least one occurrence of at least one of D 2 and D 3 of formula (II) is a group of formula (III):
  • X 1 and X 2 are each independently selected from is O, S and NR 1 wherein R 1 is H or a substituent, with the proviso that at least one of X 1 and X 2 is NR 1 .
  • one of X 1 and X 2 is selected from O and S and the other of X 1 and X 2 is NR 1 wherein R 1 is H or a substituent, i.e., X 1 is selected from O and S and X 2 is NR 1 or X 2 is is selected from O and S and X 1 is NR 1 .
  • Y is O or S, preferably S.
  • R 1 is preferably selected from H or a C1-20 hydrocarbyl group.
  • a C1-20 hydrocarbyl group as described anywhere herein may be selected from C1-20 alkyl; unsubstituted phenyl; and phenyl substituted with one or more C1-12 alkyl groups.
  • R 2 in each occurrence is independently a substituent, preferably a substituent selected from :
  • C1-20 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO, CONR 6 or CO and one or more H atoms of the alkyl may be replaced with F; and aryl or heteroaryl, preferably phenyl, which is unsubstituted or substituted with one or more substituents, optionally one or more substituents R 9 selected from F, Cl, NO2 and C1-12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO CONR 6 or CO and one or more H atoms of the alkyl may be replaced with F.
  • R 6 in each occurrence is independently H or a substituent, preferably H or a C1-20 hydrocarbyl group.
  • Each R 2 may be selected according to a required solubility of the compound of formula (I) or (II). Further, the choice of R 2 groups may be selected to influence packing of the compound of formula (I) or (II); for example, alkyl groups R 2 may allow for closer packing than aromatic groups R 2 .
  • Ar 1 and Ar 2 are each independently a monocyclic or fused bicyclic or tricyclic aromatic or heteroaromatic group or is absent.
  • Ar 1 is not present and the group of formula (III) has formula (III-A) :
  • Ar 2 is not present and the group of formula (III) has formula (III-B):
  • R 3 and R 4 are each independently selected from H and a substituent selected from F; CN; NO2; C1-20 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO, CONR 6 or CO wherein R 6 is as described above and one or more H atoms of the alkyl may be replaced with F; and phenyl which is unsubstituted or substituted with one or more substituents, optionally one or more substituents R 9 as described above.
  • R 3 and R 4 are each H.
  • neither Ar 1 nor Ar 2 is present and the group of formula
  • Ar 1 and Ar 2 are preferably each independently selected from monocyclic aromatic or heteroaromatic groups, optionally thiophene; furan; pyrrole; or benzene, and bicyclic or tricyclic fused aromatic or heteroaromatic groups, wherein each ring is selected from thiophene; furan; pyrrole; and benzene; or wherein the fused aromatic or heteroaromatic group is cyclopentadiene fused to at least one of thiophene; furan; pyrrole; and benzene.
  • Ar 1 and Ar 2 are each independently a group of formula (IV):
  • Bridging units B 1 , B 2 and B 3 are preferably each selected from vinylene, arylene, heteroarylene, arylenevinylene and heteroarylenevinylene wherein the arylene and heteroarylene groups are monocyclic or bicyclic groups, each of which may be unsubstituted or substituted with one or more substituents.
  • B 1 , B 2 and B 3 are selected from units of formulae (Via) - (VIo): (VII) wherein R 55 is H or a substituent, optionally H or a C1-20 hydrocarbyl group; and R 8 in each occurrence is independently H or a substituent, preferably H or a substituent selected from F; CN; NO2; C1-20 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO and one or more H atoms of the alkyl may be replaced with F; phenyl which is unsubstituted or substituted with one or more substituents; and -B(R 14 )2 wherein R 14 in each occurrence is a substituent, optionally a C1-20 hydrocarbyl group.
  • R 8 groups of formulae (Via), (VIb) and (Vic) may be linked to form a bicyclic ring which may be substituted with one or more substituents, optionally one or more substituents selected from F; CN; NO2; C1-20 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO and one or more H atoms of the alkyl may be replaced with F.
  • R 8 is preferably H, C1-20 alkyl or C1-19 alkoxy.
  • R 8 groups of formulae (Via), (VIb) and (Vic) may be linked to form an optionally substituted bicyclic ring.
  • each x 1 is preferably 0 or 1.
  • x 3 and x 4 are each preferably 0 and z 1 and z 2 are each preferably 0 or 1.
  • the monovalent acceptor groups A 2 and A 3 may each independently be selected from any such units known to the skilled person.
  • the A 2 and A 3 groups of the compound of formula (I) or (II) may be the same or different, preferably the same.
  • Exemplary monovalent acceptor groups include, without limitation, groups of formulae (IXa)-(IXs)
  • 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 further rings.
  • R 10 is H or a substituent, preferably a substituent selected from the group consisting of Ci- 12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO and one or more H atoms of the alkyl may be replaced with F; and an aromatic group, optionally phenyl, which is unsubstituted or substituted with one or more substituents selected from F and C1-12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO.
  • R 10 is H.
  • J is O or S, preferably O.
  • R 13 in each occurrence is a substituent, optionally C1-12 alkyl wherein one or more non- adjacent C atoms may be replaced with O, S, NR 6 , COO or CO and one or more H atoms of the alkyl may be replaced with F.
  • R 15 in each occurrence is independently H or a substituent.
  • R 15 in each occurrence is independently H; F; Cl; Br; CN; Ci i2 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO and one or more H atoms of the alkyl may be replaced with F; aromatic group Ar 2 , optionally phenyl, which is unsubstituted or substituted with one or more substituents selected from F and C1-12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO; or a group selected from :
  • each R 15 is the same or different and is selected from H, F, Cl, Br and CN.
  • R 16 is H or a substituent, preferably a substituent selected from :
  • Ar 3 in each occurrence is independently an unsubstituted or substituted aryl or heteroaryl group, preferably thiophene, and w is 1, 2 or 3;
  • Ci-12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO and one or more H atoms of the alkyl may be replaced with F.
  • Ar 6 is a 5-membered heteroaromatic group, preferably thiophene or furan, which is unsubstituted or substituted with one or more substituents.
  • Substituents of Ar 3 and Ar 6 are optionally selected from C1-12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO and one or more H atoms of the alkyl may be replaced with F.
  • T 1 , T 2 and T 3 each independently represent an aryl or a heteroaryl ring, optionally benzene, which may be fused to one or more further rings.
  • Substituents of T 1 , T 2 and T 3 , where present, are optionally selected from non-H groups of R 25 .
  • T 3 is benzothiadiazole.
  • Z 1 is N or P.
  • Ar 8 is a fused heteroaromatic group which is unsubstituted or substituted with one or more substituents, optionally one or more non-H substituents R 10 , 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 .
  • R 24 is H or a halogen, preferably H, F or Cl.
  • a 2 and A 3 are groups having a non-aromatic carbon-carbon bond which is bound directly to D 1 of formula (I) or D 2 or D 3 of formula (II) or, if present to B 1 of formula (I) or B 2 of formula (II).
  • R 10 is as described above and is preferably H
  • Ar 9 is an unsubstituted or substituted monocyclic or fused aromatic or heteroaromatic group, preferably benzene or a monocyclic or bicyclic heteroaromatic group having C or N ring atoms only; and X 60 are each independently CN, CF3 or COOR 40 wherein R 40 in each occurrence is H or a substituent, preferably H or a C1-20 hydrocarbyl group. Preferably, each X 60 is CN.
  • Ar 9 may be unsubstituted or substituted with one or more substituents.
  • Substituents of Ar 9 are preferably selected from groups R 12 as described below.
  • the group of formula (IXa-1) has formula (IXa-2) or (IXa-3):
  • each X 7 -X 10 is independently CR 12 or N wherein R 12 in each occurrence is H or a substituent selected from C1-20 hydrocarbyl and an electron withdrawing group.
  • the electron withdrawing group is F, Cl, Br or CN, more preferably F, Cl or CN; and, for example, F or CN.
  • the Ci -20 hydrocarbyl group R 12 may be selected from C1-20 alkyl; unsubstituted phenyl; and phenyl substituted with one or more C1-12 alkyl groups.
  • each of X 7 -X 10 of formula (IXa-3) is CR 12 and each R 12 is independently selected from H or an electron-withdrawing group, preferably H, F or CN.
  • R 12 of X 8 and X 9 is an electron-withdrawing group, preferably F or CN.
  • Exemplary groups of formula (IXd) include:
  • Exemplary groups of formula (IXe) include:
  • An exemplary group of formula (IXj) is: wherein Ak is a C1-12 alkylene chain in which one or more C atoms may be replaced with
  • each benzene ring is independently unsubstituted or substituted with one or more substituents selected from substituents described with reference to R 10 .
  • Groups of formula (IXo) are bound directly to a bridging group B 1 or B 2 substituted with a group of formula -B(R 14 )2 wherein R 14 in each occurrence is a substituent, optionally a Ci- 20 hydrocarbyl group; is a bond to the boron atom -B(R 14 )2; and --- is a C-C bond between formula (IXo) and the bridging group.
  • R 14 is selected from C1-12 alkyl; unsubstituted phenyl; and phenyl substituted with one or more C1-12 alkyl groups.
  • the group of formula (IXo), the B 1 or B 2 group and the B(R 14 )2 substituent of B 1 or B 2 may be linked together to form a 5- or 6-membered ring.
  • a 1 is preferably a fused heteroaromatic group comprising at least 2 fused rings, preferably at least 3 fused rings.
  • a 1 of formula (II) is a group of formula (VIII): wherein:
  • Ar 1 may be a monocyclic or polycyclic heteroaromatic group which is unsubstituted or substituted with one or more R 9 groups wherein R 9 in each occurrence is independently a substituent.
  • R 9 groups are selected from
  • substituents of an aromatic or heteroaromatic group R 9 are F, CN, NO2, and C1-12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO and one or more H atoms of the alkyl may be replaced with F.
  • R 17 as described anywhere herein may be, for example, C1-12 alkyl, unsubstituted phenyl; or phenyl substituted with one or more C1-6 alkyl groups.
  • the replaced C atom may be a terminal C atom of the alkyl group or a nonterminal C-atom.
  • non-terminal C atom of an alkyl group as used anywhere herein means a C atom other than the C atom of the methyl group at the end of an n-alkyl chain or the C atoms of the methyl groups at the ends of a branched alkyl chain.
  • 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.
  • a countercation e.g., an ammonium or metal countercation, preferably an ammonium or alkali metal cation.
  • a C atom of an alkyl substituent group which is replaced with another atom or group as described anywhere herein is preferably a non-terminal C atom, and the resultant substituent group is preferably non-ionic.
  • Exemplary monocyclic heteroaromatic groups Ar 1 are oxadiazole, thiadiazole, triazole and 1,4-diazine which is unsubstituted or substituted with one or more substituents.
  • Thiadiazole is particularly preferred.
  • Exemplary polycyclic heteroaromatic groups Ar 1 are groups of formula (V) :
  • X 1 and X 2 are each independently selected from N and CR 10 wherein R 10 is H or a substituent, optionally H or a substituent R 9 as described above.
  • X 3 , X 4 , X 5 and X 6 are each independently selected from N and CR 10 with the proviso that at least one of X 3 , X 4 , X 5 and X 6 is CR 10 .
  • each R 5 is CN, COOR 40 ; or CX 60 X 61 wherein X 60 and X 61 is independently CN, CF3 or COOR 40 and R 40 in each occurrence is H or a substituent, preferably H or a C1-20 hydrocarbyl group.
  • a 1 groups of formula (VIII) are preferably selected from groups of formulae (Villa) and (VUIb):
  • the two R 7 groups may or may not be linked.
  • each R 7 is independently selected from H; F; CN; NO2; C1-20 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , CO, COO, NR 6 , PR 6 , or Si(R 10 )2 wherein R 10 and R 6 are as described above and one or more H atoms may be replaced with F; and aryl or heteroaryl, preferably phenyl, which may be unsubstituted or substituted with one or more substituents.
  • Substituents of the aryl or heteroaryl group may be selected from one or more of F; CN; NO2; and C1-20 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , CO, COO and one or more H atoms may be replaced with F.
  • the group of formula (VUIb) has formula (VIIIb-1) or (VIIIb-2): (VIIIb-1) (VIIIb-2)
  • Ar 2 is an aromatic or heteroaromatic group, preferably benzene, which is unsubstituted or substituted with one or more substituents.
  • Ar 2 may be unsubstituted or substituted with one or more substituents selected from H, F, Cl, CN, NO2, C1-16 alkyl or C1-16 alkoxy wherein one or more H atoms of the C1-16 alkyl or C1-16 alkoxy may be replaced with F.
  • Exemplary electron-accepting groups of formula (VIII) include, without limitation : wherein Ak 1 is a C1-20 alkyl group
  • Divalent electron-accepting groups A 2 other than formula (VIII) are optionally selected from formulae (IVa)-(IVj) ⁇ IVk )
  • Y A1 is O or S, preferably S.
  • R 23 in each occurrence is a substituent, optionally C1-12 alkyl wherein one or more non- adjacent C atoms other than the C atom attached to Z 3 may be replaced with O, S, NR 6 , COO or CO and one or more H atoms of the alkyl may be replaced with F.
  • R 25 in each occurrence is independently H; F; CN; NO2; C1-12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO and one or more H atoms of the alkyl may be replaced with F; an aromatic group, optionally phenyl, which is unsubstituted or substituted with one or more substituents selected from F and C1-12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO; or wherein Z 40 , Z 41 , Z 42 and Z 43 are each independently CR 13 or N wherein R 13 in each occurrence is H or a substituent, preferably a C1-20 hydrocarbyl group;
  • Y 40 and Y 41 are each independently O, S, NX 71 wherein X 71 is CN or COOR 40 ; or CX 60 X 61 wherein X 60 and X 61 is independently CN, CF3 or COOR 40 ;
  • W 40 and W 41 are each independently O, S, NX 71 wherein X 71 is CN or COOR 40 ; or CX 60 X 61 wherein X 60 and X 61 is independently CN, CF3 or COOR 40 ; and
  • R 40 in each occurrence is H or a substituent, preferably H or a C1-20 hydrocarbyl group.
  • Z 3 is N or P.
  • T 1 , T 2 and T 3 each independently represent an aryl or a heteroaryl ring, optionally benzene, which may be fused to one or more further rings.
  • Substituents of T 1 , T 2 and T 3 , where present, are optionally selected from non-H groups of R 25 .
  • T 3 is benzothiadiazole.
  • R 12 in each occurrence is a substituent, preferably a C1-20 hydrocarbyl group.
  • Ar 5 is an arylene or heteroarylene group, optionally thiophene, fluorene or phenylene, which may be unsubstituted or substituted with one or more substituents, optionally one or more non-H groups selected from R 25 .
  • each, D 1 of formula (I) is a group of formula (III).
  • each, D 2 and D 3 of formula (II) is a group of formula (III).
  • y 1 is at least 2 then at least one D 1 is a group of formula (III) and the one or more other groups D 1 may be a donor group other than Formula (III).
  • At least one of D 2 and D 3 is optionally a donor group other than formula (III).
  • Exemplary electron-donating groups D 1 , D 2 and D 3 other than formula (III) include groups of formulae (Vlla)-(VIIp):
  • Y A in each occurrence is independently O or S; Y A1 in each occurrence is independently O or S; Z A in each occurrence is O, CO, S, NR 55 or C(R 54 )?; R 51 , R 52 R 54 and R 55 independently in each occurrence is H or a substituent; R 53 independently in each occurrence is a substituent; and Ar 4 is an optionally substituted monocyclic or fused heteroaromatic group.
  • R 51 and R 52 independently in each occurrence are selected from H; F; C1-20 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO and one or more H atoms of the alkyl may be replaced with F; and an aromatic or heteroaromatic group Ar 3 which is unsubstituted or substituted with one or more substituents.
  • Ar 3 may be an aromatic group, e.g., phenyl.
  • Ar 4 is preferably selected from optionally substituted oxadiazole, thiadiazole, triazole, and 1,4-diazine.
  • the 1,4-diazine may be fused to a further heterocyclic group, optionally a group selected from optionally substituted oxadiazole, thiadiazole, triazole, 1,4-diazine and succinimide.
  • the one or more substituents of Ar 3 may be selected from C1-12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO and one or more H atoms of the alkyl may be replaced with F.
  • each R 54 is selected from the group consisting of:
  • Substituents of Ar 7 are preferably selected from F; Cl; NO2; CN; and C1-20 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , CO or COO and one or more H atoms may be replaced with F.
  • Ar 7 is phenyl.
  • each R 51 is H.
  • R 53 independently in each occurrence is selected from C 1-20 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO and one or more H atoms of the alkyl may be replaced with F; and phenyl which is unsubstituted or substituted with one or more substituents, optionally one or more C1-12 alkyl groups wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , COO or CO and one or more H atoms of the alkyl may be replaced with F.
  • R 55 as described anywhere herein is H or C1-30 hydrocarbyl group.
  • D 1 , D 2 and D 3 are each a group of formula (Vile).
  • y 1 of formula (I) is 1.
  • y 1 of formula (I) is 2 or 3 and D 1 in each occurrence is the same.
  • y 2 and y 3 of formula (II) are each 1.
  • y 1 of formula (I) is greater than 1, e.g., 2 or 3, or at least one of y 2 and y 3 of formula (II) is greater than 1, e.g., 2 or 3, the chain of D 1 , D 2 or D 3 groups, respectively, may be linked in any orientation.
  • Exemplary electron-donating materials of a photoactive layer as described herein are disclosed in, for example, WO2013/051676, the contents of which are incorporated herein by reference.
  • the electron-donating material may be a non-polymeric or polymeric material.
  • the electron-donating material is an organic conjugated polymer, which can be a homopolymer or copolymer including alternating, random or block copolymers.
  • the conjugated polymer is preferably a donor-acceptor polymer comprising alternating electron-donating repeat units and electron-accepting repeat units.
  • the electron-donating polymer is a conjugated organic polymer with a low bandgap, typically between 2.5 eV and 1.5 eV, preferably between 2.3 eV and 1.8 eV.
  • the electron-donating polymer has a HOMO level no more than 5.5 eV from vacuum level.
  • the electron-donating polymer has a HOMO level at least 4.1 eV from vacuum level.
  • polymers selected from conjugated hydrocarbon or heterocyclic polymers including polyacene, polyaniline, polyazulene, polybenzofuran, polyfluorene, polyfuran, polyindenofluorene, polyindole, polyphenylene, polypyrazoline, polypyrene, polypyridazine, polypyridine, polytriarylamine, poly(phenylene vinylene), poly(3-substituted thiophene), poly(3,4- bisubstituted thiophene), polyselenophene, poly(3-substituted selenophene), poly(3,4- bisubstituted selenophene), poly(bisthiophene), poly(terthiophene), poly(bisselenophene), poly(terselenophene), polythieno[2,3-b]thiophene, polythieno[3,2- b] th iophene, poly be
  • donor polymers are copolymers of polyfluorenes and polythiophenes, each of which may be substituted, and polymers comprising benzothiadiazole-based and thiophene-based repeating units, each of which may be substituted.
  • a particularly preferred donor polymer comprises a repeat unit of formula (X): wherein Y A , Z A , R 51 and R 54 are as described above.
  • Another particularly preferred donor polymer comprises repeat units of formula (XI): wherein R 18 and R 19 are each independently selected from H; F; C1-12 alkyl wherein one or more non-adjacent, non-terminal C atoms may be replaced with O, S, COO or CO and one or more H atoms of the alkyl may be replaced with F; or an aromatic or heteroaromatic group Ar 6 which is unsubstituted or substituted with one or more substituents selected from F and C1-12 alkyl wherein one or more non-adjacent, non-terminal C atoms may be replaced with O, S, COO or CO.
  • R 18 and R 19 are each independently selected from H; F; C1-12 alkyl wherein one or more non-adjacent, non-terminal C atoms may be replaced with O, S, COO or CO and one or more H atoms of the alkyl may be replaced with F; or an aromatic or heteroaromatic group Ar 6 which is unsubstituted or
  • the donor polymer is preferably a donor-acceptor (DA) copolymer comprising a donor repeat unit, for example a repeat unit of formula (X) or (XI), and an acceptor repeat unit, for example divalent electron-accepting units A 2 as described herein provided as polymeric repeat units.
  • DA donor-acceptor
  • the compound of formula (I) or (II) is the only electron-accepting material of an electron-accepting sub-layer or a bulk heterojunction layer as described herein.
  • an electron-accepting layer or a bulk heterojunction layer contains a compound of formula (I) or (II) and one or more further electron-accepting materials.
  • Preferred further electron-accepting materials are fullerenes.
  • the combined weight of the compound of formula (I) or (II) : fullerene acceptor weight ratio may be in the range of about 1 : 0.1 - 1 : 1, preferably in the range of about 1 : 0.1 - 1 : 0.5.
  • Fullerenes may be selected from, without limitation, Ceo, C70, C76, C78 and Cs4 fullerenes or a derivative thereof, including, without limitation, PCBM-type fullerene derivatives including phenyl-Cei-butyric acid methyl ester (CeoPCBM), TCBM-type fullerene derivatives (e.g., tolyl-Cei-butyric acid methyl ester (CeoTCBM)), and ThCBM-type fullerene derivatives (e.g., thienyl-Cei-butyric acid methyl ester (CeoThCBM).
  • PCBM-type fullerene derivatives including phenyl-Cei-butyric acid methyl ester (CeoPCBM), TCBM-type fullerene derivatives (e.g., tolyl-Cei-butyric acid methyl ester (CeoTCBM)), and ThCBM-type fullerene derivatives
  • Fullerene derivatives may have formu wherein A, together with the C-C group of the fullerene, forms a monocyclic or fused ring group which may be unsubstituted or substituted with one or more substituents.
  • Exemplary fullerene derivatives include formulae (Via), (VIb) and (Vic): wherein R 20 -R 32 are each independently H or a substituent.
  • Substituents R 20 -R 32 are optionally and independently in 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 with O, S, NR 6 , CO or COO and one or more H atoms may be replaced with F.
  • Substituents of aryl or heteroaryl, where present, are optionally selected from C1-12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 6 , CO or COO and one or more H atoms may be replaced with F.
  • the photoactive layer may be formed by any process including, without limitation, thermal evaporation and solution deposition methods.
  • an electron-accepting sub-layer or a bulk heterojunction layer is formed by depositing a formulation comprising the compound of formula (I) or (II) and any other components of the layer, including one or more electron-donating materials in the case of a bulk heterojunction layer, dissolved or dispersed in a solvent or a mixture of two or more solvents followed by evaporation of the one or more solvents.
  • the formulation may be deposited by any coating or printing method including, without limitation, spin-coating, dip-coating, roll-coating, spray coating, doctor blade coating, wire bar coating, slit coating, ink jet 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 further solvents.
  • the one or more further solvents may be selected from esters, optionally alkyl or aryl esters of alkyl or aryl carboxylic acids, optionally a Ci- 10 alkyl benzoate, benzyl benzoate or dimethoxybenzene.
  • a mixture of trimethylbenzene and benzyl benzoate is used as the solvent.
  • a mixture of trimethylbenzene and dimethoxybenzene is used as the solvent.
  • the formulation may comprise further components in addition to the electron-accepting material, the electron-donating material and the one or more solvents.
  • adhesive agents defoaming agents, deaerators, viscosity enhancers, diluents, auxiliaries, flow improvers colourants, dyes or pigments, sensitizers, stabilizers, nanoparticles, surface-active compounds, lubricating agents, wetting agents, dispersing agents and inhibitors may be mentioned.
  • the photoactive layer is formed over one of the anode and cathode of the organic photoresponsive device and the other of the anode and cathode is formed over the photoactive layer.
  • a circuit may comprise the OPD connected to one or more of a voltage source for applying a reverse bias to the device; a device configured to measure photocurrent; and an amplifier configured to amplify an output signal of the OPD.
  • the voltage applied to the photodetector may be variable.
  • the photodetector may be continuously biased when in use.
  • a photodetector system comprises a plurality of photodetectors as described herein, such as an image sensor of a camera.
  • a sensor may comprise an OPD as described herein and a light source wherein the OPD is configured to receive light emitted from the light source.
  • the light source has a peak wavelength of at least 900 nm or at least 1000 nm, optionally in the range of 900-1500 nm.
  • the light from the light source may or may not be changed before reaching the OPD. For example, the light may be reflected, filtered, down-converted or up-converted before it reaches the OPD.
  • the organic photoresponsive 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, without limitation, detecting the presence and I or brightness of ambient light and in a sensor comprising the organic photodetector and a light source.
  • the photodetector may be configured such that light emitted from the light source is incident on the photodetector and changes in wavelength and/or brightness of the light may be detected, e.g., due to absorption by, reflection by and/or emission of light from an object, e.g., a target material in a sample disposed in a light path between the light source and the organic photodetector.
  • SWV square wave voltammetry
  • the current at a working electrode is measured while the potential between the working electrode and a reference electrode is swept linearly in time.
  • the difference current between a forward and reverse pulse is plotted as a function of potential to yield a voltammogram. Measurement may be with a CHI 660D Potentiostat.
  • the apparatus to measure HOMO or LUMO energy levels by SWV may comprise a cell containing 0.1 M tertiary butyl ammonium hexafluorophosphate in acetonitrile; a 3 mm diameter glassy carbon working electrode; a platinum counter electrode and a leak free Ag/AgCI reference electrode.
  • Ferrocene is added directly to the existing cell at the end of the experiment for calculation purposes where the potentials are determined for the oxidation and reduction of ferrocene versus Ag/AgCI using cyclic voltammetry (CV).
  • the sample is dissolved in toluene (3 mg I ml) and spun at 3000 rpm directly on to the glassy carbon working electrode.
  • LUMO 4.8-E ferrocene (peak to peak average) - E reduction of sample (peak maximum).
  • HOMO 4.8-E ferrocene (peak to peak average) + E oxidation of sample (peak maximum).
  • absorption spectra were measured using a Cary 5000 UV-VIS- NIR Spectrometer. Measurements were taken from 175 nm to 3300 nm using a PbSmart NIR detector for extended photometric range with variable slit widths (down to 0.01 nm) for optimum control over data resolution.
  • absorption values are of a solution.
  • Absorption data are obtained by measuring the intensity of transmitted radiation through a solution sample. Absorption intensity is plotted vs. incident wavelength to generate an absorption spectrum.
  • a method for measuring absorption may comprise measuring a 15 mg I ml solution in a quartz cuvette and comparing to a cuvette containing the solvent only.
  • solution absorption data as provided herein is as measured in a methylated benzene solution, optionally a 1,2,4-trimethylbenzene solution.
  • Compound Example 1 Acceptor Group 1 was prepared as described in WO2022/129137, the contents of which are incorporated herein by reference.
  • Donor Groups 2 and 3 may be reacted in the same way as Donor Group 1 to form compounds of Formula (I).
  • Acceptor Group 2
  • Acceptor Group 2 was prepared by the method described in W02024/094804, the contents of which are incorporated herein by reference.
  • Compound Example 2 illustrated below, was prepared in the same way as Compound Example 1 except that Donor Group 2 was used in place of Donor Group 1.
  • Compound Example 3 was prepared as described for Compound Examples 1 and 2, using Acceptor Group 2.
  • a glass substrate coated with a 45 nm thick layer of indium-tin oxide (ITO) was coated with a 0.2 % polyethyleneimine (PEIE) solution in water to form a ⁇ 5 nm film modifying the work function of the ITO.
  • PEIE polyethyleneimine
  • a ca. 500 nm thick bulk heterojunction layer of a mixture of Donor Polymer 1 : Compound Example 1 (1 : 0.7 by weight) was deposited over the modified ITO layer by bar coating from a 10 mg/ml solution in an o-dichlorobenzene I butylbenzoate solvent mixture (90: 10 v/v).
  • An anode stack of MoOs (lOnm) and ITO (50nm) was formed over the bulk heterojunction by thermal evaporation (MoOs) and sputtering (ITO).
  • Figure 5 is a plot of current density vs. applied voltage for Device Example 1.
  • Figure 6 is a plot of external quantum efficiency (EQE) vs. wavelength for Device Example 1.
  • a glass substrate with a 150 nm thick layer of indium-tin oxide (ITO) was coated with a 0.2 % polyethyleneimine (PEIE) solution in water to form a ⁇ 5 nm film modifying the work function of the ITO.
  • a ca. 500 nm thick bulk heterojunction layer of a mixture of Donor Polymer 1 : Compound Example 1 (1 : 0.7 by weight) was deposited over the modified ITO layer by bar coating from a 10 mg/ml solution in a 1,2,4’trimethylbenzene : o- dichlorobenzene : 1,2-dimethoxybenzene mixture (3: 1 : 1 v/v).
  • An anode stack of MoOs (lOnm) and ITO (70nm) was formed over the bulk heterojunction by thermal evaporation (MoOs) and sputtering (ITO).
  • a device was prepared as described in Device Example 2 except that Compound Example
  • a device was prepared as described in Device Example 2 except that Compound Example
  • Device performance of Device Examples 2 and 3 is set out in Table 2 and in Figures 7 and 8.
  • Device performance of Device Example 4 is set out in Table 2 and in Figures 9 and 10.
  • Device Examples 2 and 3 show high efficiencies at wavelengths above about 1000 nm, indicating that both Compound Examples 1 and 2 are suitable for use in organic photodetectors for detection of wavelengths in the range of about 1000- 1500 nm.
  • the difference in external quantum efficiencies between Device Examples 2 and 3 becomes more pronounced at wavelengths above 1000 nm and with reference to Figure 7, surprisingly, Device Example 3 has a lower dark current than Device Example 2 indicating that Compound Example 2 is particularly suited to use on an organic photodetector for detection of wavelengths in the 1000-1500 nm range.
  • the HOMO and LUMO energy levels of compounds of formula (I) and (II) containing a group of formula (III) and comparative NFAs which do not have a group of formula (III) were modelled using Gaussian09 software available from Gaussian using Gaussian09 with B3LYP (functional) and LACVP* (Basis set).
  • Results are set out in Tables 3-5in which in which Slf corresponds to oscillator strength of the transition from SI (predicting absorption intensity) and Eopt is the modelled optical gap.
  • Model Compounds 27 and 28 which are based on Compound Example 1, show different conformers of the same compound, described herein as the "S-conformer” and the “C- conformer” respectively.
  • the modelled energy of Model Compound 27 is higher than that of Model Compound 28, indicating that the C-conformation of Model
  • Compound 27 is more favoured.
  • Model Compounds 32 and 33 also show the S-conformation and C-conformation of the same compound based on Compound Example 1.
  • the C-conformer of Model Compound 32 has the lower energy.
  • data for Model Compound 29, corresponding to Compound Example 2 indicates that the S-conformer is preferred.
  • the S-conformer may pack differently in a film to the C-conformer in a way that results in lower conformational disorder and reduced defect (trap) density, resulting in lower dark current than a film of Compound Example 1.
  • Table 7 shows a comparison of modelled and experimental values for Compound Example 1 and a corresponding model compound in which alkyl and phenyl substituents have been replaced with methyl to simplify calculation.

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Abstract

L'invention concerne un composé de formule (I) ou (II) : dans laquelle : A1 est un groupe accepteur d'électrons hétéroaromatique divalent; A2 et A3 sont indépendamment à chaque occurrence un groupe accepteur d'électrons monovalent; D1, D2 et D3 dont indépendamment à chaque occurrence un groupe donneur d'électrons; B1, B2 et B3 sont indépendamment à chaque occurrence un groupe de pontage; x1 et x2 sont chacun indépendamment 0, 1, 2 ou 3; x3 et x4 sont chacun indépendamment 0, 1, 2 ou 3; y1, y2 et y3 sont chacun indépendamment au moins 1; z1 et z2 sont chacun indépendamment 0, 1, 2 ou 3; et au moins une occurrence de D1 de formule (I) ou au moins une occurrence d'au moins l'un parmi D2 et D3 de formule (II) est un groupe de formule (III) : dans laquelle : X1 et X2 sont chacun indépendamment choisis parmi O, S et NR1, R1 étant H ou un substituant, à condition qu'au moins l'un parmi X1 et X2 soit NR1; Y est O ou S; Ar1 et Ar2 sont chacun indépendamment un groupe aromatique ou hétéroaromatique monocyclique ou fusionné ou est absent; R1 est H ou un substituant; et R2 est indépendamment à chaque occurrence un substituant.
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