Patent Application
20240365662
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.
Yoon et al, “Effects of Electron Donating and Electron-Accepting Substitution on Photovoltaic Performance in Benzothiadiazole-Based A-D-A′-D-A-Type Small-Molecule Acceptor Solar Cells” ACS Appl. Energy Mater. 2020, 3, 12, 12327-12337 discloses A-D-A′-D-A-type acceptors for use in solar cells.
Gao et al, “Non-fullerene acceptors with nitrogen-containing six-membered heterocycle cores for the applications in organic solar cells” Solar Energy Materials and Solar Cells 225, 2021, 111046 discloses non-fullerene acceptors with pyrazine or pyridazine as the cores.
Wang et al, “Near-infrared absorbing non-fullerene acceptors with unfused D-A-D core for efficient organic solar cells” Organic Electronics 92, 2021, 106131 discloses a D-A-D core employing 3-bis(4-(2-ethylhexyl)-thiophen-2-yl)-5,7-bis(2ethylhexyl)benzo-[1,2:4,5-c′]-dithiophene-4,8-dione (BDD) unit as the A moiety and 4,4-dialkyl-4H-cyclopenta[2,1-b:3,4-b′]dithiophene (CPDT) unit as the D moiety.
CN110379926 discloses an organic solar cell based on a benzodithiazole near-infrared receptor.
CN112608333 discloses a small molecule based on a bisthiadiazole carbazole derivative.
CN112259687 discloses a ternary fullerene organic solar cell.
In some embodiments, the present disclosure provides a compound of formula (I):
Optionally, the group of formula (II) has formula (IIa):
Optionally, the group of formula (II) has formula (IIb):
In some embodiments, the two R1 groups are not linked. According to these embodiments, optionally each R1 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, NR4, PR4, or Si(R3)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 R3 and R4 are each independently H or a substituent.
In some embodiments, the two R1 groups are linked. According to these embodiments, optionally the compound of formula (IIb) has formula (IIb-1) or (IIb-2):
Optionally, Ar2 is benzene which is unsubstituted or substituted with one or more substituents.
Optionally, at least one of x1 and x2 is at least 1 and B1 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.
Optionally, at least one of z1 and z2 is at least 1 and B2 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.
Optionally, D1 and D2 are each independently selected from units of formulae (VIIa)-(VIIp) as described herein.
Optionally, at least one of A2 and A3 comprises a non-aromatic carbon-carbon double bond and a carbon atom of the carbon-carbon double bond is bound directly to D1 or D2 or, if present, to B2.
Optionally, A2 and A3 are each independently selected from groups of formulae (IIIa)-(IIIq) as described herein.
Optionally, at least one A is a group of formula (IIIa-1):
Optionally, the polymer has an absorption peak of greater than 900 nm.
According to some embodiments, the present disclosure provides a compound of formula (I):
D1, D2, A1, A2, A3, B1, B2, x1, x2, y1, y2, z1 and z2 according to these embodiments may be as described anywhere herein.
In some embodiments, the present disclosure provides a compound of formula (X):
D1, D2, A1, A2, A3, B1, B2, x1, x2, y1, y2, z1 and z2 of formula (X) may be as described anywhere herein, for example as described with respect to compounds of formula (I).
In some embodiments, the present disclosure provides composition comprising an electron-donating material and an electron-accepting material wherein the electron accepting material is a compound as described herein.
In some embodiments, the present disclosure provides an organic electronic device comprising an active layer comprising a compound or composition as described herein.
Optionally, 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.
Optionally, the organic photoresponsive device is an organic photodetector.
In some embodiments, 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.
Optionally, the light source emits light having a peak wavelength of greater than 900 nm.
In some embodiments, the present disclosure provides a formulation comprising a compound or composition as described herein dissolved or dispersed in one or more solvents.
In some embodiments, 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.
The disclosed technology and accompanying figures describe some implementations of the disclosed technology.
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. Moreover, while the technology is amenable to various modifications and alternative forms, 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.
Unless the context clearly requires otherwise, throughout the description and the claims, the words “comprise,” “comprising,” and the like are to be construed in an inclusive sense, as opposed to an exclusive or exhaustive sense; that is to say, in the sense of “including, but not limited to.” Additionally, the words “herein,” “above,” “below,” and words of similar import, when used in this application, refer to this application as a whole and not to any particular portions of this application. Where the context permits, words in the Detailed Description using the singular or plural number may also include the plural or singular number respectively. The word “or,” in reference to a list of two or more items, covers all of the following interpretations of the word: any of the items in the list, all of the items in the list, and any combination of the items in the list. 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.
The teachings of the technology provided herein can be applied to other systems, not necessarily the system described below. The elements and acts of the various examples described below can be combined to provide further implementations of the technology.
Some alternative implementations of the technology may include not only additional elements to those implementations noted below, but also may include fewer elements.
These and other changes can be made to the technology in light of the following detailed description. While the description describes certain examples of the technology, and describes the best mode contemplated, no matter how detailed the description appears, the technology can be practiced in many ways. As noted above, particular terminology used when describing certain features or aspects of the technology should not be taken to imply that the terminology is being redefined herein to be restricted to any specific characteristics, features, or aspects of the technology with which that terminology is associated. In general, the terms used in the following claims should not be construed to limit the technology to the specific examples disclosed in the specification, unless the Detailed Description section explicitly defines such terms. Accordingly, the actual scope of the technology encompasses not only the disclosed examples, but also all equivalent ways of practicing or implementing the technology under the claims.
To reduce the number of claims, certain aspects of the technology are presented below in certain claim forms, but the applicant contemplates the various aspects of the technology in any number of claim forms.
In the following description, for the purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of implementations of the disclosed technology. It will be apparent, however, to one skilled in the art that embodiments of the disclosed technology may be practiced without some of these specific details.
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.
In some embodiments, the bulk heterojunction layer contains two or more accepting materials and/or two or more electron-accepting materials.
In some embodiments, the weight of the electron-donating material(s) to the electron-accepting material(s) is from about 1:0.5 to about 1:2, preferably about 1:1.1 to about 1:2.
Preferably, 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. Preferably, 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.
Optionally, 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.
Unless stated otherwise, HOMO and LUMO levels of materials as described herein are as measured by square wave voltammetry (SWV).
In 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.
In some embodiments, 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.
Unless stated otherwise, 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 PbSmart 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.
Unless stated otherwise, absorption data as provided herein is as measured in toluene solution.
In some embodiments, the electron-accepting compound has formula (I):
Each of the electron-accepting groups A1, A2 and A3 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 D1 or D2, 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).
In some embodiments, A1 of formula (I) is a group of formula (II):
In some embodiments the compound of formula (I) is a “symmetric” compound in which —(B1)x1-(D1)y1-(B2)z1-A2 is the same as —(B1)x2-(D2)y2-(B2)z2-A3.
In some embodiments the compound of formula (I) is a compound in which —(B′)x1-(D1)y1-(B2)z1-A2 is different from —(B1)x2-(D2)y2-(B2)z2-A3. Such compounds are described hereinafter as “asymmetric” compounds.
In an asymmetric compound of formula (I), at least one of (i)-(iv) applies:
Optionally, D1 and D2 are different and y1 and y2 are the same or different.
Optionally, y1 and y2 are different and D1 and D2 are the same or different.
If x1 and x2 are the same or different and are both greater than 1 then optionally B1 of (B1)x1 is different from B1 of (B)x2
Optionally, x1 and x2 are different.
If z1 and z2 are the same or different and are both greater than 1 then optionally B2 of (B2)z1 is different from B2 of (B2)z2.
Optionally, z1 and z2 are different.
In some embodiments, the present disclosure provides compounds of formula (X):
wherein A1, A2, A3, B1, B2, D1, D2, x1, x2, y1 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.
In the case where A1 is a group of formula (II), Ar1 may be a monocyclic or polycyclic heteroaromatic group which is unsubstituted or substituted with one or more R2 groups wherein R2 in each occurrence is independently a substituent.
Preferred R2 groups are selected from
R7 as described anywhere herein may be, for example, C1-12 alkyl, unsubstituted phenyl; or phenyl substituted with one or more C1-6 alkyl groups.
If a C atom of an alkyl group as described anywhere herein is replaced with another atom or group, the replaced C atom may be a terminal C atom of the alkyl group or a non-terminal C-atom.
By “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.
If a terminal C atom of a group as described anywhere herein is replaced then 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 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 Ar1 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 Ar1 are groups of formula (V):
X1 and X2, are each independently selected from N and CR3 wherein R3 is H or a substituent, optionally H or a substituent R2 as described above.
X3, X4, X5 and X6 are each independently selected from N and CR3 with the proviso that at least one of X3, X4, X5 and X6 is CR3.
Z is selected from O, S, SO2, NR4, PR4, C(R3)2, Si(R3)2 C═O, C═S and C═C(R5)2 wherein R3 is as described above; R4 is H or a substituent; and R5 in each occurrence is an electron-withdrawing group.
Optionally, each R4 of any NR4 or PR4 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, NR7, 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, NR7, COO or CO and one or more H atoms of the alkyl may be replaced with F.
Preferably, each R5 is CN, COOR40; or CX60X61 wherein X60 and X61 is independently CN, CF3 or COOR40 and R40 in each occurrence is H or a substituent, preferably H or a C1-20 hydrocarbyl group.
A1 groups of formula (II) are preferably selected from groups of formulae (IIa) and (IIb):
For compounds of formula (IIb), the two R1 groups may or may not be linked.
Preferably, when the two R1 groups are not linked each R1 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, NR7, CO, COO, NR4, PR4, or Si(R3)2 wherein R3 and R4 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, NR7, CO, COO and one or more H atoms may be replaced with F.
Preferably, when the two R1 groups are linked, the group of formula (IIb) has formula (IIb-1) or (IIb-2):
Ar2 is an aromatic or heteroaromatic group, preferably benzene, which is unsubstituted or substituted with one or more substituents. Ar2 may be unsubstituted or substituted with one or more substituents R2 as described above.
X is selected from O, S, SO2, NR4, PR4, C(R3)2, Si(R3)2 C═O, C═S and C═C(R5)2 wherein R3, R4 and R5 are as described above.
Exemplary electron-accepting groups of formula (II) include, without limitation:
wherein Ak1 is a C1-20 alkyl group
Divalent electron-accepting groups other than formula (II) are optionally selected from formulae (IVa)-(IVj)
R23 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 Z1 may be replaced with O, S, NR7, COO or CO and one or more H atoms of the alkyl may be replaced with F.
R25 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, NR7, 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, NR7, COO or CO; or
T1, T2 and T3 each independently represent an aryl or a heteroaryl ring, optionally benzene, which may be fused to one or more further rings. Substituents of T1, T2 and T3, where present, are optionally selected from non-H groups of R25.
R12 in each occurrence is a substituent, preferably a C1-20 hydrocarbyl group.
Ar5 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 R25.
Electron-Accepting Groups A2, A3
The monovalent acceptor Groups A2 and A3 may each independently be selected from any such units known to the skilled person. A2 and A3 may be the same or different, preferably different.
Exemplary monovalent acceptor units include, without limitation, units of formulae (IIIa)-(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.
The N atom of formula (IIIe) may be unsubstituted or substituted.
R10 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, NR7, 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, NR7, COO or CO.
Preferably, R10 is H.
J is O or S, preferably O.
R13 in each occurrence is a substituent, optionally C1-12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR7, COO or CO and one or more H atoms of the alkyl may be replaced with F.
R15 in each occurrence is independently H; F; C1-12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR7, COO or CO and one or more H atoms of the alkyl may be replaced with F; aromatic group Ar2, 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, NR7, COO or CO; or a group selected from:
R16 is H or a substituent, preferably a substituent selected from:
Ar6 is a 5-membered heteroaromatic group, preferably thiophene or furan, which is unsubstituted or substituted with one or more substituents.
Substituents of Ar3 and Ar6, where present, are optionally selected from C1-12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR7, COO or CO and one or more H atoms of the alkyl may be replaced with F.
T1, T2 and T3 are each independently as described above.
Ar8 is a fused heteroaromatic group which is unsubstituted or substituted with one or more substituents, optionally one or more non-H substituents R10, and which is bound to an aromatic C atom of B2 and to a boron substituent of B2.
Preferred groups A2 and A3 are groups having a non-aromatic carbon-carbon bond which is bound directly to D1 or D2 or, if present to B2.
Preferably at least one of A2 and A3, preferably both of A2 and A3, are a group of formula (IIIa-1):
The C1-20 hydrocarbyl group R12 may be selected from C1-20 alkyl; unsubstituted phenyl; and phenyl substituted with one or more C1-12 alkyl groups.
Exemplary groups of formula (IIId) include:
Exemplary groups of formula (IIIe) include:
An exemplary group of formula (IIIq) is:
An exemplary group of formula (IIIg) is:
An exemplary group of formula (IIIj) is:
wherein Ak is a C1-12 alkylene chain in which one or more C atoms may be replaced with O, S, NR7, CO or COO; An is an anion, optionally —SO3—; and each benzene ring is independently unsubstituted or substituted with one or more substituents selected from substituents described with reference to R10.
Exemplary groups of formula (IIIm) are:
An exemplary group of formula (IIIn) is:
Groups of formula (IIIo) are bound directly to a bridging group B2 substituted with a —B(RM)2 wherein R14 in each occurrence is a substituent, optionally a C1-20 hydrocarbyl group; → is a bond to the boron atom —B(R14)2 of R3 or R6; and --- is the bond to B2.
Optionally, R14 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 B2 group and the B(R14)2 substituent of B2 may be linked together to form a 5- or 6-membered ring.
Optionally groups of formula (IIIo) are selected from:
Bridging units B1 and B2 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 B1 and B2 preferably are monocyclic or fused bicyclic arylene or heteroarylene groups, more preferably monocyclic or fused bicyclic heteroarylene groups.
Optionally, B1 and B2 are is selected from units of formulae (VIa)-(VIg):
wherein YA is O, S or NR5 wherein R55 is H or a substituent; R8 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, NR7, 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(R14)2 wherein R14 in each occurrence is a substituent, optionally a C1-20 hydrocarbyl group. R8 groups of formulae (VIa), (VIb) and (VIc) may be linked to form a bicyclic ring, for example thienopyrazine.
R8 is preferably H, C1-20 alkyl or C1-19 alkoxy.
Electron-Donating Groups D1 and D2
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 D1 and D2 include groups of formulae (VIIa)-(VIIp):
wherein YA in each occurrence is independently O, S or NR5, ZA in each occurrence is O, CO, S, NR55 or C(R54)2; R51, R52 R54 and R55 independently in each occurrence is H or a substituent; and R53 independently in each occurrence is a substituent.
Optionally, R51 and R52 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, NR7, COO or CO and one or more H atoms of the alkyl may be replaced with F; and an aromatic or heteroaromatic group Ar3 which is unsubstituted or substituted with one or more substituents.
In some embodiments, Ar3 may be an aromatic group, e.g., phenyl.
The one or more substituents of Ar3, if present, may be selected from C1-12 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR7, COO or CO and one or more H atoms of the alkyl may be replaced with F.
Preferably, each R54 is selected from the group consisting of:
Substituents of Ar7, if present, 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, NR7, CO or COO and one or more H atoms may be replaced with F. Preferably, Ar7 is phenyl.
Preferably, each R51 is H.
Optionally, R53 independently in each occurrence is selected from C1-20 alkyl wherein one or more non-adjacent C atoms may be replaced with O, S, NR7, 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, NR7, COO or CO and one or more H atoms of the alkyl may be replaced with F.
Preferably, R55 as described anywhere herein is H or C1-30 hydrocarbyl group.
Preferably, D1 and D2 are each independently a group of formula (VIIa). Exemplary groups of formula (VIIa) 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.
In some embodiments, y1 and y2 are each 1.
In some embodiments, at least one of y1 and y2 is greater than 1. In these embodiments, the chain of D1 and/or D2 groups, respectively, may be linked in any orientation. For example, in the case where D1 is a group of formula (VIIa) and y1 is 2, -[D1]y1-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.
In a preferred embodiment 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.
Preferred are non-crystalline or semi-crystalline conjugated organic polymers.
Further preferably 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. Optionally, the electron-donating polymer has a HOMO level no more than 5.5 eV from vacuum level. Optionally, the electron-donating polymer has a HOMO level at least 4.1 eV from vacuum level. As exemplary electron-donating polymers, 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]thiophene, polybenzothiophene, polybenzo[1,2-b:4,5-b′jdithiophene, polyisothianaphthene, poly(monosubstituted pyrrole), poly(3,4-bisubstituted pyrrole), poly-1,3,4-oxadiazoles, polyisothianaphthene, derivatives and co-polymers thereof may be mentioned.
Preferred examples of 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 (VIIa) 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.
In some embodiments, the compound of formula (I) or (X) as described herein is the only electron-accepting material of a bulk heterojunction layer.
In some embodiments, 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 electron-accepting 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 (2018), 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 C60, C70, C76, C78 and C84 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-C61-butyric acid methyl ester (C60TCBM)), and ThCBM-type fullerene derivatives (e.g. thienyl-C61-butyric acid methyl ester (CoThCBM).
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):
wherein R20—R32 are each independently H or a substituent.
Substituents R20—R32 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, NR7, 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, NR7, 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.
Preferably, 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 C1-10 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.
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. In preferred embodiments, a mixture of trimethylbenzene and benzyl benzoate is used as the solvent. In other preferred embodiments, 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. As examples of such components, 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.
Organic Electronic Device A polymer or composition as described herein may be provided as an active layer of an organic electronic device. In a preferred embodiment, a bulk heterojunction layer of an organic photoresponsive device, more preferably an organic photodetector, comprises a composition as described herein.
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. In some embodiments, 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.
The organic photoresponsive device may comprise layers other than the anode, cathode and bulk heterojunction layer shown in
The area of the OPD may be less than about 3 cm2, less than about 2 cm2, less than about 1 cm2, less than about 0.75 cm2, less than about 0.5 cm2 or less than about 0.25 cm2. Optionally, each OPD 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 mm2, optionally in the range of 0.5 micron2-900 micron2.
The substrate may be, without limitation, a glass or plastic substrate. The substrate can be an inorganic semiconductor. In some embodiments, the substrate may be silicon. For example, 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 electron-accepting 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.
Applications 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. In some embodiments, the photodetector may be continuously biased when in use.
In some embodiments, a photodetector system comprises a plurality of photodetectors as described herein, such as an image sensor of a camera.
In some embodiments, 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. In some embodiments, 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.
The present inventors have found that 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.
In some embodiments, 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/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 1D 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.
Compound Example 1 (NFA1) was prepared according to the following scheme:
To a solution of Compound 1 (0.52 g, 0.94 mmol) in anhydrous THF (15 mL) at −85° C. was added LDA (0.79 mL, 0.99 mmol) dropwise. The mixture was stirred at −80° C. for 45 min. DMF (0.11 mL, 1.40 mmol) was added dropwise over 5 min and the mixture was stirred at below −80° C. for 20 min before being allowed to warm to room temperature. The reaction was quenched with 10 ml of 2M HCl, extracted with toluene, and theorganic phase washed twice with water, dried over magnesium sulfate and concentrated to dryness. Purification via column chromatography [elutant: 30% dichloromethane in heptane] gave Compound 2 as yellow oil (0.17 g, 31% yield)
Compound 2 (0.17 g, 0.29 mmol), propane-1,3-diol (0.08 ml, 1.16 mmol), tetrabutylammonium tribromide (1.4 mg, 0.003 mmol), triethyl orthoformate (0.05 mL, 0.32 mmol), p-toluenesulfonic acid monohydrate (0.07 g, 0.35 mmol) and toluene (0.4 mL) were stirred at room temperature for 1 hour, at 70° C. for 1.5 hours and then at 100° C. for 1.5 hours at. The reaction mixture was cooled to room temperature and diluted with 10 ml of toluene, and the organic phase was washed once with aqueous NaHCO3 (15 ml), and water, and dried over magnesium sulfate and concentrated to dryness. Purification via column chromatography (elutant: 2% to 5% ethyl acetate in heptane) gave Compound 3 as yellow oil (70 mg, 38% yield).
To a solution of Compound 3 (0.07 g, 0.11 mmol) in anhydrous THF (7 mL) at −93° C. was added n-butyllithium (0.05 mL, 0.13 mmol) dropwise and the mixture stirred at approximately −90° C. for 15 min. Tributyltin chloride (0.04 mL, 0.14 mmol) was added dropwise and the mixture was allowed to warm up slowly to 7° C. over 4.5 hours and then cooled down to 0° C. and water (10 mL) was added slowly maintaining an internal temperature of about approximately 0° C. The mixture was extracted with toluene and the organic phase was washed twice with water, dried over magnesium sulfate and concentrated to dryness to give Compound 4, (94.3 mg 101% yield). The product was used in the next step without further purification.
To degassed toluene (10 ml), Compound 4 (0.09 g, 0.11 mmol) and Compound 5 (0.03 g, 0.047 mmol) were added. To this mixture tris(dibenzylideneacetone) dipalladium (0.004 g, 0.003 mmol) and tris(o-tolyl)phosphine (0.003 g, 0.014 mmol) were added, the mixture was further degassed for 5 min and was then heated to 70° C. for 30 minutes. The temperature was increased to 100° C. and the mixture was stirred for 1 hour. The reaction mixture was cooled to room temperature, water (10 mL) was added and the mixture was stirred for 5 minutes. The aqueous phase was removed, water (1 mL) was added followed by trifluoroacetic acid (2 ml). The mixture was stirred at room temperature for 1 hour, water (10 ml) was added to the reaction mixture at 0° C. and stirred for 10 minutes. The organic phase was washed with saturated sodium hydrogen carbonate solution (2×15 ml) and water (2×15 ml), dried over magnesium sulfate and concentrated under reduced pressure. Purification via column chromatography (elutant: 50% to 100% dichloromethane in heptane) gave Compound 6 as a brown oil (15 mg, 62% yield).
Compound 6 (0.04 g, 0.029 mmol) was dissolved in chloroform (3 mL). The solution was degassed with nitrogen for 5 minutes and pyridine (0.02 mL, 0.29 mmol) was added. The solution was degassed for 15 minutes, cooled to 5° C. and Compound 7 (0.03, 0.112 mmol) was added as a solid in one portion. The mixture was allowed to warm to room temperature and stirred for 2 hours. Methanol was added and the mixture was concentrated to dryness. Purification by column chromatography (eluant: dichloromethane in heptane) gave Compound Example 1 (0.005 g. 9% yield).
Compound Example 2 (NFA2) was prepared according to the following reaction scheme:
n-BuLi (1.01 mL, 2.53 mmol) was added to a solution of Intermediate A (1 g, 2.48 mmol) in THF at −78° C. under nitrogen and the mixture stirred for 3 hours. After this time tributyltin chloride (0.71 mL, 2.48 mmol) was added and the mixture was slowly warmed to room temperature over 3 hours. The mixture was cooled to 0° C., quenched with water, extracted with diethyl ether, washed with water and sat. NaCl, dried over MgSO4 and filtered. The solvent was evaporated to give Intermediate A as a brown oil (1.65 g, 96% yield). The product was used in the next step without further purification. LCMS confirmed the mass of the expected product.
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.
Intermediate D (0.5 g, 0.46 mmol) was dissolved in DMF (15 ml) and cooled. Phosphorus oxychloride (0.43 mL, 4.58 mmol) was added dropwise at 2° C. The reaction mixture was stirred at this temperature for 1 hour and then at 80° C. for 2 hours after which time the reaction mixture was cooled to room temperature and saturated NaOAc was slowly. The mixture was diluted and extracted with DCM, organic phase was washed with saturated NaCl and water, dried over MgSO4, filtered and evaporated. Purification via column chromatography (eluant: 16% to 100% dichloromethane:heptane) gave Intermediate E as a black oil (0.51 g, 97% yield). LCMS confirmed the mass of the expected product.
Intermediate E (0.51 g, 0.45 mmol), Intermediate F (0.57 g, 2.22 mmol) and p-TsOH (0.63 g, 3.33 mmol) is toluene (11.5 mL) and ethanol (23 mL) was heated to 65° C. under nitrogen. After 3 hours the reaction mixture was filtered, washed with methanol, ethanol, dichloromethane and pentane to give Compound Example 2 as a black solid (0.43 g 61% yield). LCMS confirmed the mass of the expected product.
CuBr (5.24 g, 36.7 mmol) and LiBr (6.35 g, 73.1 mmol) was placed in a 500 ml round bottom flask containing a stirbar. The flask was flushed with dry N2 gas and anhydrous THF (244 ml) was added. The reaction mixture was stirred for 15 min and then cooled to −78° C. in a dry ice/acetone bath. Then a 1.0M solution of C12H25MgBr in Et2O (36.6 ml, 36.6 mmol) was added to the solution over 5 minutes. After 15 min, oxalyl chloride (2.23 g, 17.55 mmol) was added and then the reaction was stirred for 3 hours at −78° C. Then the reaction was allowed to warm to room temperature and stirred for 1 h. The reaction was quenched using a saturated aq. solution of ammonium chloride. The solvent was removed using rotary evaporation and the residue was treated with CHCl3. The organic layer was washed with water and then dried over MgSO4 and concentrated in vacuo to afford the crude product. After washing with hexane, recrystallization from CHCl3 gave the compound 1 3.60 g (9.12 mmol, yield 52%) as a white solid. 1H-NMR (400 MHz, CHLOROFORM-D) δ2.71 (4H), 1.52-1.59 (4H), 1.24-1.27 (36H), 0.83-0.88 (6H)
0.452 g (1.40 mmol) of compound 2, 0.551 g (1.40 mmol) of compound 1, 0.015 g of BHT (0.07 mmol) and 0.023 g of Mg2SO4 and were dissolved in 6.0 g of toluene and 6.0 g of AcOH and the mixture was stirred at 55° C. for 4 h. After cooling to room temperature, the mixture was poured into water and extracted with toluene. The organic extracts were washed with water twice and dried with anhydrous Na2SO4. The solvent was removed by vacuum distillation and the product was isolated by silica gel column chromatography (eluent: hexane/chloroform=50/50-10/90 wt %) to give compound 3 0.541 g (0.79 mmol, yield 57%). 1H-NMR (400 MHz, CHLOROFORM-D) δ3.08 (t, 4H), 1.94-2.02 (4H), 1.47-1.54 (4H), 1.16-1.45 (32H), 0.86 (6H)
A mixture of compound 3 (0.53 g, 0.80 mmol), compound 4 (1.17 g, 1.77 mmol), Pd2(dba)3 (0.059 g, 0.06 mmol), P(tBu3)HBF4 (0.039 g, 0.13 mmol), THF (8.0 mL), and 3 M K3PO4 aq (8.0 mL) was heated at 60° C. for 2 hours under N2. After cooling to room temperature, the organic layer was separated and after adding toluene, washed with water twice, dried over anhydrous MgSO4 and filtered. After removing solvent, the resulting solid was purified by column chromatography on silica gel (hexane:chloroform 100:0-80:20 as eluent) to give compound 5 1.07 g (yield 84%) 1H-NMR (400 MHz, CHLOROFORM-D) δ 8.87 (s, 2H), 7.04 (d, 2H), 6.71 (d, 2H), 3.16 (t, J=7.5 Hz, 4H), 1.96-2.15 (12H), 1.17-1.54 (116H) 0.82-0.88 (18H)
Compound 5 (1.00 g, 0.70 mmol) was dissolved in anhydrous chloroform (35 mL), followed by the addition of (chloromethylene)dimethyliminium chloride) (0.252 g, 1.97 mmol). This mixture was heated at 60° C. for 2 hours. After cooling to room temperature, saturated NaHCO3 aq. was added and stirred for 10 minutes. The organic layer was separated and washed with water twice, dried over anhydrous MgSO4 and filtered. After removing solvent, the resulting solid was purified by column chromatography on silica gel (hexane:ethyl acetate 96:4 as eluent) to give the compound 6 1.07 g (yield 93%). 1H-NMR (400 MHz, CHLOROFORM-D) δ 9.79 (s, 2H), 8.94 (s, 2H), 7.31 (s, 2H), 3.20 (t, J=7.5 Hz, 4H), 1.96-2.16 (m, 12H), 1.17-1.60 (m, 116H), 0.81-0.88 (m, 18H)
To a solution of compound 6 (450 mg, 0.275 mmol) and 2-(5,6-dichloro-3-oxo-indan-1-ylidene)-malononitrile (217 mg, 0.82 mmol) in anhydrous chloroform (13.6 g) was added pyridine (0.217 g, 2.74 mmol). The mixture was then degassed with nitrogen. The reaction mixture was warmed to 60° C. and stirred for 2 hours. The reaction mixture was then added to acetone and the resulting solid triturated with acetone with collection by filtration. The crude product was washed with mixture of toluene/hexane to give Compound Example 3 (277 mg, 47%) as a black solid.
1H NMR (400 MHz, CDCl3):δ 9.06 (s, 2H), 8.62 (2H), 8.56 (2H), 7.78 (2H), 7.40 (2H), 3.26 (t, 4H), 2.20-2.00 (m, 12H), 1.64 (m, 8H), 1.49-1.18 (m, 108H), 0.82 (m, 18H, —CH3).
To a solution of compound 6 (630 mg, 0.384 mmol) and 2-(3-oxo-indan-1-ylidene)-malononitrile (224 mg, 1.15 mmol) in anhydrous chloroform (19 g) was added pyridine (0.304 g, 3.84 mmol). The mixture was then degassed with nitrogen. The reaction mixture was warmed to 60° C. and stirred for 3 hours. After cooling to room temperature, the precipitate was filtered and washed with chloroform and acetone to give Compound Example 4 (324 mg, 42%) as a black solid.
1H NMR (400 MHz, CDCl3):δ 9.04 (s, 2H), 8.68 (s, 2H), 8.60 (2H), 7.84 (2H), 7.69 (4H), 7.43 (s, 2H), 3.26 (t, 4H), 2.19-2.01 (m, 12H), 1.61 (m, 8H), 1.51-1.15 (m, 108H), 0.82 (m, 18H, —CH3).
To degassed toluene (10 ml) solution, Compound 7 (1.175 g, 0.983 mmol) and Compound 8 (0.182 g, 0.409 mmol) were added. To this mixture catalyst-tris(dibenzylideneacetone) dipalladium (0.030 g, 0.030 mmol) followed by ligand-tris(o-tolyl)phosphine (0.030 g, 0.12 mmol) was added, the mixture was further degassed for 5 minutes and was then heated up to 70° C. for 2 hours. The reaction was cooled down to room temperature and 20 ml of water was added and the mixture was stirred for 5 minutes. The aqueous phase was removed, and 1 ml of water was added followed by trifluoroacetic acid (3 ml) added slowly. The mixture was stirred at room temperature for 3 hours. 20 ml of water was added to the reaction at 0° C. and stirred for 10 minutes. The phases were separated, the organic phase was washed with saturated sodium hydrogen carbonate solution followed by water, dried over magnesium sulfate and concentrated under reduced pressure. The crude product was purified via column chromatography with a dichloromethane/heptane mixture 60% to 100% of dichloromethane. After evaporation of fractions containing the product, Compound 9, 236 mg (45%) as a red oil was obtained. LCMS confirmed the expected mass of the product.
Compound 9 (0.263 g, 0.445 mmol), Intermediate F (0.246 g, 1.01 mmol) and p-TsOH (0.261 g, 1.52 mmol) were placed in a flask and toluene (6 mL) and ethanol (12 mL) were added. The mixture was heated up to 65° C. under nitrogen. After 3 hours methanol (20 mL) was added and the solution was filtered using a Buchner funnel, washed with methanol. The crude product was purified via column chromatography with chloroform. After evaporation of fractions containing the product was washed with heptane to give product, Compound Example 5, 0.113 g of a black solid (32%). LCMS confirmed the expected mass of the product.
Compound 10 (1.64 g, 2.38 mmol) and Compound 11 (0.350 g, 0.994 mmol) were placed in a flask. Toluene (20 mL) was added and degassed for 15 minutes and then tri(o-tolyl)-phosphine (0.090 g, 0.298 mmol) and Tris(dibenzylideneacetone)dipalladium(0) (0.073, 0.079 mmol) were added. The mixture was further degassed for 5 minutes and heated at 70° C. for 30 minutes, after which the temperature was increased to 100° C. for a further stirred overnight. The reaction mixture was cooled down and solvent was removed on rotary evaporator. The crude product was purified via column chromatography with a heptane/toluene mixture. The solvent was evaporated to give Compound 12, 0.935 g (94.5%) of dark brown oil. LCMS confirmed the mass of the expected product.
Compound 12 (0.935 g, 0.939 mmol) was dissolved in DMF (30 ml) and cooled. Phosphorus oxychloride (0.87 mL, 9.39 mmol) was added dropwise at 3° C. The reaction mixture was stirred at this temperature for 1 hour and then at 80° C. for 2 hours after which the reaction mixture was cooled to room temperature and saturated NaOAc was added to it slowly. The mixture was diluted and extracted with DCM. The organic phase was washed with saturated NaCl and water, dried over MgSO4, filtered and evaporated. The product was purified via column chromatography with a dichloromethane:heptane mixture of 16% to 100% dichloromethane. Fractions with the product were evaporated to give Compound 13, 0.665 g (67%) as dark red sparkly foamy solid. LCMS confirmed the mass of the expected product.
Compound 13 (0.660 g, 0.628 mmol), Intermediate F (0.800 g, 3.130 mmol) and p-TsOH (0.893 g, 4.700 mmol) were placed in a flask and toluene (16 mL) and ethanol (32 mL) were added. The mixture was heated up to 65° C. under nitrogen. After 4 hours the reaction mixture was filtered using a Buchner funnel, washed with methanol and ethanol. Crude product was purified via column chromatography with dichloromethane:heptane solvent mixture 50% to 100% of dichloromethane. Fractions containing product were evaporated and suspended in dichloromethane:chloroform mixture and filtrated, washed with toluene and heptane to give Compound Example 6, 0.496 g (52%) as a black solid, LCMS confirmed the expected mass of the product.
Compound 14 (4.2 g, 6.25 mmol) was placed in a flask under N2, dissolved in THE (55 mL) and cooled to −78° C. n-BuLi (2.55 mL, 6.37 mmol) was added and the mixture was stirred at this temperature for 3 hours. After this time warmed up to −70° C., tributyltin chloride (1.79 mL, 6.25 mmol) was added and the mixture was brought −15° C. The mixture slowly warmed up to room temperature and stirred overnight. The mixture was brought to 0° C., quenched with water, extracted with diethyl ether, washed with water and sat. NaCl, dried over MgSO4 and filtered. Most of the solvent was evaporated to give Compound 15, 6.545 g (109%) as a brown/orange oil. LCMS confirmed the expected product, used in the next step without further purification.
Compound 15 (6.545 g, 5.12 mmol) and Compound 11 (0.837 g, 2.38 mmol) were placed in a flask. Toluene (43 mL) was added and degassed for 15 minutes and then tri(o-tolyl)-phosphine (0.217 g, 0.714 mmol) and tris(dibenzylideneacetone)dipalladium(0) (0.174, 0.190 mmol) were added. The mixture was further degassed for 5 minutes and heated at 70° C. for 1 hour, after which the temperature was increased to 100° C. for a further stirred overnight. The reaction mixture was cooled down and solvent was removed on rotary evaporator. The crude product was purified via column chromatography with heptane/toluene mixture, 0% to 20% of toluene. Fractions with product were evaporated to give Compound 16, 3.212 g (89%) as a dark brown oil. LCMS confirmed the mass of the expected product.
Compound 16 (3.212 g, 2.10 mmol) was dissolved in toluene (12 mL) and heptane mixture (20 mL). To this DMF (70 ml) was added and the mixture was cooled down with ice bath. Phosphorus oxychloride (1.95 mL, 21.0 mmol) was added dropwise at 3° C. The reaction mixture was stirred at this temperature for 1 hour and then at 80° C. for 2 hours after which the reaction mixture was cooled to room temperature and saturated sodium acetate was added to it slowly. The mixture was diluted and extracted with toluene. The organic phase was washed with saturated NaCl and water, dried over MgSO4, filtered and evaporated. The product was purified via column chromatography with a dichloromethane:heptane mixture of 16% to 100% dichloromethane. Fractions with the product were evaporated to give Compound 17, 2.719 g (82%) as deep red sparkly foamy solid. LCMS confirmed the mass of the expected product.
Compound 17 (1.700 g, 1.07 mmol), Intermediate F (1.36 g, 5.35 mmol) and p-TsOH (1.52 g, 4.700 mmol) were placed in a flask and toluene (27 mL) and ethanol (55 mL) were added. The mixture was heated up to 65° C. under nitrogen. After ˜4 hours the reaction mixture was filtered using a Buchner funnel, washed with methanol and ethanol. Crude product was purified via column chromatography with chloroform:heptane solvent mixture from 50% to 100% of chloroform. Fractions containing product were evaporated and dissolved in dichloromethane and precipitated into pentane, washed with dichloromethane and pentane to give Compound Example 7, 0.298 g (21%) as a black solid, LCMS confirmed the expected mass of the product.
Toluene (60 ml) was added to CPDT-SnBu3 (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.
A solution of Compound 18 (0.5 g, 0.50 mmol) in THF (5 ml) and cooled to −40° C. and N-bromosuccinimide (0.18 g, 1 mmol) was added portion-wise. The mixture was stirred at this temperature for 4.5 hours and quenched with 10% sodium thiosulfate solution, extracted with heptane, dried over magnesium sulphate, and evaporated to give Compound 19 as a black oil.
A solution of Compound 19 (0.53 g, 0.46 mmol) and Thiophene-SnBu3 (1.03 g, 1.67 mmol) in toluene (9 ml) was degassed for 15 minutes. Tris(2-methylphenyl)phosphine (0.04 g, 0.14 mmol) and tris(dibenzylideneacetone) dipalladium (0.03 g, 0.04 mmol) were added and the mixture was degassed for additional 5 minutes. The mixture was heated at 70° C. for 30 min and then at 100° C. overnight. Upon completion it was diluted with toluene and extracted with water. The organic phase was placed in a flask, trifluoroacetic acid (4 ml) was added, and it was stirred for 30 minutes at room temperature and then at 40° C. for another 30 minutes. The reaction mixture was cooled to room temperature, water (10 ml) was added followed by a saturated solution of sodium hydrogen carbonate, it was transferred to separating funnel and further extracted with this solution. The organic phase was dried over magnesium sulphate, filtered and concentrated under vacuum to give a purple oil. Purification via column chromatography (silca-gel; heptane/toluene) gave Compound 20 (0.25 g) as a purple solid.
Compound 20 (0.25 g, 0.17 mmol), IC2CN (0.21 g, 0.83 mmol) and para-toluenesulfonic acid (0.24 g, 1.24 mmol) were placed in a flask, toluene (6 ml) and ethanol (8 ml) were added, and the mixture was degassed for 15 minutes with nitrogen and heated at 70° C. overnight. After this time the mixture was filtered and the resulting solid was washed with hot ethanol, methanol and pentane. Purification via column chromatography (silica gel; toluene DCM and THF) gave Compound Example 8 (0.07 g).
1H NMR (300 MHz, THF-d8): δ 9.28 (s, 2H), 8.98 (s, 2H), 8.79 (s, 2H), 8.35 (s, 2H), 7.97 (t, 2H), 7.83 (s, 2H), 4.35 (d, 4.7 Hz, 4H), 2.22 (m, 8H), 1.96 (m, 2H), 1.49-1.44 (m, 9H), 1.12-0.93 (m, 54H), 0.75-0.60 (m, 27H).
LCMS (APCI+ve): 1924.91 ([M+H]+).
Compound 21 was prepared as described in Zhang et al, “Electron-Deficient and Quinoid Central Unit Engineering for Unfused Ring-Based A1-D-A2-D-A1-Type Acceptor Enables High Performance Nonfullerene Polymer Solar Cells with High Voc and PCE Simultaneously” Small 2020, 16, 1907681.
A solution of Compound 21 (3.94 g, 1.97 mmol) in toluene (100 mL) was degassed for 45 minutes. Intermediate 1 (0.29 g, 0.82 mmol), Pd2(dba)3 (0.06 g, 0.07 mmol), and P(o-Tol)3 (0.08 g, 0.25 mmol) were added, and the mixture was heated to 65° C. for 3.5 hours under nitrogen and stirred at room temperature overnight. After this time, additional catalyst (60 mg) and ligand (75 mg) were added, and the solution was heated to 100° C. for 1 hour. An additional 90 mg of BisBT-diBr was added (50 mg), and the solution was heated at 100° C. for a further 4.5 hours. After this time the mixture was cooled to room temperature and the solvent was removed in vacuo to give a red/brown solid. The crude residue was purified by column chromatography (heptane/dichloromethane and toluene/heptane. to give Compound 22 (100 g) as a dark red/brown solid.
Compound 22 (0.90 g, 0.45 mmol) was added to DMF (30 mL) under nitrogen and the mixture was heated gently until it dissolved. The mixture was then cooled to −2° C. with an ice bath. POCl3 (0.45 mL, 4.47 mmol) was added dropwise (maintaining temperature <5° C.). Once the addition was complete the mixture was stirred at room temperature for 15 minutes before being heated to 80° C. for 3.5 hours. The reaction was then cooled to room temperature and quenched with saturated sodium acetate, then additional water was added. The mixture was extracted three times with toluene and the organic phases were combined and extracted with aqueous NaCl to remove any residual DMF. The crude residue was purified by column chromatography (toluene) to give Compound 23 (0.99 g) as a red/brown solid.
Compound 23 (0.63 g, 0.30 mmol), Intermediate 2 (0.39 g, 1.52 mmol) and p-toluenesulfonic acid (0.43 g, 2.28 mmol) were placed in a flask under nitrogen. Toluene (8 mL) and ethanol (16 mL) were added and the mixture purged with nitrogen for 15 minutes. It was then was heated up to 65° C. overnight. After cooling to room temperature, it was filtered, washed twice with hot EtOH (25 mL), three times with hot MeOH (25 mL), and three times with pentane (25 mL) to give 0.66 g of a black solid The crude solid was purified via column chromatography (dichloromethane/heptane), dissolved in dichloromethane (10 mL) and reprecipitated into pentane (100 mL) to give Compound Example 9 (0.23 g) as a black solid.
1H NMR (300 MHz, THF-d8): δ 9.15 (bs, 2H), 9.01 (d, 3.93 Hz, 2H), 8.42 (s, 2H), 8.12 (s, 2H), 8.05 (bs, 2H), 7.88 (s, 2H), 7.38 (d, 8.11 Hz, 8H), 7.27 (d, 7.73 Hz, 8H), 7.13 (t, 7.93 Hz, 16H), 2.58 (t, 7.01 Hz, 16H), 1.62-1.57 (m, 16H), 1.36-1.28 (m, 48H), 0.89-0.85 (m, 24H).
LCMS (APCI+ve): 2513.45 ([M]+).
A compound in which the donor groups are different may be prepared according to the following reaction scheme.
Absorption spectra for Compound Examples 1-4 were measured in xylene solution or in a film formed by spin-coating a xylene solution of the compound.
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.
The absorption spectrum for Comparative Compound 2 is taken from CN11260833.
Each of Compound Examples 1-4 show strong absorption in film at wavelengths above 1000 nm.
Absorption spectra for Compounds 5-7 in 1×10−6 M o-dichlorobenzene solution are shown in
An absorption spectrum for an o-dichlorobenzene solution of Compound Example 8 containing thiophene bridges is shown in
An absorption spectrum for Compound Example 9 in o-dichlorobenzene solution is shown in
As shown in
HOMO and LUMO energy levels of films of the example compounds were measured by square wave voltammetry.
An organic photodetector having the following structure was prepared:
Cathode/Donor:Acceptor layer/Anode
A glass substrate coated with a layer of indium-tin oxide (ITO) was treated with polyethyleneimine (PEIE) to modify the work function of the ITO.
A mixture of Donor Polymer 1 (donor) and Compound Example 1 (acceptor) in a donor 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 (VIIa) 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 anode stack of MoO3 (10 nm) and ITO (50 nm) was formed over the bulk heterojunction by thermal evaporation (MoO3) and sputtering (ITO).
External quantum efficiency (EQE) was measured across a range of wavelengths. Results are shown in
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 (50 nm) 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.
As shown in
As shown in
A device was prepared as described for Device Example 2 except that Compound Example 4 was used in place of Compound Example 3.
The external quantum efficiency for this device across a range of wavelengths at an applied bias of −5V is shown in
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.
The external quantum efficiencies for these devices across a range of wavelengths at an applied bias of −5V is shown in
All modelling as described in these examples was performed using Gaussian09 software available from Gaussian using Gaussian09 with B3LYP (functional).
HOMO and LUMO levels were modelled for individual donor and acceptor units. Results are set out in Tables 1-3
Acceptor units A1 preferably have a modelled LUMO of at least 2.9 eV or at least 3.0 eV from vacuum level.
HOMO and LUMO levels were modelled for compounds of formula (I) in which there is no bridge between A2 and D1 (z1=0) or between A3 and D2 (z2=0).
Results are set out in Table 4. Sif corresponds to oscillator strength of the transition from S1 (predicting absorption intensity), Eopt is the modelled optical gap.
HOMO and LUMO levels were modelled for compounds of formula (I) in which there is a bridge between A2 and D1 (z1=1) and between A3 and D2 (z2=1).
| Number | Date | Country | Kind |
|---|---|---|---|
| 2111398.0 | Aug 2021 | GB | national |
| 2204177.6 | Mar 2022 | GB | national |
| 2204179.2 | Mar 2022 | GB | national |
| 2208329.9 | Jun 2022 | GB | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/EP2022/072160 | 8/5/2022 | WO |
