Polymethine compounds and photoelectric conversion elements

Abstract

To provide a novel polymethine compound that absorbs light incident from wavelengths near the near-infrared to those near the infrared, while transmitting more incident visible light, and also demonstrates enhanced heat resistance.SOLUTION: A polymethine compound is an ion pair composed of an anion and a cation, the anion represented by the following formula (I-1). (In the formula (I-1), R1 and R2 independently represent a hydrogen atom or a monovalent organic group, R3 and R4 independently represent a monovalent group such as a phenyl group, X represents -NZ1Z2, -C≡C-Z3, -O-Z4, -SO2-Z5, or -S-Z6, and Y represent a divalent group such as a n-propenyl group).SELECTED DRAWING: None

Claims

1. A polymethine compound which is a counterionic bond consisting of an anion and a cation, wherein the anion is represented by the following formula (I-1). 【Chemistry 1】 (In formula (I-1), R 1 and R 2 Each of these independently represents a hydrogen atom or a monovalent organic group, R 3 and R 4 Each of these independently represents a monovalent group represented by the following formula (I-1-1), where X is, 【Chemistry 2】 This indicates that Y represents a divalent group represented by the following formula (I-1-2) or (I-1-3). 【Transformation 3】 (In formula (I-1-1), R a , R b , R c , R d , and R e each independently represent a hydrogen atom, a monovalent hydrocarbon group, or a monovalent electron-withdrawing group. However, among R a , R b , R c , R d , and R e , one or more represent the monovalent electron-withdrawing group. When only one of R a , R b , R c , R d , and R e is a halogen atom, one or more of the remaining R a , R b , R c , R d , and R e represent the monovalent hydrocarbon group or the monovalent electron-withdrawing group (excluding the halogen atom).) 【Chemistry 4】 (In formula (I-1-2), R f , R g , R h , R i , R j and R k Each of these independently represents a monovalent hydrocarbon group which may contain a hydrogen atom, or an oxygen atom, a nitrogen atom, or a sulfur atom. 【Transformation 5】 (In formula (I-1-3), R l , R m , R n and R o Each of these independently represents a monovalent hydrocarbon group which may contain a hydrogen atom, or an oxygen atom, a nitrogen atom, or a sulfur atom.

2. The polymethine compound according to claim 1, wherein the cation comprises one or more selected from the group consisting of alkali metal cations, alkaline earth metal cations, ammonium cations, sulfonium cations, phosphonium cations, and cationic polymethines.

3. The polymethine compound according to claim 2, wherein the cation comprises one or more selected from the group consisting of alkali metal cations, ammonium cations, and cationic polymethines.

4. The polymethine compound according to claim 3, wherein the cationic polymethine is a cation represented by the following formulas (I-2-1), (I-2-2), (I-2-3), or (I-2-4). 【Transformation 6】 (In formulas (I-2-1), (I-2-2), (I-2-3), and (I-2-4), E independently represents a carbon atom, a nitrogen atom, an oxygen atom, or a sulfur atom.) R p , R q , R r , R s , R t , R u , R v , R w and R x Each of these is independently a hydrogen atom, halogen atom, hydroxyl group, carboxyl group, nitro group, amino group, amide group, imide group, cyano group, silyl group, and -L. 1 , -S-L 2 , -SS-L 2 , -SO 2 -L 3 -N = N - L 4 , or R q and R r , R s and R t , R t and R u , R u and R v , R v and R w and R w and R x It represents one or more groups selected from the group consisting of groups represented by the following formulas (A), (B), (C), (D), (E), (F), (G), and (H), which are formed by the combination of one or more of the above, The amino group, amide group, imide group, and silyl group may be further substituted with one or more groups L selected from the group consisting of a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, a monovalent halogen-substituted alkyl group having 1 to 12 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 14 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms, and a monovalent heterocyclic group having 3 to 14 carbon atoms. Said L 1 and L 4 This is a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, a monovalent halogen-substituted alkyl group having 1 to 12 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 14 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms, or a heterocyclic group having 3 to 14 carbon atoms, which may be further substituted with the aforementioned group L. Said L 2 This is a hydrogen atom, or a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, a monovalent halogen-substituted alkyl group having 1 to 12 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 14 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms, or a heterocyclic group having 3 to 14 carbon atoms, which may be further substituted with the aforementioned group L. Said L 3 is a hydroxyl group, or a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, a monovalent halogen-substituted alkyl group having 1 to 12 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 14 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms, or a heterocyclic group having 3 to 14 carbon atoms, which may be further substituted with the aforementioned group L. Q 1 Q indicates an acetyl group, 2 This represents a structure expressed by the following formulas (q1), (q2), or (q3). 【Transformation 7】 (In formulas (A), (B), (C), (D), (E), (F), (G), and (H), the combination of Rx and Ry is R q and R r , R s and R t , R t and R u , R u and R v , R v and R w or R w and R x It is a combination of, R A 、 R B 、 R C 、 R D 、 R E 、 R F 、 R G 、 R H 、 R I 、 R J 、 R K and R L are each independently a hydrogen atom, a halogen atom, a hydroxyl group, a carboxy group, a nitro group, an amino group, an amide group, an imide group, a cyano group, a silyl group, -L 1 、 -S-L 2 、 -SS-L 2 、 -SO 2 -L 3 or -N=N-L 4 represents, and L 1 、 L 2 、 L 3 and L 4 are synonymous with L 1 、 L 2 、 L 3 and L 4 in the formulas (I-2-1) and (I-2-2), and the amino group, amide group, imide group and silyl group may be substituted with the group L.) -C m H m+1 (q1) -C a H a+1 -OC b H b+1 (q2) (In equation (q1), m represents an integer from 1 to 5, and in equation (q2), a and b each represent integers from 1 to 5.) 【Transformation 8】 (In equation (q3), n represents an integer from 1 to 5, and T 1 , T 2 , T 3 , T 4 and T 5 Each is independently a hydrogen atom or -OC p H p+1 (This shows that p is an integer between 1 and 5.)

5. The aforementioned R 1 and R 2 The polymethine compound according to claim 1, wherein the monovalent organic group in is a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, a monovalent halogen-substituted alkyl group having 1 to 12 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 14 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms, or a heterocyclic group having 3 to 14 carbon atoms, which may be further substituted with a monovalent hydrocarbon group or a monovalent electron-withdrawing group.

6. The aforementioned R 1 and R 2 The polymethine compound according to claim 5, wherein each of them is independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 3 carbon atoms, or a monovalent group represented by the formula (I-1-1).

7. The aforementioned R a , R b , R c , R d and R e The polymethine compound according to claim 1, wherein the monovalent hydrocarbon group in is a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 14 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms, which may be further substituted with one or more groups selected from the group consisting of a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 14 carbon atoms, or a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms.

8. The aforementioned R a , R b , R c , R d and R e The monovalent electron-withdrawing group in this is a halogen atom, a carboxyl group, a nitro group, a cyano group, a group represented by -COR, and -CONR 2 The group represented by -SO 2 The group represented by R or -SO 3 The polymethine compound according to claim 1, wherein the group is represented by R, and R is synonymous with the monovalent hydrocarbon group or a hydrogen atom.

9. The aforementioned R a , R b , R c , R d and R e Each of these independently represents a hydrogen atom or a halogen atom, and R a , R b , R c , R d and R e The polymethine compound according to claim 8, wherein two or more of the atoms are halogen atoms.

10. The aforementioned R f , R g , R h , R i , R j , R k , R l , R m , R n and R o The polymethine compound according to claim 1, wherein the monovalent hydrocarbon group which may have an oxygen atom, a nitrogen atom, or a sulfur atom is a monovalent hydrocarbon group which may have an oxygen atom, a nitrogen atom, or a sulfur atom, and may be further substituted with one or more groups selected from the group consisting of a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 14 carbon atoms, and a monovalent aromatic hydrocarbon group having 6 to 14 carbon atoms.

11. R f , R g , R h , R i , R j , R k , R l , R m , R n and R o The polymethine compound according to claim 10, wherein each independently represents a hydrogen atom or a monovalent aliphatic hydrocarbon group having 1 to 12 carbon atoms.

12. A photoelectric conversion element comprising an infrared photoelectric conversion section including a pair of electrodes and an organic infrared photoelectric conversion film provided between the pair of electrodes, The organic infrared photoelectric conversion film comprises a polymethine compound according to any one of claims 1 to 11, and is used as a photoelectric conversion element.

13. The photoelectric element according to claim 12, wherein the organic infrared photoelectric conversion film contains an organic n-type semiconductor and / or an organic p-type semiconductor.

14. The photoelectric conversion element according to claim 12, wherein the infrared photoelectric conversion unit contains one or more selected from the group consisting of a hole transport layer, an electron transport layer, a hole blocking layer, and an electron blocking layer between the electrode and the organic infrared photoelectric conversion film.

15. The photoelectric conversion element according to claim 12, wherein the wavelength of maximum absorption and the wavelength of maximum absorption of the optical absorption spectrum in the infrared region of the infrared photoelectric conversion unit is 700 nm or more and 2500 nm or less.

16. The photoelectric conversion element according to claim 12, wherein the photoelectric conversion element further comprises a visible photoelectric conversion unit that is sensitive to visible light.

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