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Definitions

• Embodiments of the present disclosure relate to electron-accepting compounds and more specifically, but not by way of limitation, to compounds containing electron-accepting and electron donating units, the compounds being suitable for use as an electron-accepting material in a photoresponsive device.
• Electron-accepting non-fullerene compounds are known.
• Non-fullerene acceptors with nitrogen-containing six-membered heterocycle cores for the applications in organic solar cells discloses non-fullerene acceptors with pyrazine or pyridazine as the cores.
• CN110379926 discloses an organic solar cell based on a benzodithiazole near-infrared receptor.
• CN112608333 discloses a small molecule based on a bi sthiadi azole carbazole derivative.
• CN112259687 discloses a ternary fullerene organic solar cell.
• the present disclosure provides a compound of formula (I): wherein:
• D 1 and D 2 independently in each occurrence is an electron-donating group
• a 2 and A 3 are each independently an electron-accepting group
• B 1 and B 2 in each occurrence are independently a bridging group; xl and x2 are each independently 0, 1, 2 or 3; yl and y2 are each independently at least 1; zl and z2 are each independently 0, 1, 2 or 3; and
• a 1 is a group of formula (II): wherein:
• Ar 1 is an aromatic or heteroaromatic group
• Y is O, S, NR 4 or Rj-C ⁇ -R 1 wherein R 1 in each occurrence is independently H or a substituent wherein two substituents R 1 may be linked to form a monocyclic or polycyclic ring and R 4 is H or a substituent.
• R 1 in each occurrence is independently H or a substituent wherein two substituents R 1 may be linked to form a monocyclic or polycyclic ring and R 4 is H or a substituent.
• the group of formula (II) has formula (Ila):
• the group of formula (II) has formula (lib) :
• each R 1 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, CO, COO, NR 4 , PR 4 , or Si(R 3 )2 and one or more H atoms may be replaced with F; and aryl or heteroaryl which may be unsubstituted or substituted with one or more substituents, wherein R 3 and R 4 are each independently H or a substituent.
• the two R 1 groups are linked.
• the compound of formula (lib) has formula (IIb-1) or (IIb-2):
• Ar 2 is an aromatic or heteroaromatic group which is unsubstituted or substituted with one or more substituents
• Ar 2 is benzene which is unsubstituted or substituted with one or more substituents.
• At least one of xl and x2 is at least 1 and B 1 in each occurrence is independently selected from vinylene, arylene, heteroarylene, arylenevinylene and heteroarylenevinylene, each of which is unsubstituted or substituted with one or more substituents.
• At least one of zl and z2 is at least 1 and B 2 in each occurrence is independently selected from vinylene, arylene, heteroarylene, arylenevinylene and heteroarylenevinylene, each of which is unsubstituted or substituted with one or more substituents.
• D 1 and D 2 are each independently selected from units of formulae (Vlla)-(VIIp) as described herein.
• 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 or D 2 or, if present, to B 2 .
• a 2 and A 3 are each independently selected from groups of formulae (Illa)-(IIIq) as described herein.
• At least one A is a group of formula (Illa- 1): wherein: each X 3 -X 4 is independently CR 12 or N wherein R 12 in each occurrence is H or a substituent selected from Ci-2ohydrocarbyl and an electron-withdrawing group and wherein R 10 is H or a substituent.
• the polymer has an absorption peak of greater than 900 nm.
• the present disclosure provides a compound of formula (I): wherein:
• a 1 is an electron-accepting group
• D 1 and D 2 independently in each occurrence is an electron-donating group
• a 1 , A 2 and A 3 are each independently an electron-accepting group; B 1 and B 2 in each occurrence are independently a bridging group; xl and x2 are each independently 0, 1, 2 or 3; yl and y2 are each independently at least 1; zl and z2 are each independently 0, 1, 2 or 3; and at least one of (i)-(iv) applies:
• a 2 and A 3 are different;
• D 1 , D 2 , A 1 , A 2 , A 3 , B 1 , B 2 , xl, x2, yl, y2, zl and z2 may be as described anywhere herein.
• the present disclosure provides a compound of formula (X): wherein:
• a 1 , A 2 and A 3 are each independently an electron-accepting group
• D 1 and D 2 independently in each occurrence is an electron-donating group
• B 1 and B 2 independently in each occurrence is a bridging group; xl and x2 are each independently 0, 1, 2 or 3; yl and y2 are each independently at least 1; and z 3 and z 4 are each independently 0, 1, 2 or 3 with the proviso that at least one of z 3 and z 4 is at least 1.
• D 1 , D 2 , A 1 , A 2 , A 3 , B 1 , B 2 , xl, x2, yl, y2, zl and z2 of formula (X) may be as described anywhere herein, for example as described with respect to compounds of formula (I).
• the present disclosure provides composition comprising an electrondonating material and an electron-accepting material wherein the electron accepting material is a compound as described herein.
• the present disclosure provides an organic electronic device comprising an active layer comprising a compound or composition as described herein.
• the organic electronic device is an organic photoresponsive device comprising a bulk heterojunction layer disposed between an anode and a cathode and wherein the bulk heterojunction layer comprises 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 or 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 according as described herein onto a surface and evaporation of the one or more solvents.
• Figure 1 illustrates an organic photoresponsive device according to some embodiments.
• Figure 2A shows absorption spectra for films of Compound Examples 1 and 2 a compound according to embodiments of the present disclosure and Comparative Compound 1
• Figure 2B shows absorption spectra for films of Compound Examples 1 and 2 a compound according to embodiments of the present disclosure and Comparative Compound 2;
• Figure 3A shows an absorption spectrum for a film of Compound Example 3
• Figure 3B shows a long wavelength range detail of the spectrum of Figure 3 A
• Figure 3C shows an absorption spectrum for a solution of Compound Example 3
• Figure 3D shows a long wavelength range detail of the spectrum of Figure 3C
• Figure 4A shows an absorption spectrum for a film of Compound Example 4.
• Figure 4B shows a long wavelength range detail of the spectrum of Figure 4A
• Figure 4C shows an absorption spectrum for a solution of Compound Example 4.
• Figure 4D shows a long wavelength range detail of the spectrum of Figure 4C
• Figure 5 shows absorption spectra for o-dichlorobenzene solutions of Compound Examples 5, 6 and 7;
• Figure 6 shows absortion spectra in o-dichlorobenzene for Compound Examples 6 and 8;
• Figure 7 shows absorption spectra in o-dichlorobenzene for Compound Example 9 and a comparative compound
• Figure 8 is a graph of external quantum efficiencies between 500 and 1700 nm for an organic photodetector containing Compound Example 1 according to an embodiment of the present disclosure
• Figure 9A is a graph of current density vs. reverse bias voltage for an organic photodetector containing Compound Example 3 according to an embodiment of the present disclosure under dark conditions and under illumination at 940 nm, 1200 nm and white light;
• Figure 9B is a graph of external quantum efficiency vs. wavelength at -2V applied voltage for the device of Figure 6A;
• Figure 10 is a graph of external quantum efficiency vs wavelength at a -5V applied voltage for an organic photodetector containing Compound Example 4 according to an embodiment of the present disclosure;
• Figure 11 is graphs of external quantum efficiency vs wavelength at a -5V applied voltage for organic photodetectors containing Compound Example 5, 6 and 7 according to an embodiment of the present disclosure.
• 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 are 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.
• a compound of formula (I) or (X) as described herein may be provided in a bulk heterojunction layer of a photoresponsive device, preferably a photodetector, in which the bulk heterojunction layer is disposed between an anode and a cathode.
• the bulk heterojunction layer comprises or consists of an electron-donating material and an electron-accepting compound of formula (I) or (X) as described herein.
• the bulk heterojunction layer contains two or more accepting materials and / or two or more 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 electron-accepting material, i.e. the electron-donating material has a shallower HOMO and LUMO that the corresponding HOMO and LUMO levels of the electron-accepting material.
• the compound of formula (I) or (X) has a HOMO level that is at least 0.05 eV deeper, optionally at least 0.10 eV deeper, than the HOMO of the electron-donating material.
• the gap between the HOMO level of the electron-donating material and the LUMO level of the electron-accepting compound of formula (I) or (X) is less than 1.4 eV.
• HOMO and LUMO levels of materials as described herein are as measured by square wave voltammetry (SWV).
• 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/AgCl 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/AgCl using cyclic voltammetry (CV).
• the sample is dissolved in toluene (3 mg / 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).
• a typical SWV experiment runs at 15 Hz frequency; 25 mV amplitude and 0.004 V increment steps. Results are calculated from 3 freshly spun film samples for both the HOMO and LUMO data.
• the compound of formula (I) or (X) has an absorption peak greater than 900 nm, optionally greater than 1000 nm, optionally greater than 1200 nm.
• absorption spectra of materials as described herein are measured using a Cary 5000 UV-VIS-NIR Spectrometer. Measurements were taken from 175 nm to 3300 nm using a Pb Smart NIR detector for extended photometric range with variable slit widths (down to 0.01 nm) for optimum control over data resolution.
• 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 film absorption may comprise measuring a 15 mg / ml solution in a quartz cuvette and comparing to a cuvette containing the solvent only.
• absorption data as provided herein is as measured in toluene solution.
• the electron-accepting compound has formula (I):
• D 1 and D 2 independently in each occurrence is an electron-donating group.
• a 1 , A 2 and A 3 are each independently an electron-accepting group.
• B 1 and B 2 in each occurrence are independently a bridging group.
• xl and x2 are each independently 0, 1, 2 or 3, preferably 0 or 1.
• yl and y2 are each independently at least 1, preferably 1, 2 or 3, more preferably 1.
• zl and z2 are each independently 0, 1, 2 or 3, preferably 0 or 1.
• Each of the electron-accepting groups A 1 , A 2 and A 3 has a lowest unoccupied molecular orbital (LUMO) level that is deeper (i.e., further from vacuum) than the LUMO of either of the electron-donating groups D 1 or D 2 , preferably at least 1 eV deeper.
• LUMO lowest unoccupied molecular orbital
• 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).
• a 1 of formula (I) is a group of formula (II): wherein:
• Ar 1 is an aromatic or heteroaromatic group
• the compound of formula (I) is a “symmetric” compound in which - (B 1 )xl-(D 1 )yl-(B 2 )zl-A 2 is the same as -(B 1 )x2-(D 2 )y2-(B 2 )z2-A 3 .
• the compound of formula (I) is a compound in which -(B 1 )xl-(D 1 )yl- (B 2 )zl-A 2 is different from -(B 1 )x2-(D 2 )y2-(B 2 )z2-A 3 .
• Such compounds are described hereinafter as “asymmetric” compounds.
• D 1 and D 2 are different and yl and y2 are the same or different.
• yl and y2 are different and D 1 and D 2 are the same or different.
• xl and x2 are different.
• B 2 of (B 2 ) zi is different from B 2 of (B 2 ) Z 2.
• zl and z2 are different.
• the present disclosure provides compounds of formula (X): wherein A 1 , A 2 , A 3 , B 1 , B 2 , D 1 , D 2 , xl, x2, yl and y2 are as described above with respect to formula (I) and z3 and z4 are each independently 0, 1, 2 or 3 with the proviso that at least one of z3 and z4 is at least 1.
• Ar 1 may be a monocyclic or polycyclic heteroaromatic group which is unsubstituted or substituted with one or more R 2 groups wherein R 2 in each occurrence is independently a substituent.
• R 2 groups are selected from
• C1-20 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 7 wherein R 7 is a C1.12 hydrocarbyl, COO or CO and one or more H atoms of the alkyl may be replaced with F; an aromatic or heteroaromatic group, preferably phenyl, which is unsubstituted or substituted with one or more substituents; and a group selected from 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 or CX 60 X 61 wherein
• substituents of an aromatic or heteroaromatic group R 2 are F, CN, NO2, and C1-12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 7 , COO or CO and one or more H atoms of the alkyl may be replaced with F.
• R 7 as described anywhere herein may be, for example, C1-12 alkyl, unsubstituted phenyl; or phenyl substituted with one or more C1-6 alkyl groups.
• 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 3 wherein R 3 is H or a substituent, optionally H or a substituent R 2 as described above.
• X 3 , X 4 , X 5 and X 6 are each independently selected from N and CR 3 with the proviso that at least one of X 3 , X 4 , X 5 and X 6 is CR 3 .
• each R 4 of any NR 4 or PR 4 described anywhere herein is independently selected from H; C1-20 alkyl wherein one or more non-adjacent C atoms other than the C atom bound to N or P may be replaced with O, S, NR 7 , 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 of the alkyl may be replaced with O, S, NR 7 , COO or CO and one or more H atoms of the alkyl may be replaced with F.
• 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 (II) are preferably selected from groups of formulae (Ila) and (lib):
• the two R 1 groups may or may not be linked.
• each R 1 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 7 , CO, COO, NR 4 , PR 4 , or Si(R 3 )2 wherein R 3 and R 4 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 7 , CO, COO and one or more H atoms may be replaced with F.
• the group of formula (lib) has formula (IIb-1) or (IIb-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 R 2 as described above.
• Exemplary electron-accepting groups of formula (II) include, without limitation:
• 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 1 may be replaced with O, S, NR 7 , 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 7 , 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 7 , 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 1 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 .
• 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 .
• the monovalent acceptor Groups A 2 and A 3 may each independently be selected from any such units known to the skilled person.
• a 2 and A 3 may be the same or different, preferably different.
• Exemplary monovalent acceptor units include, without limitation, units of formulae (Illa)- (iiiq)
• 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.
• N atom of formula (Ille) may be unsubstituted or substituted.
• R 10 is H or a substituent, preferably a substituent selected from the group consisting of C1.12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 7 , 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 7 , 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 7 , 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; F; C1-12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 7 , 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 7 , COO or CO; or a group selected from:
• 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; and Ci-12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 7 , 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 7 , COO or CO and one or more H atoms of the alkyl may be replaced with F.
• T 1 , T 2 and T 3 are each independently as described above.
• 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 2 and to a boron substituent of B 2 .
• Preferred groups A 2 and A 3 are groups having a non-aromatic carbon-carbon bond which is bound directly to DI or D2 or, if present to B2.
• At least one of A 2 and A 3 are a group of formula (IIIa-1): wherein:
• R 10 is as described above; 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;
• X 60 and X 61 is 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.
• R 40 in each occurrence is H or a substituent, preferably H or a C1-20 hydrocarbyl group.
• X 60 and X 61 are each CN.
• the C 1-20 hydrocarbyl group R 12 may be selected from C1.20 alkyl; unsubstituted phenyl; and phenyl substituted with one or more C1-12 alkyl groups.
• Exemplary groups of formula (Hid) include: Exemplary groups of formula (Hie) include:
• An exemplary group of formula (Illj) is: wherein Ak is a C1-12 alkylene chain in which one or more C atoms may be replaced with O, S, NR 7 , CO or COO; An is an anion, optionally -SOs’; and each benzene ring is independently unsubstituted or substituted with one or more substituents selected from substituents described with reference to R 10 .
• An exemplary group of formula (Ilin) is: Groups of formula (IIIo) are bound directly to a bridging group B 2 substituted with a -B(R 14 )2 wherein R 14 in each occurrence is a substituent, optionally a Ci-2o hydrocarbyl group; — > ⁇ is a bond to the boron atom -B(R 14 )2 of R 3 or R 6 ; and — is the bond to B 2 .
• 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 (IIIo), the B 2 group and the B(R 14 )2 substituent of B 2 may be linked together to form a 5- or 6-membered ring.
• groups of formula (IIIo) are selected from:
• Bridging units B 1 and B 2 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.
• Bridging units B 1 and B 2 preferably are monocyclic or fused bicyclic arylene or heteroarylene groups, more preferably monocyclic or fused bicyclic heteroarylene groups.
• B 1 and B 2 are is selected from units of formulae (Via) - (VIg): (Vie) (VIf) (VIg) wherein Y A is O, S or NR 55 wherein R 55 is H or a substituent; R 8 in each occurrence is independently H or a substituent, preferably H or a substituent selected from F; CN; NO2; Ci- 20 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 7 , COO or
• R 8 groups of formulae (Via), (VIb) and (Vic) may be linked to form a bicyclic ring, for example thienopyrazine.
• R 8 is preferably H, C1.20 alkyl or C1-19 alkoxy.
• Electron-donating groups preferably are fused aromatic or heteroaromatic groups, more preferably fused heteroaromatic groups containing 3 or more rings.
• Particularly preferred electron-donating groups comprise fused thiophene or furan rings, optionally fused rings containing thiophene or furan rings and one or more rings selected from benzene, cyclopentadiene, tetrahydropyran, tetrahydrothiopyran and piperidine rings, each of said rings being unsubstituted or substituted with one or more substituents.
• Exemplary electron-donating groups D 1 and D 2 include groups of formulae (Vlla)-(VIIp):
• Y A in each occurrence is independently O, S or NR 55
• Z A in each occurrence is O, CO, S, NR 55 or C(R 54 )2
• 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.
• R 51 and R 52 independently in each occurrence are selected from H; F; C 1-20 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 7 , 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.
• 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 7 , 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 7 , 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 C1-20 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR 7 , 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 7 , 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 and D 2 are each independently a group of formula (Vila).
• exemplary groups of formula (Vila) include, without limitation: wherein He in each occurrence is independently a C1-20 hydrocarbyl group, e.g., C1-20 alkyl, unsubstituted aryl, or aryl substituted with one or more C1-12 alkyl groups.
• the aryl group is preferably phenyl.
• yl and y2 are each 1. In some embodiments, at least one of yl and y2 is greater than 1.
• the chain of D 1 and / or D 2 groups, respectively, may be linked in any orientation. For example, in the case where D 1 is a group of formula (Vila) and yl is 2, -[D ⁇ yi-may be selected from any of:
• a bulk heterojunction layer as described herein comprises an electron-donating material and a compound of formula (I) or (X) as described herein.
• exemplary donor materials are disclosed in, for example, WO2013051676, 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, polytri aryl amine, poly(phenylene vinylene), poly(3 -substituted thiophene), poly(3,4-bi substituted 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]thiophene, polybenzothi
• 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 donor unit (Vila) provided as a repeat unit of the polymer, most preferably with an electron-accepting repeat unit, for example divalent electron-accepting units as described herein provided as polymeric repeat units.
• the compound of formula (I) or (X) as described herein is the only electron-accepting material of a bulk heterojunction layer.
• the bulk heterojunction layer contains a compound of formula (I) or (X) and one or more further electron-accepting materials.
• the one or more further electronaccepting materials may be selected from non-fullerene acceptors and fullerenes.
• Non-fullerene acceptors are described in, for example, Cheng et. al., “Next-generation organic photovoltaics based on non-fullerene acceptors”, Nature Photonics volume 12, pages 131-142 (2016), the contents of which are incorporated herein by reference, and which include, without limitation, PDI, ITIC, ITIC, IEICO and derivatives thereof, e.g., fluorinated derivatives thereof such as ITIC-4F and IEICO-4F.
• Exemplary fullerene electron-accepting compounds are C 60 , C 70 , C 76 , C 78 and C 84 fullerenes or a derivative thereof, including, without limitation, PCBM-type fullerene derivatives including phenyl-C61-butyric acid methyl ester (C60PCBM), 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).
• PCBM-type fullerene derivatives including phenyl-C61-butyric acid methyl ester (C60PCBM)
• TCBM-type fullerene derivatives e.g. tolyl-C 61 -butyric acid methyl ester (C 60 TCBM)
• Fullerene derivatives may have formula (V): 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 (Va), (Vb) and (Vc): (Va) (Vb) (Vc) 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 7 , 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 7 , CO or COO and one or more H atoms may be replaced with F.
• the bulk heterojunction layer may be formed by any process including, without limitation, thermal evaporation and solution deposition methods.
• the bulk heterojunction layer is formed by depositing a formulation comprising the electron-donating material(s), the electron-accepting material(s) and any other components of the bulk heterojunction layer dissolved or dispersed in a solvent or a mixture of two or more solvents.
• the formulation may be deposited by any coating or printing method including, 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 one or more solvents of the formulation may optionally comprise or consist of benzene substituted with one or more substituents selected from chlorine, C1-10 alkyl and Ci-io alkoxy wherein two or more substituents may be linked to form a ring which may be unsubstituted or substituted with one or more C1-6 alkyl groups, optionally toluene, xylenes, trimethylbenzenes, tetramethylbenzenes, anisole, indane and its alkyl-substituted derivatives, and tetralin and its alkyl-substituted derivatives.
• substituents selected from chlorine, C1-10 alkyl and Ci-io alkoxy wherein two or more substituents may be linked to form a ring which may be unsubstituted or substituted with one or more C1-6 alkyl groups, optionally toluene, xylenes, trimethylbenzenes, tetramethylbenzenes, anisole
• 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 C1-10 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.
• a polymer or composition as described herein may be provided as an active layer of an organic electronic device.
• a bulk heterojunction layer of an organic photoresponsive device more preferably an organic photodetector, comprises a composition as described herein.
• FIG. 1 illustrates an organic photoresponsive device according to some embodiments of the present disclosure.
• the organic photoresponsive device comprises a cathode 103, an anode 107 and a bulk heterojunction layer 105 disposed between the anode and the cathode.
• the organic photoresponsive device may be supported on a substrate 101, optionally a glass or plastic substrate.
• 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 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 bulk heterojunction layer shown in Figure 1.
• a hole-transporting layer is disposed between the anode and the bulk heterojunction layer.
• an electron-transporting layer is disposed between the cathode and the bulk heterojunction layer.
• a work function modification layer is disposed between the bulk heterojunction layer and the anode, and/or between the bulk heterojunction layer and the cathode.
• the area of the OPD may be less than about 3 cm 2 , less than about 2 cm 2 , less than about 1 cm 2 , less than about 0.75 cm 2 , less than about 0.5 cm 2 or less than about 0.25 cm 2 .
• each OPD may be part of an OPD array wherein each OPD is a pixel of the array having an area as described herein, optionally an area of less than 1 mm 2 , optionally in the range of 0.5 micron 2 - 900 micron 2 .
• 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.
• the bulk heterojunction layer contains a polymer as described herein and an electronaccepting compound.
• the bulk heterojunction layer may consist of these materials or may comprise one or more further materials, for example one or more further electron-donating materials and / or one or more further electron-accepting compounds.
• a circuit may comprise the OPD connected to a voltage source for applying a reverse bias to the device and / or a device configured to measure photocurrent.
• 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 1000-1500 nm.
• a material comprising an electron-accepting unit of formula (I) may be used for the detection of light at longer wavelengths, particularly 1300- 1400 nm.
• the light from the light source may or may not be changed before reaching the OPD.
• 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 / 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.
• the sample may be a non-biological sample, e g. a water sample, or a biological sample taken from a human or animal subject.
• the sensor may be, without limitation, a gas sensor, a biosensor, an X-ray imaging device, an image sensor such as a camera image sensor, a motion sensor (for example for use in security applications) a proximity sensor or a fingerprint sensor.
• a ID or 2D photosensor array may comprise a plurality of photodetectors as described herein in an image sensor.
• the photodetector may be configured to detect light emitted from a target analyte which emits light upon irradiation by the light source or which is bound to a luminescent tag which emits light upon irradiation by the light source.
• the photodetector may be configured to detect a wavelength of light emitted by the target analyte or a luminescent tag bound thereto.
• Tri(o-tolyl)-phosphine (0.09 g, 0.30 mmol) and Tris(dibenzylideneacetone)dipalladium(0) (0.07 g, 0.08 mmol) were added to a solution of Intermediate C (0.45 g, 0.99 mmol) and Intermediate B (1.63 g, 2.37 mmol) in toluene and the mixture was heated at 70 °C for 30 minutes, after which time the temperature was increased to 100 °C for a further 2 hours . The reaction mixture was then cooled, diluted with toluene and filtered through a silica plug and washed with toluene. Purification via column chromatography (eluant 5-10% of toluene in heptane) gave Intermediate D as deep green oil (1.03 g, 95.3 % yield) LCMS confirmed the mass of the expected product.
• Toluene 60 ml was added to CPDT-SnBus (4.84 g, 7.00 mmol) and BisBT-diBr (1.15 g, 3.26 mmol) under nitrogen. The mixture was degassed for 15 minutes and tris(2- methylphenyl)phosphine (0.30 g, 0.98 mmol) and tris(dibenzylideneacetone) dipalladium (0.24 g, 0.26 mmol) were added and the mixture was degassed for additional 5 minutes. The mixture was heated at 70 °C for 30 minutes and then at 100 °C overnight. Upon completion, solvent was removed on a rotary evaporator and purification by column chromatography (silica gel; heptane/toluene)gave Compound 18 (2.37 g) as a dark brown oil.
• Compound 21 was prepared as described in Zhang et al, “Electron-Deficient and Quinoid Central Unit Engineering for Unfused Ring-Based Ai-D-A2-D-Ai-Type Acceptor Enables High Performance Nonfullerene Polymer Solar Cells with High F O c and PCE Simultaneously” Small 2020, 16, 1907681.
• a compound in which the donor groups are different may be prepared according to the following reaction scheme.
• Comparative Compound 1 The absorption spectrum for Comparative Compound 1 is taken from Pang et al, “Nonfused Nonfullerene Acceptors with an A-D-A'-D-A Framework and a Benzothiadiazole Core for High-Performance Organic Solar Cells”, ACS Appl. Mater. Interfaces 2020, 12, 14, 16531- 16540.
• Figure 2B shows the absorption spectrum of films of Compound Examples 1 and 2 compared to the Comparative Compound 2:
• Comparative Compound 2 The absorption spectrum for Comparative Compound 2 is taken from CN 11260833.
• Figures 3 A and 3B show the film absorption spectrum of Compound Example 3.
• FIGS 3C and 3D show the solution absorption spectrum of Compound Example 3.
• Figures 4A and 4B show the film absorption spectrum of Compound Example 4.
• Figures 4C and 4D show the solution absorption spectrum of Compound Example 4.
• Each of Compound Examples 1-4 show strong absorption in film at wavelengths above 1000 nm.
• HOMO and LUMO energy levels of films of the example compounds were measured by square wave voltammetry.
• Cathode / Donor Acceptor layer / Anode
• ITO indium-tin oxide
• PEIE polyethyleneimine
• Donor Polymer 1 Donor
• Compound Example 1 acceptor mas ratio of 1:1.5 was deposited over the modified ITO layer by blade coating from a 15 mg / ml solution in 1,2,4 Trimethylbenzene; 1,2-Dimethoxybenzene 95:5 v/v solvent mixture.
• the film was dried at 80°C to form a ca. 500 nm thick bulk heterojunction layer.
• Donor Polymer 1 is a donor-acceptor polymer shown below, having a donor repeat unit of formula (Vila) and an acceptor repeat unit.
• Donor Polymer 1 may be prepared as described in WO2013/051676, the contents of which are incorporated herein by reference.
• Donor Polymer 1 has a peak absorption wavelength of 933 nm.
• An organic photodetector was prepared as follows:
• a formulation of Donor Polymer 2 (1 wt%) and Compound Example 3 (1 wt %) in ortho- dichlorobenzene was deposited by spin-coating onto a glass substrate coated with a layer of indium-tin oxide (ITO) (45 nm) and dried to form a bulk heterojunction layer (300 nm) which was followed by a layer of ZnO (50nm) and a layer of silver (60 nm). The device was annealed at 100°C for 10 minutes and sealed to the substrate using a cover glass.
• ITO indium-tin oxide
• a device was prepared as described for Device Example 2 except that Compound Example 4 was used in place of Compound Example 3.
• Device Examples 4-6 were prepared as described for Device Example 1 except that Compound Examples 5-7, respectively, were used in place of Compound Example 1.
• Acceptor units A 1 preferably have a modelled LUMO of at least 2.9 eV or at least 3.0 eV from vacuum level.

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  • 2022-08-05 TW TW111129514A patent/TW202315183A/zh unknown
  • 2022-08-05 TW TW111129530A patent/TW202315184A/zh unknown
  • 2022-08-05 US US18/294,514 patent/US20240349600A1/en active Pending

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