Classifications

• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
  • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
  • C07D495/04—Ortho-condensed systems
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
  • C07D495/12—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains three hetero rings
  • C07D495/14—Ortho-condensed systems
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
  • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
  • C07F7/02—Silicon compounds
  • C07F7/08—Compounds having one or more C—Si linkages
  • C07F7/10—Compounds having one or more C—Si linkages containing nitrogen having a Si-N linkage
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
  • H10K30/60—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation in which radiation controls flow of current through the devices, e.g. photoresistors

Definitions

• the present invention relates to compounds useful as organic optical semiconductors.
• Organic optical semiconductors are used in optoelectronic devices such as organic solar cells (OSCs) and organic photodetectors (OPDs), and various p-type materials (donor materials) and n-type materials (acceptor materials) are used. has been done.
• OSCs organic solar cells
• OPDs organic photodetectors
• p-type materials donor materials
• n-type materials acceptor materials
• narrow bandgap n-type low-molecular materials have attracted attention in the field of infrared photoelectronic optical devices, and COI-4Cl and COTIC-4F shown below are known as non-fullerene acceptor materials.
• the present invention has been made with attention to the above-mentioned circumstances, and its objectives are to lengthen the infrared absorption wavelength, reduce dark current Id , and improve the ON/OFF ratio of photodetection.
• the aim is to achieve at least one thing.
• the present inventors have found that by adopting a new compound with a specific structure as a non-fullerene acceptor material, the infrared absorption wavelength can be increased to a longer wavelength, and the dark current I d can be reduced.
• the present invention has been completed by achieving at least one of the following: reduction and improvement of the ON/OFF ratio of photodetection.
• a compound represented by formula (1) (In the formula, X 1 is a carbon atom, a nitrogen atom, or a silicon atom. When X 1 is a carbon atom or a silicon atom, m1 is 1, and when X 1 is a nitrogen atom, m1 is 0.
• a 1 and A 2 each independently represent a benzene ring which may have a substituent or a thiophene ring which may have a substituent.
• R 1 and R 2 each independently represent C(CN) 2 or O.
• R 1 is C(CN) 2
• R 1 is O and X 1 is a nitrogen atom
• a 2 is a benzene ring
• R 11 , R 12 , R 21 and R 22 each independently represent an alkyl group having 6 to 30 carbon atoms
• R 31 and R 32 each independently represent hydrogen or an alkyl group having 1 to 30 carbon atoms.
• n1 and n2 are each independently 0 or 1.
• [3] An organic thin film containing the compound described in [1] or [2] above.
• An organic photodetector comprising the organic thin film described in [3] above in a light receiving section.
• At least one of increasing the infrared absorption wavelength, reducing dark current I d , and improving the ON/OFF ratio of photodetection can be achieved.
• Compound The compound of the present invention is a compound represented by the following formula (1).
• X 1 is a carbon atom, a nitrogen atom, or a silicon atom.
• X 1 is a carbon atom or a silicon atom
• m1 is 1, and when X 1 is a nitrogen atom, m1 is 0.
• a 1 and A 2 each independently represent a benzene ring which may have a substituent or a thiophene ring which may have a substituent.
• R 1 and R 2 each independently represent C(CN) 2 or O.
• a 1 is a benzene ring
• (1) R 1 is C(CN) 2
• R 1 is O and X 1 is a nitrogen atom
• a 2 is a benzene ring.
• R 2 is C(CN) 2 or (4) R 2 is O and X 1 is a nitrogen atom.
• R 11 , R 12 , R 21 and R 22 each independently represent an alkyl group having 6 to 30 carbon atoms.
• R 31 and R 32 each independently represent hydrogen or an alkyl group having 1 to 30 carbon atoms.
• n1 and n2 are each independently 0 or 1.
• X1 may be a carbon atom, a nitrogen atom, or a silicon atom, but from the viewpoint of improving the ON/OFF ratio and reducing the dark current Id , X1 should be a carbon atom or a silicon atom. is preferable, and a carbon atom is more preferable.
• R 11 and R 12 are each independently preferably an alkyl group having 6 to 25 carbon atoms, more preferably an alkyl group having 7 to 20 carbon atoms, and preferably an alkyl group having 8 to 15 carbon atoms. An alkyl group is more preferable, and an alkyl group having 8 to 12 carbon atoms is particularly preferable. More preferably, R 11 and R 12 are the same.
• R 21 and R 22 are each independently preferably an alkyl group having 6 to 25 carbon atoms, and preferably an alkyl group having 7 to 20 carbon atoms. is more preferred, an alkyl group having 8 to 15 carbon atoms is even more preferred, and an alkyl group having 8 to 12 carbon atoms is particularly preferred. More preferably, R 21 and R 22 are the same.
• R 21 is preferably an alkyl group having 6 to 30 carbon atoms, more preferably an alkyl group having 7 to 25 carbon atoms, and R 21 is an alkyl group having 8 to 20 carbon atoms.
• An alkyl group is more preferable, and an alkyl group having 8 to 17 carbon atoms is particularly preferable.
• R 21 is preferably an alkyl group having 6 to 30 carbon atoms, more preferably an alkyl group having 8 to 28 carbon atoms, and even more preferably an alkyl group having 12 to 25 carbon atoms.
• R 11 , R 12 , R 21 , and R 22 are each independently preferably an aliphatic hydrocarbon group, more preferably a linear or branched alkyl group, and a branched alkyl group.
• An alkyl group is more preferable, and a group in which a linear alkyl group is bonded to a linear alkyl group (n-alkyl-n-alkyl group) is even more preferable.
• Particularly preferred are alkyl groups (1- or 2-alkylalkyl groups such as 1-n-alkyl-n-alkyl group and 2-n-alkyl-n-alkyl group).
• the number of carbon atoms in the main alkyl group is one more than the alkyl group bonded to the 1-position (i.e., 1-C x alkyl- C x+1 alkyl group; C x is (indicating that the number of carbon atoms in the alkyl group is x) is preferred.
• R 11 , R 12 , R 21 , and R 22 include an alkyl group having 6 carbon atoms such as n-hexyl group; an alkyl group having 7 carbon atoms such as n-heptyl group; n-octyl group; 1-n-butyl-n-butyl group, 1-n-propyl-n-pentyl group, 1-ethyl-n-hexyl group, 2-ethyl-n-hexyl group, 3-ethylhexyl group, 4-ethylhexyl group, C8 alkyl group such as 1-methylheptyl group, 2-methylheptyl group, 6-methylheptyl group, 2,4,4-trimethylpentyl group, 2,5-dimethylhexyl group; n-nonyl group, 1 -n-propylhexyl group, 2-n-propylhexyl group, 1-ethylheptyl group, 2-
• R 31 and R 32 each independently represent hydrogen or an alkyl group having 1 to 30 carbon atoms.
• Examples of the alkyl group having 6 to 30 carbon atoms in R 31 and R 32 are the same as those for R 11 , R 12 , R 21 , R 22 , etc. described above, and examples of the alkyl group having 1 to 5 carbon atoms include includes an alkyl group having 1 carbon number such as a methyl group; an alkyl group having 2 carbon atoms such as an ethyl group; an alkyl group having 3 carbon atoms such as n-propyl group; an alkyl group having 4 carbon atoms such as n-butyl group. ; C5 alkyl group such as n-pentyl group; and the like.
• a 1 and A 2 each independently represent a benzene ring which may have a substituent or a thiophene ring which may have a substituent.
• the substituent is not particularly limited and includes, for example, a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and among them, a halogen atom is preferable, and a fluorine atom , more preferably a chlorine atom or a bromine atom, and even more preferably a chlorine atom. Further, it is preferable that 0 to 2 halogen atoms are independently bonded to A 1 and A 2 , and more preferably 0 or 1 halogen atom.
• At least one of A 1 and A 2 is a thiophene ring which may have a substituent, and A 1 , A 2 are both preferably thiophene rings which may have a substituent.
• R 1 and R 2 each independently represent C(CN) 2 or O.
• a 1 is a thiophene ring, it may be C(CN) 2 or O, but from the viewpoint of reducing the dark current I d and improving the ON/OFF ratio of photodetection, R 1 , Preferably, both R 2 are O.
• R 1 is a benzene ring
• R 1 is C(CN) 2 or R 1 is O and X 1 is a nitrogen atom
• a 2 is a benzene ring
• R 2 is C(CN) 2 .
• CN) 2 or R 1 is O and X 1 is a nitrogen atom.
• a 1 and A 2 are thiophene rings which may have substituents, and X 1 is a carbon atom or a silicon atom. It is preferable that A 1 and A 2 are a thiophene ring which may have a substituent, X 1 is a carbon atom or a silicon atom, and R 1 and R 2 are O. preferable.
• (Z-1) to (Z-3), and (Z-2) or (Z-3). is more preferable.
• (Z-1) A 1 and A 2 are a thiophene ring which may have a substituent, and X 1 is a nitrogen atom.
• (Z-2) A 1 and A 2 have a substituent, and R 1 and R 2 are C(CN) 2
• (Z-3) A 1 and A 2 are benzene rings which may have substituents, and R 1 and R 2 are is O, and X 1 is a nitrogen atom
• n1 and n2 are each independently 0 or 1, but from the viewpoint of increasing the infrared absorption wavelength, it is preferable that at least one of n1 and n2 is 1, and both n1 and n2 are 1. It is more preferable that there be.
• (A-2), (A-8), (A-10), (A-14), or (A-16) is more preferable.
• (A-2), (A-8), (A-10) or (A-16) are more preferable.
• (A-5), (A-6), (A-19), or (A-20) is more preferable, (A-5), (A-6), or (A-20) is even more preferable, and (A-5) or (A-6) is particularly preferable.
• the benzene rings and thiophene rings listed in the columns A 1 and A 2 in Table 1 include those having substituents.
• the molecular weight of the compound of the present invention is preferably from 500 to 5,000, more preferably from 700 to 3,500, and even more preferably from 1,000 to 2,000.
• X 1 , m1, A 1 , A 2 , R 1 , R 2 , R 11 , R 12 , R 21 , R 22 , R 31 , R 32 , n1, and n2 each have the same meaning as above;
• Y 1 and Y 2 are each independently a hydrogen atom or a halogen atom, and Z represents an alkyl group having 1 to 4 carbon atoms.
• the tin compound represented by the formula (3) is prepared by first reacting the above compound (2) with an organolithium compound in a solvent to activate the thiophene ring, and then reacting with Z 3 SnX 2 . can be obtained.
• each of the three Z's independently represents an alkyl group having 1 to 4 carbon atoms, and X 2 represents a halogen group.
• organic lithium compound examples include n-butyllithium, sec-butyllithium, tert-butyllithium, and lithium diisopropylamide, with n-butyllithium (n-BuLi) being preferred.
• the three Z's may be the same or different, but from the viewpoint of ease of synthesis, they are preferably the same, and it is more preferable that all the three Z's are butyl groups.
• X 2 is preferably a chlorine atom or a bromine atom, more preferably a chlorine atom.
• Z 3 SnX 2 is preferably a tri-C 1-4 alkyltin halide such as trimethyltin chloride, trimethyltin bromide, triethyltin chloride, or tributyltin chloride, more preferably a C 1-4 alkyltin chloride, and particularly preferably is tributyltin chloride (SnBu 3 Cl).
• Z 3 SnX 2 is preferably added in an amount of 2 to 3 equivalents, more preferably 2.3 to 2.5 equivalents, relative to the compound (2).
• reaction temperature can be, for example, -70 to -90°C.
• a compound represented by formula (4) is produced by reacting a tin compound represented by formula (3) with a compound represented by formula (5) below.
• the amount of the compound (5) is preferably 1.2 to 10 mol, more preferably 1.5 to 7 mol, even more preferably 2 to 5 mol, per 1 mol of the compound (3). .
• R 11 and n1 each have the same meaning as above, and X 3 represents a halogen atom. ]
• a catalyst may be present together.
• the catalyst in step B include metal catalysts, preferably palladium-based catalysts, nickel-based catalysts, iron-based catalysts, copper-based catalysts, rhodium-based catalysts, ruthenium-based catalysts, and the like. Among these, palladium catalysts are more preferred. Palladium in the palladium-based catalyst may be zero-valent or divalent.
• Examples of the palladium-based catalyst include palladium (II) chloride, palladium (II) bromide, palladium (II) iodide, palladium (II) oxide, palladium (II) sulfide, palladium (II) telluride, and hydroxide.
• catalysts may be used alone or in combination of two or more.
• tetrakis(triphenylphosphine)palladium(0), tris(dibenzylideneacetone)dipalladium(0), dichlorobis(triphenylphosphine)palladium(II), tris(dibenzylideneacetone)dipalladium(0)chloroform Adducts are particularly preferred.
• a specific ligand may be coordinated to the catalyst.
• the above-mentioned ligand include trimethylphosphine, triethylphosphine, tri(n-butyl)phosphine, tri(isopropyl)phosphine, tri(tert-butyl)phosphine, tri-tert-butylphosphonium tetrafluoroborate, bis( tert-butyl)methylphosphine, tricyclohexylphosphine, diphenyl(methyl)phosphine, triphenysphosphine, tris(o-tolyl)phosphine, tris(m-tolyl)phosphine, tris(p-tolyl)phosphine, tris(2-furyl) ) phosphine, tris(2-methoxyphenyl)phosphine, tris(3-methoxyphenyl)phosphine, tris(4-methoxy
• solvents that do not affect the reaction can be used, such as ether solvents, aromatic solvents, ester solvents, hydrocarbon solvents, halogen solvents, ketone solvents, and amide solvents.
• a solvent etc. can be used.
• the ether solvent include diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, tetrahydrofuran, methyltetrahydrofuran, dimethoxyethane, cyclopentyl methyl ether, tert-butyl methyl ether, and dioxane.
• Examples of the aromatic solvent include benzene, toluene, xylene, mesitylene, chlorobenzene, and dichlorobenzene.
• Examples of the ester solvent include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, and butyl acetate.
• Examples of the hydrocarbon solvent include pentane, hexane, heptane, and the like.
• Examples of the halogenated solvent include dichloromethane, chloroform, dichloroethane, and dichloropropane.
• Examples of the ketone solvent include acetone, methyl ethyl ketone, methyl isobutyl ketone, and the like.
• amide solvent examples include N,N-dimethylformamide, N,N-dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, 1,3-dimethyl-3,4,5,6-tetrahydro -(1H)-pyrimidine and the like.
• nitrile solvents such as acetonitrile, sulfoxide solvents such as dimethyl sulfoxide, and sulfone solvents such as sulfolane can be used.
• aromatic solvents are preferred, toluene or xylene is more preferred, and toluene is even more preferred.
• the amount of the solvent is generally about 1 mL or more and 100 mL or less, preferably 3 mL or more and 70 mL or less, and 5 mL or more and 40 mL or less, per 1 g of compound (3). The following are more preferred.
• the reaction temperature is preferably 0°C or higher and 220°C or lower, more preferably 40°C or higher and 200°C or lower, and even more preferably 60°C or higher and 180°C or lower, from the viewpoint of increasing reaction efficiency.
• the reaction temperature may be adjusted using microwaves.
• step B When the compound represented by formula (5) is reacted with the compound represented by formula (3) in step B, R 11 and R 12 become the same, and n1 and n2 become the same.
• the amount of the compound (5) is preferably 1.2 to 10 mol, more preferably 1.5 to 7 mol, and still more preferably 2 to 4 mol, per 1 mol of the compound (3). .
• R 11 and R 12 and/or n1 and n2 are different, a compound represented by formula (5) and a compound represented by formula (6) below are added to the compound represented by formula (3).
• the compound represented by formula (5) may be reacted after converting the three SnZ groups near R32 into an inert functional group (protecting group), and then, after the desired reaction is completed, the protecting group is removed.
• the compound represented by formula (6) may be reacted at the end.
• the total amount of the above compound (5) and the above compound (6) is 1.2 to 10 mol per 1 mol of the above compound (3). is preferable, more preferably 1.5 to 7 mol, still more preferably 2 to 4 mol.
• R 12 and n2 each have the same meaning as above, and X 4 represents a halogen atom. ]
• a compound represented by formula (1) is produced by reacting a compound represented by formula (4) with a compound represented by formula (7) below.
• the amount of the compound (7) is preferably 1.2 to 10 mol, more preferably 1.5 to 7 mol, even more preferably 1.8 to 5 mol, per 1 mol of the compound (4). It is.
• a 1 and A 2 become the same, and R 1 and R 2 become the same.
• a 1 and A 2 and/or R 11 and R 12 are different, the compound represented by formula (4) is reacted with the compound represented by formula (7) and the following formula (8).
• the oxygen atom in the thiophene ring having R 12 in the compound represented by formula (4) is converted into an inert functional group (protecting group), and then the compound represented by formula (7) is reacted. Then, after the desired reaction is completed, a step of removing the protecting group may be performed, and finally, the compound represented by formula (8) may be reacted.
• the total amount of the above compound (7) and the above compound (8) is 1.2 to 10 mol per 1 mol of the above compound (4). The amount is preferably 1.5 to 7 mol, and even more preferably 1.8 to 5 mol.
• Step C a solvent that does not affect the reaction can be used, and the solvents listed as the solvent in Step B above can be used, and among them, chloroform or acetic anhydride is more preferable.
• the amount of the solvent is generally about 1 mL or more and 100 mL or less, preferably 3 mL or more and 80 mL or less, and 5 mL or more and 60 mL or less, per 1 g of compound (4). The following are more preferred.
• the reaction temperature is preferably 40°C or higher and 150°C or lower, more preferably 50°C or higher and 100°C or lower, from the viewpoint of increasing reaction efficiency.
• the reaction temperature may be adjusted using microwaves.
• the compound represented by the above formula (1) can be used as an acceptor material.
• electronic devices containing the compound represented by the above formula (1) include organic photodetectors (for example, sensors such as image sensors), organic field effect transistors (OFETs), organic thin film transistors (OTFTs), and organic light emitting diodes (OLEDs). ), organic light emitting transistor (OLET), organic photovoltaic device (OPV), organic solar cell, dye-sensitized solar cell (DSSC), perovskite solar cell, solar cell, laser diode, Schottky diode, photoconductor, Examples include thermoelectric devices.
• the donor material and the compound of the present invention may be in contact with each other, and a layer containing the donor material and a layer containing the acceptor material may be laminated, or the donor material and the acceptor material may be stacked. It may be a mixed layer containing.
• the present invention also includes an organic thin film containing the compound represented by the above formula (1).
• the present invention also includes an organic photodetection element and an organic photodetector having an organic photodetection element, and the organic photodetection element includes an organic thin film in a light receiving section.
• the reaction solution was allowed to cool, and a 10% aqueous sodium hydrogen carbonate solution was added to separate the layers.
• the aqueous layer was extracted with toluene, and the organic layers were combined and concentrated under reduced pressure.
• Example 1 Synthesis of EHCyDTh-2OEHTh-TCN2
• EHCyDTh-OEHThCHO 75 mg obtained in Synthesis Example 1 above
• TCN 46 mg
• pyridine 0.8 mL
• the reaction solution was allowed to cool and concentrated under reduced pressure.
• the obtained crude product was purified with a silica gel column (dichloromethane) to obtain EHCyDTh-2OEHTh-TCN2 (64 mg, yield 61%).
• Example 2 Synthesis of EHCyDTh-2EHTh-TCN2
• EHCyDTh-EHThCHO (240 mg) obtained in Synthesis Example 2 above, TCN (250 mg), and pyridine (0.9 mL) were placed in a 20 mL Schlenk tube under a nitrogen atmosphere and dissolved in chloroform (4 mL). After degassing the reaction solvent, the mixture was stirred at 60°C for 17 hours. The reaction solution was allowed to cool and concentrated under reduced pressure. The obtained crude product was purified with a silica gel column (dichloromethane) to obtain EHCyDTh-2EHTh-TCN2 (245 mg, yield 72%).
• Example 3 (Synthesis of EHNCyDTh-2OEHTh-TCN2) EHNCyDTh-OEHThCHO (36 mg) obtained in Synthesis Example 3 above, TCN (24 mg), and pyridine (0.1 mL) were placed in a 20 mL Schlenk tube under a nitrogen atmosphere and dissolved in chloroform (1 mL). After degassing the reaction solvent, the mixture was stirred at 60°C for 17 hours. The reaction solution was allowed to cool and concentrated under reduced pressure. The obtained crude product was purified with a silica gel column (dichloromethane) to obtain EHNCyDTh-2OEHTh-TCN2 (17 mg, yield 31%).
• Example 4 (Synthesis of EHNCyDTh-2OEHTh-CI2) EHNCyDTh-OEHThCHO (47 mg) obtained in Synthesis Example 3 above, CI (33 mg), and pyridine (0.1 mL) were placed in a 20 mL Schlenk tube under a nitrogen atmosphere and dissolved in ethanol (2 mL). After degassing the reaction solvent, the mixture was stirred at 70°C for 17 hours. The reaction solution was allowed to cool and concentrated under reduced pressure. The obtained crude product was purified with a silica gel column (dichloromethane) to obtain EHNCyDTh-2OEHTh-CI2 (26 mg, yield 38%).
• Example 5 Synthesis of EHCyDTh-2OEHTh-CNI2
• EHCyDTh-OEHThCHO 36 mg obtained in Synthesis Example 1 above and CNI (30 mg) were placed in a 20 mL Schlenk tube under a nitrogen atmosphere and dissolved in acetic anhydride (2 mL). After degassing the reaction solvent, the mixture was stirred at 80°C for 17 hours. The reaction solution was allowed to cool and concentrated under reduced pressure. The obtained crude product was purified with a silica gel column (dichloromethane) to obtain EHCyDTh-2OEHTh-CNI2 (33 mg, yield 62%).
• Example 6 Synthesis of EHSiCyDTh-2OEHTh-TCN2 Under a nitrogen atmosphere, EHSiCyDTh-OEHThCHO obtained in Synthesis Example 4 (235 mg), TCN (137 mg), and pyridine (1.3 mL) were placed in a 20 mL Schlenk tube and dissolved in chloroform (13 mL). After degassing the reaction solvent, the mixture was stirred at 60°C for 17 hours. The reaction solution was allowed to cool and concentrated under reduced pressure. The obtained crude product was purified with a silica gel column (dichloromethane) to obtain EHSiCyDTh-2OEHTh-TCN2 (120 mg, yield 36%).
• Example 7 (Synthesis of EHSiCyDTh-2OEHTh-CNI2) EHSiCyDTh-OEHThCHO (292 mg) obtained in Synthesis Example 4 above and CNI (206 mg) were placed in a 20 mL Schlenk tube under a nitrogen atmosphere and dissolved in acetic anhydride (10 mL). After degassing the reaction solvent, the mixture was stirred at 80°C for 17 hours. The reaction solution was allowed to cool and concentrated under reduced pressure. The obtained crude product was purified with a silica gel column (dichloromethane) to obtain EHSiCyDTh-2OEHTh-CNI2 (315 mg, yield 72%).
• Example 8 (Synthesis of EHNCyDTh-2OEHTh-CNI2) EHNCyDTh-OEHThCHO (74 mg) obtained in Synthesis Example 3 above and CNI (49 mg) were placed in a 20 mL Schlenk tube under a nitrogen atmosphere and dissolved in acetic anhydride (1.5 mL). After degassing the reaction solvent, the mixture was stirred at 90°C for 17 hours. The reaction solution was allowed to cool and concentrated under reduced pressure. The obtained crude product was purified with a silica gel column (dichloromethane) to obtain EHNCyDTh-2OEHTh-CNI2 (45 mg, yield 38%).
• Example 9 (Synthesis of ONNCyDTh-2OEHTh-TCN2) ONNCyDTh-OEHThCHO (62 mg) obtained in Synthesis Example 5 above, TCN (36 mg), and pyridine (0.1 mL) were placed in a 20 mL Schlenk tube under a nitrogen atmosphere and dissolved in chloroform (1 mL). After degassing the reaction solvent, the mixture was stirred at 60°C for 17 hours. The reaction solution was allowed to cool and concentrated under reduced pressure. The obtained crude product was purified with a silica gel column (dichloromethane) to obtain ONNCyDTh-2OEHTh-TCN2 (48 mg, yield 55%).
• Example 10 Synthesis of ONNCyDTh-2OEHTh-CI2 ONNCyDTh-OEHThCHO (38 mg) obtained in Synthesis Example 5 above, CI (26 mg), and pyridine (0.1 mL) were placed in a 20 mL Schlenk tube under a nitrogen atmosphere, and dissolved in chloroform (1 mL). After degassing the reaction solvent, the mixture was stirred at 60°C for 17 hours. The reaction solution was allowed to cool and concentrated under reduced pressure. The obtained crude product was purified with a silica gel column (dichloromethane) to obtain ONNCyDTh-2OEHTh-CI2 (3 mg, yield 5%).
• Example 11 Synthesis of ONNCyDTh-2OEHTh-CNI2 ONNCyDTh-OEHThCHO (97 mg) obtained in Synthesis Example 5 above and CNI (64 mg) were placed in a 20 mL Schlenk tube under a nitrogen atmosphere and dissolved in acetic anhydride (1 mL). After degassing the reaction solvent, the mixture was stirred at 90°C for 17 hours. The reaction solution was allowed to cool and concentrated under reduced pressure. The obtained crude product was purified with a silica gel column (dichloromethane) to obtain ONNCyDTh-2OEHTh-CNI2 (123 mg, yield 92%).
• Example 12 Synthesis of OSiCyDTh-2OEHTh-CNI2
• OSiCyDTh-OEHThCHO 31 mg obtained in Synthesis Example 6 above and CNI (21 mg) were placed in a 20 mL Schlenk tube under a nitrogen atmosphere and dissolved in acetic anhydride (1 mL). After degassing the reaction solvent, the mixture was stirred at 90°C for 17 hours. The reaction solution was allowed to cool and concentrated under reduced pressure. The obtained crude product was purified with a silica gel column (dichloromethane) to obtain OSiCyDTh-2OEHTh-CNI2 (43 mg, yield 91%).
• the energy gap Eg was calculated based on the rise of UV by performing UV measurement of the organic thin film. That is, a low molecular weight compound was dissolved in chlorobenzene to a concentration of 8 mg/mL, and the resulting solution was spin coated onto a glass substrate to form an organic thin film. This thin film was subjected to UV measurement at room temperature and pressure using an ultraviolet/visible spectrometer (manufactured by Shimadzu Corporation, "UV-3600i Plus”), and the energy gap Eg (eV) was calculated by the following method.
• the peak showing the maximum absorption was defined as the wavelength ⁇ max .
• a tangent line is drawn as an auxiliary line to the curve showing the peak showing the maximum absorption in the region where absorption increases from the high wavelength side to the low wavelength side, and this tangent line and the absorbance are The wavelength at the intersection with the horizontal axis indicating 0 was read, and this wavelength was defined as the UV rising wavelength ⁇ edge [nm].
• ⁇ Method for manufacturing organic photodetector> (Preparation of mixed solution of p-type semiconductor compound and n-type semiconductor compound)
• a polymer compound having a structure of PTB7 (Aldrich) was prepared as a p-type semiconductor compound, and the above-mentioned low-molecular compound was prepared as an n-type semiconductor compound.
• a solution was prepared in which the total concentration of the p-type semiconductor compound and the n-type semiconductor compound was 3.2% by mass.
• the solution was stirred and mixed on a hot stirrer at a temperature of 100° C. for 2 hours or more, and then filtered through a 0.45 ⁇ m filter to obtain a mixed solution of a p-type semiconductor compound and an n-type semiconductor compound.
• the manufacturing methods described in (1) to (4) below are performed in order to produce an organic photodetecting element having an inverted structure in which a transparent electrode layer, an electron transport layer, an active layer, a hole transport layer, and an electrode layer are laminated in this order. Obtained.
• the organic photodetecting element includes an active layer, which is an organic thin film, in the light receiving section.
• molybdenum oxide was vapor-deposited on the surface of the active layer to form a hole transport layer on the active layer.
• silver as an electrode was deposited on the surface of the hole transport layer to obtain an organic photodetector.

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• 2023
  • 2023-05-11 WO PCT/JP2023/017803 patent/WO2023228773A1/ja not_active Ceased
  • 2023-05-11 JP JP2023564078A patent/JP7448103B1/ja active Active
  • 2023-05-17 TW TW112118230A patent/TW202406911A/zh unknown

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