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Definitions

• Embodiments of the present disclosure relate to photoactive compounds and more specifically, but not by way of limitation, to photoactive compounds comprising electron donating groups.
• OPDs organic photodetectors
• JP2015189853 relates to a polymer compound and an electronic element using the same.
• WO 2017/155030 and WO 2019/054402 relate to tetrazolopyridine compounds.
• WO 2017/078182 relates to benzimidazole fused heteroaryls.
• WO 2012/146504 is directed to semiconductor materials based on dithienopyridone copolymers.
• CN 104211926 relates to a polymerization monomer for a donor material of a polymer solar battery.
• KR2013070431 is directed to a multicyclic aromatic compound and organic light emitting device including the same.
• US 2018/0175307 relates to organic electroluminescent materials and devices.
• Pan et al., RSC Advances, volume 7, pages 3439-3442 is directed to a facilely synthesized lactam acceptor unit for high-performance polymer donors.
• Cao et al., Dyes and Pigments, volume 139, pages 201-207 relates to D-A copolymers based on lactam acceptor unit and thiophene derivatives for efficient polymer solar cells.
• the present disclosure provides a material comprising an electron donor material.
• the material may comprise a group of formula (I): wherein:
• X and Y are each independently selected from S, O or Se;
• Ar 1 , Ar 2 , Ar 3 and Ar 4 are each independently an unsubstituted or a substituted benzene, an unsubstituted or a substituted 5- or 6- membered heteroaromatic group or are absent;
• a 1 and A 2 are each independently an unsubstituted or a substituted benzene, an unsubstituted or a substituted 5- or 6- membered heteroaromatic group, a non-aromatic 6-membered ring having ring atoms selected from C, N, S and O or are absent;
• R 1 is H or a substituent
• R 2 and R 3 are each independently H or a substituent
• X, Y, R 1 , R 2 and R 3 and * are as defined previously; and R 4 and R 5 are each independently H or a substituent.
• Ar 1 , A 1 , Ar 2 , Ar 3 A 2 and Ar 4 are absent and the group of formula (I) has formula (Ic): wherein:
• the material is a polymer comprising a repeat unit of formula (Id): formula (Id) wherein X, Y, R 1 to R 5 , Ar 1 to Ar 4 , A 1 and A 2 are as previously defined previously.
• Exemplary repeat units of formula (Id) are formulae (Ie), (If) and (Ig): formula (Ig)
• the material comprises an electron accepting group, EAG.
• the compound comprising the group of formula (I) has formula (Ih), (Ii), (Ij) or formula (Ik): formula (Ik) wherein: n is an integer of 1 or more; m and o are each independently 0 or an integer of 1 or more; L 1 and L 2 each independently represent a bridging group when m and o are 1 or more or a direct bond when m and o are 0;
• EAG represents an electron accepting group
• X, Y, R 1 to R 4 , Ar 1 to Ar 4 , A 1 and A 2 are as previously defined previously.
• L 1 and L 2 are each independently a group of formula (II) or formula (III): wherein:
• X 1 , X 2 and X 3 are each independently S, O or Se;
• ** represents a point of attachment to EAG
• R 6 , R 7 , R 8 and R 9 are each independently H or a substituent.
• each EAG is a group of formula (Via): (Vla) wherein:
• R 10 in each occurrence is H or a substituent selected from the group consisting of: C 1-12 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; and an aromatic group Ar 2 which is unsubstituted or substituted with one or more substituents selected from F and C 1-12 alkyl wherein one or more non-adjacent, nonterminal C atoms may be replaced with O, S, COO or CO;
• each X 1 -X 4 is independently CR 12 or N wherein R 12 in each occurrence is H or a substituent selected from C 1-12 hydrocarbyl and an electron withdrawing group.
• At least one R 12 is an electron- withdrawing group selected from F, Br, Cl and CN.
• composition comprising an electron donor and an electron acceptor wherein at least one of the electron donor and electron acceptor is a material comprising a group of formula (I).
• the material or composition as described herein is dissolved or dispersed in one or more solvents.
• the present disclosure provides a photoresponsive device comprising an anode, a cathode and a photosensitive layer disposed between the anode and the cathode, wherein the photosensitive layer comprises a material as previously described.
• the photoresponsive device may be an organic photodetector.
• the present disclosure provides a photosensor comprising a light source and a photoresponsive device as described previously, wherein the photosensor is configured to detect light emitted from the light source.
• the present disclosure provides a method of forming the organic photoresponsive device described previously comprising formation of the photosensitive organic layer over one of the anode and cathode and formation of the other of the anode and cathode over the photosensitive organic layer.
• formation of the photosensitive organic layer comprises deposition of a formulation comprising a composition as described herein dissolved or dispersed in one or more solvents.
• the light source emits light having a peak wavelength greater than 750 nm.
• the photosensor is configured to receive a sample in a light path between the organic photodetector and the light source.
• the present disclosure provides a method of determining the presence and / or concentration of a target material in a sample, the method comprising illuminating the sample and measuring a response of a photoresponsive device as described previously.
• Figure 1 illustrates an organic photoresponsive device according to some embodiments.
• Figure 2 shows absorption spectra for a polymer according to some embodiments of the present disclosure and a comparative polymer.
• the drawings are not drawn to scale and have various viewpoints and perspectives.
• the drawings are some implementations and examples. Additionally, some components and/or operations may be separated into different blocks or combined into a single block for the purposes of discussion of some of the embodiments of the disclosed technology.
• specific embodiments have been shown by way of example in the drawings and are described in detail below. The intention, however, is not to limit the technology to the particular implementations described. On the contrary, the technology is intended to cover all modifications, equivalents, and alternatives falling within the scope of the technology as defined by the appended claims.
• materials comprising a group of formula (I) may be used in a donor- acceptor system used in an organic photoresponsive device, e.g. a photovoltaic device such as a solar cell or an organic photodetector.
• an organic photoresponsive device e.g. a photovoltaic device such as a solar cell or an organic photodetector.
• the materials may absorb long wavelengths of light, e.g. greater than about 750 nm, making them suitable for use in organic photodetectors for detection of light in the near- infrared range such as in the range of greater than about 750 nm, greater than 850 nm or greater than about 1000 nm.
• the materials may absorb wavelengths of light that are between about 750 nm and about 2000 nm, between about 750 nm and about 1000 nm or between about 1000 nm to about 2000 nm.
• 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.
• 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.
• 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 bulk heterojunction layer comprises an electron donor and an electron acceptor.
• the bulk heterojunction layer consists of the electron donor and the electron acceptor.
• Each of the anode and cathode may independently be a single conductive layer or may comprise a plurality of layers.
• the organic photoresponsive device may comprise layers other than the anode, cathode and bulk heterojunction layer shown in Figure 1.
• a holetransporting 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 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 acceptor material and the electron donor material 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, C 1-10 alkyl and C 1-10 alkoxy wherein two or more substituents may be linked to form a ring which may be unsubstituted or substituted with one or more C 1-6 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, C 1-10 alkyl and C 1-10 alkoxy wherein two or more substituents may be linked to form a ring which may be unsubstituted or substituted with one or more C 1-6 alkyl groups, optionally toluene, xylenes, trimethylbenzenes, tetramethylbenzenes, anisole, indan
• 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 C 1-10 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 acceptor, the electron donor 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 organic photoresponsive device is an organic photodetector (OPD)
• OPD organic photodetector
• it may be 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 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.
• At least one of the electron donor and electron acceptor of the bulk heterojunction layer is a material comprising a group of formula (I):
• Ar 1 , Ar 2 , Ar 3 and Ar 4 are each independently an unsubstituted or a substituted benzene, an unsubstituted or a substituted 5- or 6- membered heteroaromatic group or are absent;
• a 1 and A 2 are each independently an unsubstituted or a substituted benzene, an unsubstituted or a substituted 5- or 6- membered heteroaromatic group, a non-aromatic 6-membered ring having ring atoms selected from C, N, S and O or are absent;
• R 1 is H or a substituent
• R 2 and R 3 are each independently H or a substituent; and * represents a point of attachment to a hydrogen or non-hydrogen substituent.
• a 1 and A 2 are each independently a cyclohexane, wherein optionally one or more carbon atoms are replaced with S, NR 1 or O.
• the material comprising the group of formula (I) is a polymer comprising a repeat unit of formula (I).
• the polymer is an electron donor of the bulk heterojunction layer.
• the material comprising the group of formula (I) is a non- polymeric compound containing at least one group of formula (I), optionally 1 or 2 groups of formula (I).
• the non-polymeric compound is an electron acceptor of the bulk heterojunction layer and comprises at least one, optionally 1 or 2, electron donating groups of formula (I) and at least one electron- accepting group.
• the group of formula (I) has one of the following formulae:
• R 1 is H or a substituent
• R 2 and R 3 are each independently H or a substituent; and * represents a point of attachment to a hydrogen or non-hydrogen group.
• the group of formula (I) is a group of formula (la) or formula
• X, Y, R 1 , R 2 and R 3 and * are as described previously for formula (I); and R 4 and R 5 are each independently H or a substituent.
• R 1 is selected from: H; C 1-12 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; and phenyl which is unsubstituted or substituted with one or more substituents, optionally one or more C 1-12 alkyl groups 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.
• R 2 and R 3 are each independently selected from H; C 1-20 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; and an aromatic group Ar 2 , optionally phenyl, which is unsubstituted or substituted with one or more substituents selected from F and C 1-12 alkyl wherein one or more non-adjacent, non-terminal C atoms may be replaced with O, S, COO or CO.
• R 2 and R 3 may be linked to form a ring, e.g. a cycloalkyl ring or an aromatic or heteroaromatic ring, e.g. fluorene.
• R 4 and R 5 are each independently selected from H; F; and C 1-20 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.
• Ar 1 -Ar 4 are preferably each benzene or thiophene, each of which is optionally and independently unsubstituted or substituted with one or more substituents, optionally one or more substituents of formula R 4 .
• the group of formula (I) is a group of one of the following formulae: wherein:
• R 1 , R 2 , R 3 , R 4 and R 5 are as defined previously for formulae la and lb;
• R 10 , R 11 and R 12 are each independently H or a substituent, preferably a substituent selected from the group consisting of C 1-12 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; and an aromatic group Ar 2 , optionally phenyl, which is unsubstituted or substituted with one or more substituents selected from F and C 1-12 alkyl wherein one or more non-adjacent, non-terminal C atoms may be replaced with O, S, COO or CO.
• Ar 1 , A 1 , Ar 2 , Ar 3 A 2 and Ar 4 of formula (I) are absent and the material has formula (Ic):
• the group of formula (I) is selected from the following formulae:
• one X is CR 2 R 3 and the other X is O, S or NR 1 .
• the polymer comprises a repeat unit of formula (Id): formula (Id)
• the repeat unit of formula (Id) has formula (Ie), (If) or (Ig): wherein X, Y, R 1 to R 5 , Ar 1 to Ar 4 , A 1 and A 2 are as previously defined.
• the polymer is preferably a copolymer comprising electron-donating repeat units of formula (Id) and electron-accepting co-repeat units.
• Repeat units of formula (I) and the electron- accepting co-repeat units may together form a repeating structure in the polymer backbone of formula:
• each EAG repeat unit of the polymer (except any terminal EAG repeat unit) is adjacent to a repeat unit of formula (Id).
• each repeat unit of formula (Id) of the polymer is adjacent to an EAG repeat unit.
• the compound preferably contains at least one electron accepting group (EAG) which may be directly or indirectly bound to the group of formula (I).
• EAG electron accepting group
• a 1 and A 2 are each independently a cyclohexane, wherein optionally one or more carbon atoms are replaced with S, NR 1 or O.
• The, or each, EAG has a LUMO level that is deeper (i.e. further from vacuum) than EDG, preferably at least 1 eV deeper.
• the LUMO levels of EAG and EDG may be as determined by modelling the LUMO level of EAG-H or H-EAG-H with that of H- EDG-H, i.e. by replacing the bonds between EAG and EDG with bonds to a hydrogen atom. Modelling may be performed using Gaussian09 software available from Gaussian using Gaussian09 with B3LYP (functional) and LACVP* (Basis set).
• a material comprising a group of (Ih), formula (Ii), formula (Ij) or formula (Ik):
• n is an integer of 1 or more; m and o are each independently 0 or an integer of 1 or more; L 1 and L 2 each independently represent a bridging group when m and o are 1 or more or a direct bond when m and o are 0;
• EAG represents an electron accepting group
• X, Y, R 1 to R 4 , Ar 1 to Ar 4 , A 1 and A 2 are as previously defined.
• L 1 and L 2 may each independently be a group of formula (II) or formula (III): formula (II) wherein:
• X 1 , X 2 and X 3 are each independently S, O or Se;
• ** represents a point of attachment to EAG
• R 6 , R 7 , R 8 and R 9 are each independently H or a substituent.
• L 1 and L 2 are each independently selected from the following formulae:
• the groups of formula (I) may be linked in any orientation.
• the two groups of formula (I) may be linked as:
• Ar 1 -Ar 4 , A 1 , A 2 , R 1 -R 3 X and Y independently in each occurrence may be the same or different.
• each EAG of formula (Ih) is selected from formulae (III)-(XIV):
• A 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 C 1-12 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; and an aromatic group Ar 2 , optionally phenyl, which is unsubstituted or substituted with one or more substituents selected from F and C 1-12 alkyl wherein one or more non- adjacent, non-terminal C atoms may be replaced with O, S, COO or CO.
• R 10 is H.
• J O or S.
• R 13 in each occurrence is a substituent, optionally C 1-12 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.
• R 15 in each occurrence is independently H; F; C 1-12 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 group Ar 2 , optionally phenyl, which is unsubstituted or substituted with one or more substituents selected from F and C 1-12 alkyl wherein one or more non-adjacent, non-terminal C atoms may be replaced with O, S, COO or CO.
• R 16 is a substituent, preferably a substituent selected from: -(Ar 3 ) w wherein Ar 3 in each occurrence is independently an unsubstituted or substituted aryl or heteroaryl group, preferably thiophene, and w is 1, 2 or 3; C 1-12 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.
• Ar 4 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 4 are optionally selected from C 1-12 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.
• Z 1 is N or P
• 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. Substituents of T 1 , T 2 and T 3 , where present, are optionally selected from non-H groups of R 15 .
• Ar 8 is a fused heteroaromatic group which is unsubstituted or substituted with one or more non-H substituents R 10 .
• a preferred group of formula (III) is formula (Ilia).
• EAG is a group of formula (Ilia): (Illa) wherein:
• R 10 is as described above;
• each X 1 -X 4 is independently CR 12 or N wherein R 12 in each occurrence is H or a substituent selected from C 1-20 hydrocarbyl and an electron withdrawing group.
• the electron withdrawing group is F, Cl, Br or CN.
• the C 1-20 hydrocarbyl group R 12 may be selected from C 1-20 alkyl; unsubstituted phenyl; and phenyl substituted with one or more C 1-12 alkyl groups.
• Exemplary compounds of formula (IVa) or (IVb) include: wherein Ak is a C 1-12 alkylene chain in which one or more C atoms may be replaced with O, S, CO or COO;An is an anion, optionally -SO 3 -; and each benzene ring is independently unsubstitued or substituted with one or more substituents selected from substituents described with reference to R 10 .
• Exemplary EAGs of formula (XI) are:
• An exemplary EAG group of formula (XII) is: In the case where at least one EAG is a group of formula (XIII), the group of formula (I) is substituted with a group of formula -B(R 14 ) 2 wherein R 14 in each occurrence is a substituent, optionally a C 1-20 hydrocarbyl group; — is bound to a position denoted by * in Formula (I); and ⁇ is a bond to the boron atom of -B(R 14 ) 2 .
• R 14 is selected from C 1-12 alkyl; unsubstituted phenyl; and phenyl substituted with one or more C 1-12 alkyl groups.
• the group of formula (I), the group of formula (XIII) and the B(R 14 ) 2 substituent of formula (I) may be linked together to form a 5- or 6-membered ring.
• EAG of formula (XIII) is selected from formulae (XIIIa) ,(XIIIb) and (XIIIc):
• Divalent EAGs for example of formula (Ii), (Ij) or (Ik) or EAG co-repeat units of a polymer comprising a repeat unit of formula (Id), are optionally selected from: - divalent analogues of formulae (VIII)-(X) wherein R 16 is a bond to L 1 , L 2 or * of formula (I); and analogues (XIa) and (Xlla) of formulae (XI) and (XII), respectively:
• EAG repeat units of a polymer or EAG groups of a compound of formula (Ii), (Ij) or (Ik) are:
• Y is H or a substituent, e.g. a C 1-12 alkyl or F.
• a photosensitive layer of an organic photoresponsive device as described herein may comprise or consist of a composition comprising an electron donor and an electron acceptor wherein at least one, optionally both, of the electron donor and electron acceptor is a material comprising a group of formula (I).
• the composition may contain only one electron acceptor and / or only one electron donor.
• the composition may comprise one or more electron acceptors selected from non-fullerene acceptors, which may or may not comprise a group of formula (I), and fullerene acceptors.
• 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, PD I, ITIC, ITIC, IEICO and derivatives thereof, e.g. fluorinated derivatives thereof such as ITIC-4F and IEICO-4F.
• Exemplary fullerene electron acceptor materials 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 (C 60 PCBM), TCBM-type fullerene derivatives (e.g. tolyl-C61 -butyric acid methyl ester (C60TCBM)), and ThCBM-type fullerene derivatives (e.g. thienyl-C61 -butyric acid methyl ester (C 60 ThCBM).
• PCBM-type fullerene derivatives including phenyl-C61-butyric acid methyl ester (C 60 PCBM)
• TCBM-type fullerene derivatives e.g. tolyl-C61 -butyric acid methyl ester (C60TCBM)
• ThCBM-type fullerene derivatives e.g.
• a compound of formula (Id) may be prepared according to the following reaction scheme: wherein Ar is an aromatic group, optionally phenyl.
• Isopropylmagnesium chloride (2 M in THF, 78.7 ml, 157.4 mmol, 1.7 equiv.) was added dropwise to a cold (0 °C) solution of 1 (30.0 g, 92.6 mmol) in anhydrous THF (250 ml) over twenty minutes. The solution was allowed to stir at 0 °C for one hour before warming to room temperature while stirring. The solution was briefly warmed to 45 °C before being allowed to cool back to room temperature and stirring at room temperature for 30 minutes. Consumption of starting material was confirmed by 'H NMR spectroscopy of a 1 ml sample of the reaction mixture after quenching with methanol and removal of solvent.
• the flask was flushed with nitrogen for 20 minutes.
• 25 ml dry toluene was added via cannula under nitrogen and the mixture was slowly stirred while degassing through an inlet tube for 20 minutes.
• the mixture was heated to 100 °C for 48 hours, allowed to cool and further portions of Pd2dba3.CHCl3 (7.76 mg, 7.5 pmol, 0.5 mol%) and /n.s(2-mcthoxyphcnyl (phosphine (10.57 mg, 30.0 pmol, 2.0 mol%) were added before heating was resumed at 100 °C for 10 days.
• HOMO and LUMO levels of Polymer Example 1 were measured by square wave voltammetry (SWV) in solution and the values are provided in Table 1 with values for Comparative Polymer 1. As shown in Table 1 the HOMO-LUMO bandgap of Polymer Example 1 is significantly smaller than that of Comparative Polymer 1.
• 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 and LUMO energy levels by SWV comprises 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 (3mg/ml).
• 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 samples for both the HOMO and LUMO data.
• Polymer Example 1 has a peak of 752 nm and absorption of Polymer Example 1 is stronger at wavelengths above about 850 nm.
• HOMO and LUMO levels of the following compounds were modelled and results are set out in Table 2.
• Quantum chemical modelling was performed using Gaussian09 software available from Gaussian using Gaussian09 with B3LYP (functional) and LAC VP* (Basis set).
• Model Compound Example 1 comprising an N-substituted methyl group has a smaller band gap than the Model Comparative Compound with a different central fused group, indicating that Model Compound 1 is capable of absorbing light at longer wavelengths than the Model Comparative Compound.
• Model Compound 2 in which the donor group comprises an N-substituted p-tolyl group, has an even smaller band gap than both the Model Comparative Compound and Model Compound 1 and is capable of absorbing light at longer wavelengths than the Model Comparative Compound.

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