Polycyclic fused ring conjugated macromolecules, methods of making and using the same

Abstract

The present application relates to the field of solar cells and light detectors, and particularly relates to a multi-fused ring conjugated macromolecule, a preparation method and application thereof. The conjugated macromolecule is a compound shown in the following formula (1). The multi-fused ring conjugated macromolecule provided by the present application has strong light absorption, high charge transport performance and suitable electronic energy level, and is suitable for being applied to the preparation of solar cells or light detectors as photovoltaic materials or light detection materials.

Description

Technical Field

[0001] This invention relates to the fields of solar cells and photodetectors, specifically to multi-fused cyclic conjugated macromolecules, their preparation methods, and applications. Background Technology

[0002] In recent years, organic solar cells have developed rapidly. Due to their advantages such as light weight, high flexibility, simple processing, large-area fabrication, and low cost, they have attracted widespread attention from academia and industry. Perovskite solar cells, in particular, have received significant attention from both academia and industry in recent years due to their rapid efficiency improvements. Organic photodetectors, as a novel type of photodetector, are also an important direction in organic electronics research. Currently, the photoelectric conversion efficiency of organic solar cells based on polymer donor-fullerene acceptor blends has exceeded 11%. This demonstrates the enormous application potential of organic solar cells. Polymer materials, due to their high molar extinction coefficient and broad solar spectrum absorption, result in high photoelectric conversion efficiency for photovoltaic devices. However, polymers also have drawbacks, such as uncertain molecular structures, polydisperse molecular weight distributions, difficulty in batch reproducibility, and difficulty in purification. Unlike polymers, organic fused-ring small molecule and macromolecule semiconductor materials, due to their definite molecular structures and molecular weights, as well as their advantages of batch stability, simple purification, and high purity, have made research on organic fused-ring small molecule and macromolecule solar cells increasingly popular.

[0003] Fullerene derivatives possess advantages such as sufficiently high electron affinity, isotropic electron transport properties, and well-matched electronic energy levels, making them suitable for various applications. 61 BM and PC 71 PCBMs have become star molecules in acceptor materials, consistently holding a dominant position. However, PCBMs also have many drawbacks, such as weak visible light absorption, difficulty in energy level tuning, and complex and cumbersome purification processes. Novel organic polycyclic fused-ring macromolecules possess strong visible light absorption characteristics, making them particularly suitable as photovoltaic materials for organic solar cells and photodetectors. Due to their easily tunable energy levels, they can also serve as modification layers, electron transport layers, or dopants in perovskite solar cells. Therefore, the synthesis of novel acceptor materials remains highly necessary. Summary of the Invention

[0004] The purpose of this invention is to provide a novel multi-fused-ring conjugated macromolecule with strong light absorption, high charge transport performance and suitable electronic energy levels that can be used as an electron donor or electron acceptor material in solar cells and photodetectors, as well as its preparation method and application.

[0005] To achieve the above objectives, the present invention provides a multi-fused-ring conjugated macromolecule, wherein the conjugated macromolecule is a compound represented by formula (1):

[0006]

[0007] In this system, groups B, C, and D form a conjugated system; each group B independently represents 1-10 thiophene conjugated fused ring structures or 1-10 furan conjugated fused ring structures; each group C independently represents 0-10 thiophene conjugated fused ring structures or 0-10 furan conjugated fused ring structures; group D represents a substituted or unsubstituted naphthalene ring structure; and when both groups B are 1 thiophene structure, C is not always 0.

[0008] The two groups A are each independently selected from the following structures:

[0009]

[0010] Each R1 is selected independently from the formula. The groups shown; each R2 is independently selected from the formula The indicated groups;

[0011] Each Z is independently selected from C, N, Si, and Ge;

[0012] Each X, each X', and each Y is independently selected from O, S, or Se;

[0013] m is an integer between 0 and 6; n is an integer between 0 and 6; p is an integer between 0 and 6; q is an integer between 0 and 6;

[0014] Each of R3-R9 is independently selected from H, halogen, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, and C6-C30 aryl.

[0015] A second aspect of the present invention provides a method for preparing the above-mentioned multi-fused-ring conjugated macromolecule, the method comprising:

[0016] In the presence of a basic compound and in an organic solvent, the compound shown in formula (2) is subjected to a dehydration condensation reaction with the compound shown in formula (a) to obtain the compound shown in formula (1); wherein,

[0017]

[0018] Formula (a) is selected from one or more of the following compounds:

[0019]

[0020] A third aspect of the present invention provides a photovoltaic material or photodetector material containing one or more of the above-mentioned multi-fused cyclic conjugated macromolecules.

[0021] A fourth aspect of the present invention provides a solar cell in which the photovoltaic material contains the aforementioned polycyclic fused ring conjugated macromolecules.

[0022] The fifth aspect of the present invention provides a method for preparing the above-mentioned solar cell, the method comprising: configuring the multi-fused-ring conjugated macromolecule in a light-harvesting layer and / or an electron transport layer and / or a modification layer.

[0023] A sixth aspect of the present invention provides a photodetector comprising a light-trapping active layer, wherein the electron donor material and / or electron acceptor material in the light-trapping active layer contains one or more of the aforementioned multi-fused-ring conjugated macromolecules.

[0024] A seventh aspect of the present invention provides a method for fabricating a photodetector, wherein the method includes using one or more electron donor materials and / or electron acceptor materials containing the above-mentioned multi-fused-ring conjugated macromolecules to form an active layer for light trapping.

[0025] The multi-fused-ring conjugated macromolecules provided by this invention have strong light absorption, high charge transport performance and suitable electronic energy levels, making them suitable as photovoltaic materials or photodetector materials for use in the preparation of solar cells or photodetectors. Attached Figure Description

[0026] Figure 1 The UV-Vis absorption spectrum of the multi-fused-ring conjugated macromolecule of formula (1-8-a-3) obtained in Example 1 of the present invention is shown, wherein the solution refers to a solution prepared with chloroform as solvent (10 -6 (mol / L), the thin film refers to a thin film (100 nanometers thick) spin-coated with chloroform solution.

[0027] Figure 2 The cyclic voltammetry curves are for the multi-fused-ring conjugated macromolecules of formula (1-8-a-3) obtained in Example 1 of the present invention.

[0028] Figure 3 The current-voltage (IV) curve of the solar cell obtained in Example 8 is shown.

[0029] Figure 4 The image shows the IV curve of the solar cell obtained in Example 9.

[0030] Figure 5 The image shows the IV curve of the solar cell obtained in Example 10.

[0031] Figure 6 The image shows the IV curve of the solar cell obtained in Example 11.

[0032] Figure 7 The image shows the IV curve of the solar cell obtained in Example 12.

[0033] Figure 8 The image shows the IV curve of the solar cell obtained in Example 13.

[0034] Figure 9 The image shows the IV curve of the solar cell obtained in Example 14.

[0035] Figure 10 The image shows the IV curve of the perovskite solar cell obtained in Example 15. Detailed Implementation

[0036] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0037] In this invention, each group is independently selected and represented. When each group appears simultaneously and in multiple places in the compound, they are chosen independently and can be the same or different. For example, although... The shown group has 4 R8s, but these 4 R8s can be selected independently; they can be the same or different.

[0038] In this invention, In structures with dashed connecting keys, the dashed lines indicate the connection points and represent connecting keys; In structures with solid-lined connecting bonds, the solid lines outside the brackets that do not connect any groups or atoms also indicate the connection sites, representing connecting bonds.

[0039] In this invention, there is the following: The term "group" refers to the situation where the F-F interlaced bond is replaced on both sides. For example, the following formula (1-8-a-F1) actually refers to a mixture of compounds represented by formula (1-8-a-5) where both A groups are A-2, formula (1-8-a-9) where both A groups are A-3, and formula (1-8-a-25) where one A group is A-2 and the other is A-3.

[0040] The first aspect of this invention provides a multi-fused-ring conjugated macromolecule, characterized in that the conjugated macromolecule is a compound represented by formula (1):

[0041]

[0042] Each group in formula (1) is defined as defined in the content of the invention.

[0043] According to the present invention, in order to obtain conjugated molecules with stronger light absorption, higher charge transport performance, and more suitable electronic energy levels, preferably, each group B independently represents 1-5 thiophene conjugated fused ring structures or 1-5 furan conjugated fused ring structures; each group C independently represents 0-5 thiophene conjugated fused ring structures or 0-5 furan conjugated fused ring structures; each Z is independently selected from C, N, and Si; each X, each X', and each Y is independently selected from O or S; m is an integer from 0 to 4; n is an integer from 0 to 4; p is an integer from 0 to 4; q is an integer from 0 to 4; each R3-R9 is independently selected from H, halogens, C1-C20 alkyl groups, C1-C20 alkoxy groups, C1-C20 alkylthio groups, and C6-C24 aryl groups.

[0044] More preferably, each group B independently represents 1-4 thiophene conjugated fused ring structures; each group C independently represents 0-4 thiophene conjugated fused ring structures or 0-4 furan conjugated fused ring structures; each R3-R5 and each R7-R8 is independently selected from H, halogen, C1-C10 alkyl, C1-C10 alkoxy, C1-C10 alkylthio and C6-C12 aryl; each R6 and each R9 is independently selected from H, halogen, C4-C15 alkyl, C4-C15 alkoxy, C4-C15 alkylthio and C6-C12 aryl.

[0045] More preferably, each Z is selected from C; each R3-R5 and each R7-R8 are independently selected from H, F, Cl, Br, I, methyl, ethyl, n-propyl, n-butyl, methoxy, ethoxy, n-propoxy, n-butoxy, methylthio, ethylthio, n-propylthio, and n-butylthio; each R6 and each R9 are independently selected from H, n-butyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-butoxy, n-pentoxy, n-hexoxy, n-octyloxy, 2-ethylhexoxy, n-butylthio, n-pentylthio, n-hexylthio, n-octylthio, and 2-ethylhexylthio.

[0046] In a preferred embodiment of the present invention, each group B independently represents 1-3 thiophene conjugated fused ring structures; each group C independently represents 1-3 thiophene conjugated fused ring structures or 1-3 furan conjugated fused ring structures.

[0047] Where n is 0, it can be assumed that R2 does not exist. Then, group A is directly connected to the fused ring unit of the compound shown in formula (1) to form a conjugated structure.

[0048] Specific examples of C1-C30 alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, 2-ethylhexyl, etc. Alkyl groups from other ranges of the present invention may also be selected from these specific examples as appropriate.

[0049] Specific examples of C1-C30 alkoxy groups include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentoxy, n-hexoxy, n-heptoxy, n-octoxy, n-nonoxy, n-decoxy, 2-ethylhexoxy, etc. Alkoxy groups from other ranges of the present invention may also be selected from these specific examples as appropriate.

[0050] Specific examples of C1-C30 alkylthio groups include: methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, tert-butylthio, n-pentylthio, n-hexylthio, n-heptylthio, n-octylthio, n-nonylthio, n-decylthio, 2-ethylhexylthio, etc. Alkylthio groups within other ranges of the present invention may also be selected from these specific examples as appropriate.

[0051] Specific examples of aryl groups with C6-C30 groups include phenyl, benzyl, and p-tolyl. Other aryl groups within the scope of this invention may also be selected from these specific examples as appropriate.

[0052] In this context, the two groups B located on either side of the structure of compound (1) should be understood as forming a conjugated structure together with the middle and end structures of compound (1). Each group independently represents 1-10 thiophene conjugated fused ring structures or 1-10 furan conjugated fused ring structures. When group B is a thiophene conjugated fused ring structure or a furan conjugated fused ring structure, there is actually one thiophene or furan group on each side that forms the basic structure of the conjugated macromolecule with the middle and end structures. For example, when group B is a thiophene conjugated fused ring structure with more than two thiophene groups, it can be understood as a normal thiophene structure. With antithiophene structure Alternating conjugate connections, as shown in the structural formula. The two carbon atoms connected by the dashed line share space between the two rings to form the structure shown in the formula. For a thiophene conjugated fused ring structure, if it consists of three thiophene rings, then a structure 2 can be connected to the left of structure 1, or a structure 1 can be connected to the right of structure 2, forming an alternating thiophene conjugated fused ring structure like 1-2-1. The same understanding applies to multiple furan conjugated fused ring structures. The same principle applies to the understanding of the C group.

[0053] For group D, which is a substituted or unsubstituted naphthalene ring structure, such a naphthalene ring structure forms a fused ring structure with group C shown in formula (1). Such a fused ring structure can be, for example, as shown in the following formula: Group R 10 -R 11 As defined below.

[0054] Preferably, the conjugated macromolecule is one of the compounds shown in the following formula:

[0055]

[0056] Among them, each R 10 and each R 11 Each of the components is independently selected from H, halogen, C1-C30 alkyl, C1-C30 alkoxy, and C1-C30 alkylthio, preferably from H, halogen, C1-C20 alkyl, C1-C20 alkoxy, and C1-C20 alkylthio, more preferably from H, halogen, C4-C15 alkyl, C4-C15 alkoxy, and C4-C15 alkylthio, and even more preferably from H, n-butyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-butoxy, n-pentoxy, n-hexoxy, n-octyloxy, 2-ethylhexoxy, n-butthio, n-pentylthio, n-hexylthio, n-octylthio, and 2-ethylhexylthio.

[0057] Specific examples of the multi-fused-ring conjugated macromolecules of the present invention are selected from compounds represented by the following formulas:

[0058] Definition: Group A-1 is Group A-2 is Group A-3 is Group A-4 is Group A-5 is Group A-6 is

[0059] The multi-fused-ring conjugated macromolecule is one of the compounds shown in the following formula:

[0060] Formula (1-8-a-1): In formula (1-8-a), Z is always C, A is always group A-1, R2 does not exist, R 10 and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-8-a-2): In formula (1-8-a), Z is always C, A is always group A-1, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-8-a-3): In formula (1-8-a), Z is C, A is the group A-1, R2 does not exist, R 10All are hexyl and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-8-a-4): In formula (1-8-a), Z is always C, A is always group A-1, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-8-a-5): In formula (1-8-a), Z is C, A is the group A-2, R2 does not exist, R 10 and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-8-a-6): In formula (1-8-a), Z is always C, A is always the group A-2, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-8-a-7): In formula (1-8-a), Z is C, A is the group A-2, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-8-a-8): In formula (1-8-a), Z is always C, A is always group A-2, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-8-a-9): In formula (1-8-a), Z is C, A is the group A-3, R2 does not exist, R 10 and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-8-a-10): In formula (1-8-a), Z is always C, A is always the group A-3, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-8-a-11): In formula (1-8-a), Z is C, A is the group A-3, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-8-a-12): In formula (1-8-a), Z is always C, A is always the group A-3, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-8-a-13): In formula (1-8-a), Z is C, A is the group A-4, R2 does not exist, R 10 and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-8-a-14): In formula (1-8-a), Z is always C, A is always the group A-4, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-8-a-15): In formula (1-8-a), Z is C, A is the group A-4, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-8-a-16): In formula (1-8-a), Z is always C, A is always the group A-4, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-8-a-17): In formula (1-8-a), Z is C, A is the group A-5, R2 does not exist, R 10 and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-8-a-18): In formula (1-8-a), Z is always C, A is always the group A-5, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-8-a-19): In formula (1-8-a), Z is C, A is the group A-5, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-8-a-20): In formula (1-8-a), Z is always C, A is always the group A-5, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-8-a-21): In formula (1-8-a), Z is C, A is the group A-6, R2 does not exist, R 10 and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-8-a-22): In formula (1-8-a), Z is always C, A is always the group A-6, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-8-a-23): In formula (1-8-a), Z is C, A is the group A-6, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-8-a-24): In formula (1-8-a), Z is always C, A is always the group A-6, R2 does not exist, R10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-8-a-25): In formula (1-8-a), Z is C, one A is group A-2, the other A is group A-3, R2 does not exist, R 10 and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-8-a-26): In formula (1-8-a), Z is always C, one A is always group A-2, the other A is always group A-3, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-8-a-27): In formula (1-8-a), Z is C, one A is group A-2, the other A is group A-3, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-8-a-28): In formula (1-8-a), Z is always C, one A is always group A-2, the other A is always group A-3, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl;

[0061] Formula (1-10-a-1): In formula (1-10-a), Z is always C, A is always the group A-1, R2 does not exist, R 10 and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-10-a-2): In formula (1-10-a), Z is always C, A is always group A-1, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-10-a-3): In formula (1-10-a), Z is C, A is the group A-1, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-10-a-4): In formula (1-10-a), Z is always C, A is always group A-1, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-10-a-5): In formula (1-10-a), Z is C, A is the group A-2, R2 does not exist, R 10 and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-10-a-6): In formula (1-10-a), Z is always C, A is always the group A-2, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-10-a-7): In formula (1-10-a), Z is C, A is the group A-2, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-10-a-8): In formula (1-10-a), Z is always C, A is always the group A-2, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-10-a-9): In formula (1-10-a), Z is C, A is the group A-3, R2 does not exist, R 10 and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-10-a-10): In formula (1-10-a), Z is always C, A is always the group A-3, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-10-a-11): In formula (1-10-a), Z is C, A is the group A-3, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-10-a-12): In formula (1-10-a), Z is always C, A is always the group A-3, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-10-a-13): In formula (1-10-a), Z is C, A is A-4, R2 does not exist, R 10 and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-10-a-14): In formula (1-10-a), Z is always C, A is always the group A-4, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-10-a-15): In formula (1-10-a), Z is C, A is A-4, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-10-a-16): In formula (1-10-a), Z is always C, A is always the group A-4, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-10-a-17): In formula (1-10-a), Z is C, A is the group A-5, R2 does not exist, R 10 and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-10-a-18): In formula (1-10-a), Z is always C, A is always the group A-5, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-10-a-19): In formula (1-10-a), Z is C, A is the group A-5, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-10-a-20): In formula (1-10-a), Z is always C, A is always the group A-5, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-10-a-21): In formula (1-10-a), Z is C, A is the A-6 group, R2 does not exist, R 10 and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-10-a-22): In formula (1-10-a), Z is always C, A is always the group A-6, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-10-a-23): In formula (1-10-a), Z is C, A is the A-6 group, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-10-a-24): In formula (1-10-a), Z is always C, A is always the group A-6, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-10-a-25): In formula (1-10-a), Z is C, one A is group A-2, the other A is group A-3, R2 does not exist, R 10 and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-10-a-26): In formula (1-10-a), Z is always C, one A is always group A-2, the other A is always group A-3, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-10-a-27): In formula (1-10-a), Z is C, one A is group A-2, the other A is group A-3, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-10-a-28): In formula (1-10-a), Z is always C, one A is always group A-2, the other A is always group A-3, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl;

[0062] Formula (1-10-b-1): In formula (1-10-b), Z is always C, A is always the group A-1, R2 does not exist, R 10 and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-10-b-2): In formula (1-10-b), Z is always C, A is always group A-1, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-10-b-3): In formula (1-10-b), Z is C, A is the group A-1, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-10-b-4): In formula (1-10-b), Z is always C, A is always group A-1, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-10-b-5): In formula (1-10-b), Z is C, A is the group A-2, R2 does not exist, R 10 and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-10-b-6): In formula (1-10-b), Z is always C, A is always the group A-2, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-10-b-7): In formula (1-10-b), Z is C, A is the group A-2, R2 does not exist, R 10 All are hexyl and R 11All are H, R1 are all And R9 is n-hexyl; Formula (1-10-b-8): In formula (1-10-b), Z is always C, A is always the group A-2, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-10-b-9): In formula (1-10-b), Z is C, A is the group A-3, R2 does not exist, R 10 and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-10-b-10): In formula (1-10-b), Z is always C, A is always the group A-3, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-10-b-11): In formula (1-10-b), Z is C, A is the group A-3, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-10-b-12): In formula (1-10-b), Z is always C, A is always the group A-3, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-10-b-13): In formula (1-10-b), Z is C, A is the group A-4, R2 does not exist, R 10 and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-10-b-14): In formula (1-10-b), Z is always C, A is always the group A-4, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-10-b-15): In formula (1-10-b), Z is C, A is the A-4 group, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-10-b-16): In formula (1-10-b), Z is always C, A is always the group A-4, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-10-b-17): In formula (1-10-b), Z is C, A is A-5, R2 does not exist, R 10 and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-10-b-18): In formula (1-10-b), Z is always C, A is always the group A-5, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-10-b-19): In formula (1-10-b), Z is C, A is the group A-5, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-10-b-20): In formula (1-10-b), Z is always C, A is always the group A-5, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-10-b-21): In formula (1-10-b), Z is C, A is the group A-6, R2 does not exist, R 10 and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-10-b-22): In formula (1-10-b), Z is always C, A is always the group A-6, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-10-b-23): In formula (1-10-b), Z is C, A is the group A-6, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-10-b-24): In formula (1-10-b), Z is always C, A is always the group A-6, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-10-b-25): In formula (1-10-b), Z is C, one A is group A-2, the other A is group A-3, R2 does not exist, R 10 and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-10-b-26): In formula (1-10-b), Z is always C, one A is always group A-2, the other A is always group A-3, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-10-b-27): In formula (1-10-b), Z is C, one A is group A-2, the other A is group A-3, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-10-b-28): In formula (1-10-b), Z is always C, one A is always group A-2, the other A is always group A-3, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl;

[0063] Formula (1-12-b-1): In formula (1-12-b), Z is always C, A is always group A-1, R2 does not exist, R 10 and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-12-b-2): In formula (1-12-b), Z is always C, A is always group A-1, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-12-b-3): In formula (1-12-b), Z is C, A is the group A-1, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-12-b-4): In formula (1-12-b), Z is always C, A is always group A-1, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-12-b-5): In formula (1-12-b), Z is C, A is the group A-2, R2 does not exist, R 10 and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-12-b-6): In formula (1-12-b), Z is always C, A is always group A-2, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-12-b-7): In formula (1-12-b), Z is C, A is the group A-2, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-12-b-8): In formula (1-12-b), Z is always C, A is always the group A-2, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-12-b-9): In formula (1-12-b), Z is C, A is the group A-3, R2 does not exist, R 10 and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-12-b-10): In formula (1-12-b), Z is always C, A is always the group A-3, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-12-b-11): In formula (1-12-b), Z is C, A is the group A-3, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-12-b-12): In formula (1-12-b), Z is always C, A is always the group A-3, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-12-b-13): In formula (1-12-b), Z is C, A is the A-4 group, R2 does not exist, R 10 and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-12-b-14): In formula (1-12-b), Z is always C, A is always the group A-4, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-12-b-15): In formula (1-12-b), Z is C, A is A-4, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-12-b-16): In formula (1-12-b), Z is always C, A is always the group A-4, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-12-b-17): In formula (1-12-b), Z is C, A is A-5, R2 does not exist, R 10 and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-12-b-18): In formula (1-12-b), Z is always C, A is always the group A-5, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-12-b-19): In formula (1-12-b), Z is C, A is the group A-5, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-12-b-20): In formula (1-12-b), Z is always C, A is always the group A-5, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-12-b-21): In formula (1-12-b), Z is C, A is the group A-6, R2 does not exist, R 10 and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-12-b-22): In formula (1-12-b), Z is always C, A is always the group A-6, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-12-b-23): In formula (1-12-b), Z is C, A is the group A-6, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-12-b-24): In formula (1-12-b), Z is always C, A is always the group A-6, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-12-b-25): In formula (1-12-b), Z is C, one A is group A-2, the other A is group A-3, R2 does not exist, R 10 and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-12-b-26): In formula (1-12-b), Z is always C, one A is always group A-2, the other A is always group A-3, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-12-b-27): In formula (1-12-b), Z is C, one A is group A-2, the other A is group A-3, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is n-hexyl; Formula (1-12-b-28): In formula (1-12-b), Z is always C, one A is always group A-2, the other A is always group A-3, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl.

[0064] A second aspect of the present invention provides a method for preparing the above-mentioned multi-fused-ring conjugated macromolecule, the method comprising:

[0065] In the presence of a basic compound and in an organic solvent, the compound shown in formula (2) is subjected to a dehydration condensation reaction with the compound shown in formula (a) to obtain the compound shown in formula (1); wherein,

[0066]

[0067] Formula (a) is selected from one or more of the following compounds:

[0068]

[0069] In this method, the various groups of the compounds involved are as described above, and will not be repeated here.

[0070] The compound represented by formula (2) can be selected based on the structure of the polycyclic fused ring conjugated macromolecules mentioned above. Preferably, the compound represented by formula (2) is one or more of the following formulas:

[0071]

[0072] Specific examples of the compounds shown in formula (2) can be one or more of the following formulas:

[0073] Equation (2-8-a-1): In equation (2-8-a), Z is always C, R2 does not exist, R10 is always n-hexyl and R11 is always H, and R1 is always... And R9 is a normal hexyl group; Equation (2-8-a-2): In equation (2-8-a), Z is always C, R2 does not exist, R10 is always a normal hexyl group and R11 is always H, R1 is always a normal hexyl group; Equation (2-8-a-3): In equation (2-8-a), Z is always C, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is a positive hexyl group; Equation (2-8-a-4): In Equation (2-8-a), Z is always C, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl;

[0074] Equation (2-10-a-1): In equation (2-10-a), Z is always C, R2 does not exist, R10 is always n-hexyl and R11 is always H, and R1 is always... And R9 is a normal hexyl group; Equation (2-10-a-2): In Equation (2-10-a), Z is always C, R2 does not exist, R10 is always a normal hexyl group and R11 is always H, R1 is always a normal hexyl group; Equation (2-10-a-3): In Equation (2-10-a), Z is always C, R2 does not exist, R 10 All are hexyl and R 11All are H, R1 are all And R9 is a positive hexyl group; Equation (2-10-a-4): In Equation (2-10-a), Z is always C, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl;

[0075] Equation (2-10-b-1): In equation (2-10-b), Z is always C, R2 does not exist, R10 is always n-hexyl and R11 is always H, and R1 is always... And R9 is a normal hexyl group; Equation (2-10-b-2): In Equation (2-10-b), Z is always C, R2 does not exist, R10 is always a normal hexyl group and R11 is always H, R1 is always a normal hexyl group; Equation (2-10-b-3): In Equation (2-10-b), Z is always C, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is a positive hexyl group; Equation (2-10-b-4): In Equation (2-10-b), Z is always C, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl.

[0076] Equation (2-12-b-1): In equation (2-12-b), Z is always C, R2 does not exist, R10 is always n-hexyl and R11 is always H, and R1 is always... And R9 is n-hexyl; Equation (2-12-b-2): In Equation (2-12-b), Z is always C, R2 does not exist, R10 is always n-hexyl and R11 is always H, R1 is always n-hexyl; Equation (2-12-b-3): In Equation (2-12-b), Z is always C, R2 does not exist, R 10 All are hexyl and R 11 All are H, R1 are all And R9 is a positive hexyl group; Equation (2-12-b-4): In Equation (2-12-b), Z is always C, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl.

[0077] According to the present invention, the compound represented by formula (2) can be a commercially available product or can be prepared by conventional methods in the art, such as by reacting butyllithium with an aldehyde group (e.g., prepared by methods described in the literature such as Adv. Mater., 2015, 27, 1170–1174; J. Am. Chem. Soc., 2016, 138, 4955-4961).

[0078] According to the present invention, the compound represented by formula (a) can be appropriately selected based on group A. For example, specific examples of the compound represented by formula (a) may include:

[0079]

[0080] According to the present invention, the compound represented by formula (a) can be a commercially available product or can be prepared by conventional methods in the art, which will not be described in detail here.

[0081] According to the present invention, the aldehyde groups attached to both ends of the compound represented by formula (2) can undergo dehydration condensation with the compound represented by formula (a) to form the compound represented by formula (1). There is no particular limitation on the amount of the compound represented by formula (2) and the compound represented by formula (a), as long as the compound represented by formula (1) can be obtained. Preferably, the molar ratio of the compound represented by formula (2) to the compound represented by formula (a) is 1:2-100, more preferably 1:4-10.

[0082] According to the present invention, the reaction is carried out in the presence of a basic compound, thereby providing an alkaline environment for the reaction system. The basic compound may be one or more of piperidine, pyridine, and triethylamine, for example. There is no particular limitation on the amount of the basic compound used, as long as it provides an alkaline environment and facilitates the dehydration condensation reaction. For example, the amount of the basic compound used is 0.1-1000 mmol, more preferably 1-50 mmol, relative to 1 mmol of the compound represented by formula (2).

[0083] According to the present invention, the organic solvent is, for example, chloroform and / or dichloromethane. The amount of the organic solvent used relative to 1 mmol of the compound represented by formula (2) can be, for example, 20-500 mL (preferably 40-400 mL).

[0084] According to the present invention, in a preferred embodiment, the conditions for the dehydration condensation reaction include: a temperature of 20-100°C (e.g., 50-100°C) and a time of 10 min-48 h (e.g., 10-20 h). More preferably, the conditions for the dehydration condensation reaction include: a temperature of 60-80°C and a time of 10-15 h.

[0085] To ensure the smooth progress of the reaction, the method also includes maintaining the reaction system under an inert atmosphere before the reaction. For example, after all the raw materials have been added, an inert gas can be introduced into the reaction system for 20-40 minutes to remove air. The inert gas can be, for example, argon, helium, nitrogen, etc.

[0086] According to the present invention, in order to extract the compound represented by formula (1) from the reaction solution, the method further includes a post-processing step, for example, mixing the dehydration condensation reaction product with methanol (the amount of methanol may be, for example, 200-1000 mL relative to the total volume of 100 mL of the reaction solution), and then performing solid-liquid separation, and performing chromatographic separation of the obtained solid phase using a silica gel column (a 200-300 mesh silica gel may be used, and the eluent may be a mixture of petroleum ether and dichloromethane in a volume ratio of 1:0.2-3).

[0087] A third aspect of the present invention provides a photovoltaic material or photodetector material containing one or more of the above-mentioned multi-fused cyclic conjugated macromolecules.

[0088] According to the present invention, there is no particular limitation on the photovoltaic material, as long as it contains the above-mentioned multi-fused cyclic conjugated macromolecules of the present invention. The photovoltaic material preferably refers to the electron donor material and / or electron acceptor material in the light-harvesting active layer of the solar cell; or the photovoltaic material in the electron transport layer and / or modification layer (for example, for perovskite solar cells).

[0089] For example, the electron donor polymer material PBnDT-FTAZ can be combined with the conjugated molecules provided by the present invention in a weight ratio of 0.5-4:1 to serve as the photovoltaic material, particularly as the light-harvesting active layer material of a solar cell, wherein the multi-fused-ring conjugated macromolecules provided by the present invention are preferably used as electron acceptor materials.

[0090] The structural unit of the polymer material PBnDT-FTAZ is shown below:

[0091] Among them, -C6H 13 -C4H9 represents n-hexyl, and -C4H9 represents n-butyl. The preparation of this polymer material PBnDT-FTAZ can be carried out, for example, by the method described in the literature (J.Am.Chem.Soc.2011,133,4625), and will not be repeated here.

[0092] According to the present invention, there is no particular limitation on the photodetector material, as long as it contains the above-mentioned multi-fused cyclic conjugated macromolecules of the present invention.

[0093] A fourth aspect of the present invention provides a solar cell in which the photovoltaic material contains the aforementioned polycyclic fused ring conjugated macromolecules.

[0094] According to the present invention, there are no particular limitations on the structure of the solar cell, as long as the photovoltaic material used contains the multi-fused cyclic conjugated macromolecules of the present invention, thus effectively improving the photoelectric conversion efficiency of the solar cell. For example, the solar cell can be an organic solar cell, a perovskite solar cell, etc.

[0095] Wherein, when the battery is an organic solar cell including a light-harvesting active layer, the electron donor material and / or electron acceptor material in the light-harvesting active layer contains one or more of the polycyclic fused ring conjugated macromolecules.

[0096] When the cell is a perovskite solar cell comprising an electron transport layer, a perovskite light-harvesting layer, and a modification layer, the light-harvesting layer and / or the electron transport layer and / or the modification layer contains one or more of the multi-fused-ring conjugated macromolecules.

[0097] In particular, the conjugated molecules of the present invention are preferably combined as electron acceptor materials with other electron donor materials to form the light-harvesting active layer of a solar cell. Such electron donor materials can be, for example, the polymer material PBnDT-FTAZ, as defined above.

[0098] The polymer material PBnDT-FTAZ can be combined with the conjugated macromolecules provided in this invention at a weight ratio of 0.5-4:1 to form a light-harvesting active layer.

[0099] The fifth aspect of the present invention provides a method for preparing the above-mentioned solar cell, the method comprising: configuring the multi-fused-ring conjugated macromolecule in a layer containing photovoltaic material.

[0100] According to the present invention, there are no particular limitations on the preparation process of solar cells, and conventional methods in the art can be used.

[0101] In organic solar cells, the photovoltaic material-containing layer can be an active layer that traps light.

[0102] For perovskite solar cells, the photovoltaic material-containing layer can be a light-harvesting layer and / or an electron transport layer and / or a modification layer.

[0103] According to the present invention, the fabrication process of the organic solar cell may include, for example, the following steps: For a reverse structure device: a ZnO layer (thickness, for example, 20-50 nm) is coated on a conductive glass (e.g., indium tin oxide glass, ITO) serving as the cathode as a cathode modification layer. After drying, a mixture of polymer material PBnDT-FTAZ and the conjugated macromolecules provided by the present invention is coated on the ZnO layer as an active layer. After drying, molybdenum oxide (thickness, for example, 5-10 nm) and Ag (thickness, for example, 50-100 nm) are vacuum-deposited as the anode. For a forward structure device: Unlike the reverse structure device, a polymer layer formed, for example, of a polymer combination of poly(3,4-ethylenedioxythiophene-polystyrene sulfonate) is used instead of the ZnO layer. Poly(3,4-ethylenedioxythiophene-polystyrene sulfonate) is also represented as PEDOT:PSS; metallic calcium is used instead of molybdenum oxide; and Al is used instead of Ag.

[0104] According to the present invention, the fabrication process of perovskite solar cells may include, for example, cleaning the indium tin oxide (ITO) glass used as the cathode with a detergent, then ultrasonically cleaning it sequentially with deionized water, acetone, and isopropanol, drying it, spin-coating an electron transport layer (e.g., SnO2) about 30 nm thick, annealing it for 30 minutes, and then setting it aside. The aforementioned multi-fused-ring conjugated macromolecules were dissolved in DMF (e.g., concentration 0.25 mg / mL), and an appropriate amount of PbI2 was added. The homogeneous solution was then spin-coated onto the electron transport layer and annealed at 70°C for 20 minutes. After cooling, a methylammonium iodide (FAI) / methylamine iodide (MAI) 2:1 mixture was spin-coated onto the layer and annealed at 150°C for 15 minutes to obtain the conjugated macromolecule-doped perovskite layer provided by this invention. Finally, an 80 mg / mL solution of 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (spiro-OMeTAD) was spin-coated as a hole transport layer. A vacuum (absolute pressure 2 × 10⁻⁶) was applied to the active layer. -5 A metallic Ag with a vapor deposition thickness of approximately 150 nm is used as the anode of a solar cell.

[0105] The conjugated molecule provided by this invention has strong absorption peaks in the visible and near-infrared regions, for example, strong absorption peaks in the wavelength range of 600-800 nm; the conjugated molecule has good thermal stability and can withstand temperatures of around 340℃ without decomposition; cyclic voltammetry test results show that its HOMO and LUMO energy levels can match the energy levels of most common electron donor materials, and it has good electron or hole acceptance capabilities, which is very advantageous as a photovoltaic material for solar cells, especially as an electron acceptor and / or electron donor material, particularly as an electron acceptor material.

[0106] A sixth aspect of the present invention provides a photodetector comprising a light-trapping active layer, wherein the electron donor material and / or electron acceptor material in the light-trapping active layer contains one or more of the aforementioned multi-fused-ring conjugated macromolecules.

[0107] The present invention does not impose any particular limitation on the construction of the photodetector. Conventional constructions in the field can be adopted, as long as they include the multi-fused-ring conjugated macromolecules described above in the present invention, thus achieving excellent photodetection performance.

[0108] A seventh aspect of the present invention provides a method for fabricating a photodetector, wherein the method includes using one or more electron donor materials and / or electron acceptor materials containing the above-mentioned multi-fused-ring conjugated macromolecules to form an active layer for light trapping.

[0109] The present invention does not impose any particular limitation on the fabrication process of the photodetector. The fabrication process of photodetectors in the art can be used, as long as it includes the above-mentioned multi-fused cyclic conjugated macromolecules of the present invention, thus obtaining excellent photodetector performance.

[0110] The present invention will be described in detail below through embodiments.

[0111] In the following examples: the molecular structure formula contains -C6H 13 All are n-hexyl, -C4H9 are all n-butyl, and -C2H5 are all ethyl. 1 H NMR was measured using a Bruker AVANCE 400 / 300 nuclear magnetic resonance spectrometer. MS (MALDI) was measured using a Bruker Daltonics Biflex III MALDI-TOF Analyzer. UV-Vis absorption and visible light transmission spectra were measured using a Jasco V-570 spectrophotometer. Cyclic voltammetry was measured using a CHI660C electrochemical workstation. IV curves were measured using a B2912A Precision Source / Measure Unit (Agilent Technologies), from which parameters such as short-circuit current, open-circuit voltage, fill factor, and photoelectric conversion efficiency were obtained. The preparation of the polymer material PBnDT-FTAZ can be performed, for example, by referring to the methods described in the literature (e.g., J. Am. Chem. Soc. 2011, 133, 4625). The compounds represented by formulas (a-2-2, a-2-3, a-2-4) were prepared according to the method in "J.Am.Chem.Soc.2017,139,1336–1343".

[0112] Preparation Example 1

[0113] This preparation example illustrates the method for preparing the compound shown in formula (2-8-a-3).

[0114]

[0115] As shown in the reaction formula above, the compound represented by formula IB1 (124 mg, 0.1 mmol; purchased from Suzhou Nakai Technology Co., Ltd.) and tetrahydrofuran (20 mL) were added to the reaction vessel, purged with argon gas, and stirred at -78 °C for 1 h. Then, n-butyllithium (0.19 mL, 0.3 mmol, 1.6 M) was slowly added dropwise, and the mixture was stirred at -78 °C for 2 h. Next, N,N-dimethylformamide (36.6 mg, 0.5 mmol) was added, and the reaction product was slowly brought back to room temperature (approximately 25 °C) and stirred overnight (approximately 12 h). Then, water (0.2 mL) was added to quench the precipitate, and the mixture was extracted with saturated saline and dichloromethane. The precipitate was dried with magnesium sulfate and then evaporated to dryness. The precipitate was separated by silica gel chromatography (using 200-300 mesh silica gel, with petroleum ether / dichloromethane as the eluent at a volume ratio of 2:1) to obtain a bright yellow solid (98 mg, yield 75.6%), which is the compound shown in formula (2-8-a-3). 1 H NMR (400MHz, CDCl3): δ9.72(s,2H),7.93(d,J=8.7Hz,2H),7.60(m,2H),7.19(d,J=8.1Hz,8H), 7.08(d,J=8.1Hz,8H),2.58(m,12H),1.59(m,12H),1.31(m,36H),0.89(m,18H).MS(MALDI):m / z 1294.2(M+).

[0116] Preparation Example 2

[0117] This preparation example illustrates the method for preparing the compound shown in formula (2-10-a-3).

[0118]

[0119] As shown in the reaction formula above, the compound represented by formula IB2 (135 mg, 0.1 mmol; purchased from Suzhou Nakai Technology Co., Ltd.) and tetrahydrofuran (20 mL) were added to the reaction vessel, purged with argon gas, and stirred at -78 °C for 1 h. Then, n-butyllithium (0.19 mL, 0.3 mmol, 1.6 M) was slowly added dropwise, and the mixture was stirred at -78 °C for 2 h. Next, N,N-dimethylformamide (36.6 mg, 0.5 mmol) was added, and the reaction product was slowly brought back to room temperature (approximately 25 °C) and stirred overnight (approximately 12 h). Then, water (0.2 mL) was added to quench the precipitate, and the mixture was extracted with saturated saline and dichloromethane. The precipitate was dried with magnesium sulfate and then evaporated to dryness. The precipitate was separated by silica gel chromatography (using 200-300 mesh silica gel, with petroleum ether / dichloromethane as the eluent at a volume ratio of 2:1) to obtain a bright yellow solid (105 mg, yield 75.2%), which is the compound represented by formula (2-10-a-3). 1 H NMR (400MHz, CDCl3): δ9.73 (s, 2H), 7.96 (d, J = 8.7Hz, 2H), 7.62 (m, 2H), 7.16 (d, J = 8.1Hz, 8H), 7.09(d,J=8.1Hz,8H),2.56(m,12H),1.55(m,12H),1.32(m,36H),0.88(m,18H).MS(MALDI):m / z 1405.3(M+).

[0120] Preparation Example 3

[0121] This preparation example illustrates the method for preparing the compound shown in formula (2-10-b-3).

[0122]

[0123] As shown in the reaction formula above, the compound represented by formula IB3 (135 mg, 0.1 mmol; purchased from Suzhou Nakai Technology Co., Ltd.) and tetrahydrofuran (20 mL) were added to the reaction vessel, purged with argon gas, and stirred at -78 °C for 1 h. Then, n-butyllithium (0.19 mL, 0.3 mmol, 1.6 M) was slowly added dropwise, and the mixture was stirred at -78 °C for 2 h. Next, N,N-dimethylformamide (36.6 mg, 0.5 mmol) was added, and the reaction product was slowly brought back to room temperature (approximately 25 °C) and stirred overnight (approximately 12 h). Then, water (0.2 mL) was added to quench the precipitate, and the mixture was extracted with saturated saline and dichloromethane. The precipitate was dried with magnesium sulfate and then evaporated to dryness. The precipitate was separated by silica gel chromatography (using 200-300 mesh silica gel, with petroleum ether / dichloromethane as the eluent at a volume ratio of 2:1) to obtain a bright yellow solid (107 mg, yield 76.3%), which is the compound represented by formula (2-10-b-3). 1H NMR (400MHz, CDCl3): δ9.74(s,2H),7.95(d,J=8.7Hz,2H),7.62(m,2H),7.17(d,J=8.1Hz,8H), 7.07(d,J=8.1Hz,8H),2.55(m,12H),1.56(m,12H),1.32(m,36H),0.88(m,18H).MS(MALDI):m / z 1404.1(M+).

[0124] Preparation Example 4

[0125] This preparation example illustrates the method for preparing the compound shown in formula (2-12-b-3).

[0126]

[0127] As shown in the reaction formula above, the compound represented by formula IB4 (146 mg, 0.1 mmol; purchased from Suzhou Nakai Technology Co., Ltd.) and tetrahydrofuran (20 mL) were added to the reaction vessel, purged with argon gas, and stirred at -78 °C for 1 h. Then, n-butyllithium (0.56 mL, 0.9 mmol, 1.6 M) was slowly added dropwise, and the mixture was stirred at -78 °C for 2 h. Next, N,N-dimethylformamide (36.6 mg, 0.5 mmol) was added, and the reaction product was slowly brought back to room temperature (approximately 25 °C) and stirred overnight (approximately 12 h). Then, water (0.2 mL) was added to quench the precipitate, and the mixture was extracted with saturated saline and dichloromethane. The precipitate was dried with magnesium sulfate and then evaporated to dryness. The precipitate was separated by silica gel chromatography (using 200-300 mesh silica gel and petroleum ether / dichloromethane in a volume ratio of 2:1) to obtain a bright yellow solid (114 mg, yield 74.9%), which is the compound represented by formula (2-12-b-3). 1 H NMR (400MHz, CDCl3): δ9.77(s,2H),7.95(d,J=8.7Hz,2H),7.61(m,2H),7.14(d,J=8.1Hz,8H), 7.07(d,J=8.1Hz,8H),2.54(m,12H),1.57(m,12H),1.31(m,36H),0.86(m,18H).MS(MALDI):m / z 1518.3(M+).

[0128] Preparation Example 5

[0129] This preparation example illustrates the method for preparing the compound shown in formula (a-4-1).

[0130]

[0131] As shown in the above reaction formula, compound T1 (200 mg, 1.3 mmol; synthesized according to the method in Dyes and Pigments 2016, 134, 129), malononitrile (171 mg, 2.6 mmol), and ethanol (20 mL) were added to a reaction vessel, purged with argon gas, and stirred at 25 °C for 30 minutes. Sodium acetate (132 mg, 1.6 mmol) was slowly added, and the mixture was stirred at 25 °C for 2 hours. Water (30 mL) was then added, and the mixture was stirred for 1.5 hours. The pH was then adjusted to 2 with concentrated hydrochloric acid, filtered through filter paper, and washed with water (400 mL). The precipitate was separated by silica gel chromatography (using 200-300 mesh silica gel, with chloroform as the eluent) to obtain an orange solid (85 mg, yield 32%), which is the compound shown in formula (a-4-1). 1 H NMR (400MHz, CDCl3): δ8.64 (d, J = 2.4Hz, 1H), 8.07 (d, J = 2.4Hz, 1H), 4.00 (s, 2H). MS (EI): m / z 200 (M + ).

[0132] Preparation Example 6

[0133] This preparation example illustrates the method for preparing the compounds shown in formulas (a-2-2) and (a-2-3).

[0134]

[0135] As shown in the reaction formula above, 5-fluoro-1,3-indanedione (820 mg, 5 mmol; purchased from Ark), malononitrile (660 mg, 10 mmol), and ethanol (30 mL) were added to a reaction vessel, purged with argon gas, and stirred at 25 °C for 30 minutes. Sodium acetate (492 mg, 6 mmol) was slowly added, and the mixture was stirred at 25 °C for 2 hours. Water (40 mL) was then added, and the mixture was stirred for 1.5 hours. The pH was adjusted to 2 with concentrated hydrochloric acid, filtered through filter paper, and washed with water (300 mL). The precipitate was separated by silica gel chromatography (using 200-300 mesh silica gel, with methanol / chloroform as eluent at a volume ratio of 1:5), yielding a grayish-white solid (610 mg, yield 57.5%), which is a mixture of the compound shown in formula (a-2-2) (71 mol%) and the compound shown in formula (a-2-3) (29 mol%). The mixture... 1H NMR (400MHz, CDCl3): δ8.68 (dd, J=8.8Hz, 0.28H), 7.61 (dd, J=8.2Hz, 0.72H), 8.01 (m, 0.76H), 7.61 (m, 0.36H), 7.55 (m, 1H), 3.76 (d, 2H). MS (EI): m / z 212(M + ).

[0136] Preparation Example 7

[0137] This preparation example illustrates the method for preparing the compound shown in formula (a-2-4).

[0138]

[0139] As shown in the reaction formula above, 5,6-difluoro-1,3-indanedione (201 mg, 1.1 mmol; synthesized according to the method in Planells, M.; Robertson, N. Eur. J. Org. Chem. 2012, 4947), malononitrile (145 mg, 2.2 mmol), and ethanol (20 mL) were added to a reaction vessel, and argon gas was introduced. The mixture was stirred at 25 °C for 30 minutes. Sodium acetate (107 mg, 1.3 mmol) was slowly added, and the mixture was stirred at 25 °C for 2 hours. Water (30 mL) was then added, and the mixture was stirred for 1.5 hours. Then, concentrated hydrochloric acid was added to adjust the pH to 2, and the mixture was filtered through filter paper and washed with water (400 mL). The precipitate was separated by chromatography using a silica gel column (200-300 mesh silica gel, with methanol / chloroform as the eluent in a volume ratio of 1:1) to obtain a brown solid (115 mg, yield 44.6%), which is the compound shown in formula (a-2-4). 1 H NMR (400MHz, CDCl3): δ8.46 (dd, J=6.4Hz, 1H), 7.76 (t, J=7.6Hz, 1H), 3.76 (s, 2H). MS (EI): m / z 230 (M + )

[0140] Example 1

[0141] This embodiment is used to illustrate the conjugated macromolecule and its preparation method of the present invention.

[0142]

[0143] As shown in the reaction formula above, the compound (129 mg, 0.1 mmol) of formula (2-8-a-3) obtained in Preparation Example 1, the compound (92 mg, 0.4 mmol) of formula (a-2-1), pyridine (0.8 mL, 0.96 mmol), and chloroform (30 mL) were added to the reaction vessel, purged with argon gas for 25 min, and then refluxed at 65 °C for 12 h. After cooling to room temperature (approximately 25 °C), the reaction product was poured into 200 mL of methanol and filtered. The resulting precipitate was separated by silica gel chromatography (using 200-300 mesh silica gel, with petroleum ether / dichloromethane at a volume ratio of 1:2) to obtain a blue solid (147 mg, yield 89.1%), which is the polycyclic fused-ring conjugated macromolecule of formula (1-8-a-3). 1 H NMR (400MHz, CDCl3): δ8.95(s,2H),8.75(m,2H),7.98(m,2H),7.76(m,8H),7.23(d,J=8.4Hz,8H) ,7.14(d,J=8.1Hz,8H),2.57(m,12H),1.59(m,12H),1.26(m,36H),0.87(m,18H).MS(MALDI):m / z 1645.3(M+).

[0144] The UV-Vis absorption spectrum of the multi-fused-ring conjugated macromolecule shown in equation (1-8-a-3) is as follows: Figure 1 As shown, it exhibits a strong absorption peak in the wavelength range of 600-800 nm, with a maximum molar extinction coefficient of 2.7 × 10⁻⁶. 5 M –1 ·cm –1 The film absorbs most strongly at around 710 nm; the maximum absorption peak of the film is redshifted by 30 nm compared to that in the solution.

[0145] The cyclic voltammetry curve obtained by cyclic voltammetry is as follows: Figure 2 As shown, the HOMO energy level is -5.49 eV, the LUMO energy level is -3.73 eV, and the band gap is 1.59 eV, indicating that the multi-fused-ring conjugated macromolecule shown in formula (1-8-a-3) has good electron acceptance ability and can match the energy levels of most common electron donor materials.

[0146] Example 2

[0147] This embodiment is used to illustrate the conjugated macromolecule and its preparation method of the present invention.

[0148]

[0149] As shown in the reaction formula above, the compound (129 mg, 0.1 mmol) of formula (2-8-a-3) obtained in Preparation Example 1, the compound (80 mg, 0.4 mmol) of formula (a-4-1) obtained in Preparation Example 5, pyridine (0.8 mL, 0.96 mmol), and chloroform (30 mL) were added to a reaction vessel, purged with argon gas for 25 min, and then refluxed at 65 °C for 15 h. After cooling to room temperature (approximately 25 °C), the reaction product was poured into 200 mL of methanol and filtered. The resulting precipitate was separated by chromatography using a silica gel column (200-300 mesh silica gel, eluent of petroleum ether / dichloromethane at a volume ratio of 1:2) to obtain a blue solid (145 mg, yield 87.6%), which is the polycyclic fused-ring conjugated macromolecule of formula (1-8-a-19). 1 H NMR (400MHz, CDCl3): δ8.95(s,2H),8.79(m,2H),7.96(m,2H),7.75(m,4H),7.24(d,J=8.4Hz,8H ),7.17(d,J=8.4Hz,8H),2.56(m,8H),1.56(m,12H),1.23(m,20H),0.86(m,12H).MS(MALDI):m / z 1657.2(M+).

[0150] The UV-Vis absorption spectrum of the multi-fused-ring conjugated macromolecule shown in equation (1-8-a-19) indicates that it has a strong absorption peak in the wavelength range of 600-800 nm, and the maximum molar extinction coefficient is 2.9 × 10⁻⁶. 5 M –1 ·cm –1 The film absorbs most strongly at around 720 nm; the maximum absorption peak of the film is redshifted by 32 nm compared to that in the solution.

[0151] Cyclic voltammetry measurements revealed that its HOMO level was -5.47 eV, its LUMO level was -3.76 eV, and its band gap was 1.57 eV, indicating that the multi-fused-ring conjugated macromolecule shown in formula (1-8-a-19) has good electron acceptance capability and can match the energy levels of most commonly used electron donor materials.

[0152] Example 3

[0153] This embodiment is used to illustrate the conjugated macromolecule and its preparation method of the present invention.

[0154]

[0155] As shown in the above reaction formula, the compound (129 mg, 0.1 mmol) of formula (2-8-a-3) obtained in Preparation Example 1, the mixture of the compounds (a-2-2) and (a-2-3) obtained in Preparation Example 6 (85 mg, 0.4 mmol), pyridine (0.8 mL, 0.96 mmol) and chloroform (30 mL) were added to the reaction vessel, purged with argon gas for 25 min, and then refluxed at 65 °C for 15 h. After cooling to room temperature (approximately 25°C), the reaction product was poured into 200 mL of methanol and filtered. The resulting precipitate was separated by chromatography using a silica gel column (200-300 mesh silica gel, with petroleum ether / dichloromethane at a volume ratio of 1:2) to obtain a blue solid (156 mg, yield 91.2%), which is the polycyclic fused-ring conjugated macromolecule of formula (1-8-a-F1), a mixture of compounds of formulas (1-8-a-7), (1-8-a-11), and (1-8-a-27). 1 H NMR (400MHz, CDCl3): δ8.86 (s, 2H), 8.71 (dd, J = 4.0Hz, 0.5H), 8.36 (dd, J = 1.6Hz, 1.5H), 7.92 (dd, J = 5.2Hz, 1.5H), 7.59 (dd, J = 2.8Hz,0.5H),7.48(m,4H),7.42(m,2H),7.11(m,16H),2.58(m,12H),1.54(m,12H),1.31(m,36H),0.94(m,18H).MS(MALDI):m / z 1714.2(M+).

[0156] The UV-Vis absorption spectrum of the mixture of the three polycyclic fused-ring conjugated macromolecules shown in formula (1-8-a-F1) indicates that it has a strong absorption peak in the wavelength range of 600-800 nm, and the maximum molar extinction coefficient is 3.2 × 10⁻⁶. 5 M –1 ·cm –1 The film absorbs most strongly at around 733 nm; the maximum absorption peak of the film is redshifted by 25 nm compared to that in the solution.

[0157] Cyclic voltammetry measurements showed that the HOMO level was -5.48 eV, the LUMO level was -3.81 eV, and the band gap was 1.54 eV, indicating that the mixture of the three polycyclic fused ring conjugated macromolecules shown in formula (1-8-a-F1) has good electron acceptance ability and can match the energy levels of most common electron donor materials.

[0158] Example 4

[0159] This embodiment is used to illustrate the conjugated macromolecule and its preparation method of the present invention.

[0160]

[0161] As shown in the reaction formula above, the compound (259 mg, 0.2 mmol) of formula (2-8-a-3) obtained in Preparation Example 1, the compound (166 mg, 0.72 mmol) of formula (a-2-4) obtained in Preparation Example 7, pyridine (0.8 mL, 0.96 mmol), and chloroform (30 mL) were added to the reaction vessel, purged with argon gas for 25 min, and then refluxed at 65 °C for 15 h. After cooling to room temperature (approximately 25 °C), the reaction product was poured into 200 mL of methanol and filtered. The resulting precipitate was separated by silica gel chromatography (using 200-300 mesh silica gel, with petroleum ether / dichloromethane at a volume ratio of 1:2) to obtain a blue solid (298 mg, yield 87%), which is the polycyclic fused-ring conjugated macromolecule of formula (1-8-a-15). 1 H NMR (300MHz, CDCl3): δ8.79(s,2H),8.51(m,2H),7.73(s,2H),7.65(m,4H),7.31(d,J=7.5Hz,8H),7.10 (d,J=7.2Hz,8H),2.58(m,12H),1.56(m,12H),1.25(m,36H),0.87(m,18H).MS(MALDI):m / z1718.5(M+).

[0162] The UV-Vis absorption spectrum of the multi-ring conjugated macromolecule shown in equation (1-8-a-15) indicates that it has a strong absorption peak in the wavelength range of 600-800 nm, and the maximum molar extinction coefficient is 2.8 × 10⁻⁶. 5 M –1 ·cm –1 The film absorbs most strongly at around 743 nm; the maximum absorption peak of the film is redshifted by 26 nm compared to that in the solution.

[0163] Cyclic voltammetry measurements revealed that its HOMO level was -5.50 eV, its LUMO level was -3.86 eV, and its band gap was 1.51 eV, indicating that the multi-fused-ring conjugated macromolecule shown in formula (1-8-a-15) has good electron acceptance capability and can match the energy levels of most commonly used electron donor materials.

[0164] Example 5

[0165] This embodiment is used to illustrate the conjugated macromolecule and its preparation method of the present invention.

[0166]

[0167] As shown in the reaction formula above, the compound (280 mg, 0.2 mmol) of formula (2-10-a-3) obtained in Preparation Example 2, the compound (166 mg, 0.72 mmol) of formula (a-2-4) obtained in Preparation Example 7, pyridine (0.8 mL, 0.96 mmol), and chloroform (30 mL) were added to the reaction vessel, purged with argon gas for 25 min, and then refluxed at 65 °C for 15 h. After cooling to room temperature (approximately 25 °C), the reaction product was poured into 200 mL of methanol and filtered. The resulting precipitate was separated by chromatography using a silica gel column (200-300 mesh silica gel, eluent of petroleum ether / dichloromethane at a volume ratio of 1:2) to obtain a blue solid (311 mg, yield 85%), which is the polycyclic fused-ring conjugated macromolecule of formula (1-10-a-15). 1 H NMR (300MHz, CDCl3): δ8.79(s,2H),8.53(m,2H),7.73(s,2H),7.65(m,4H),7.31(d,J=7.5Hz,8H),7.13 (d,J=7.2Hz,8H),2.57(m,12H),1.54(m,12H),1.24(m,36H),0.88(m,18H).MS(MALDI):m / z1829.5(M+).

[0168] The UV-Vis absorption spectrum of the multi-fused-ring conjugated macromolecule shown in equation (1-10-a-15) indicates that it has a strong absorption peak in the wavelength range of 600-900 nm, and the maximum molar extinction coefficient is 3.1 × 10⁻⁶. 5 M –1 ·cm –1 The film absorbs most strongly at around 765 nm; the maximum absorption peak of the film is redshifted by 27 nm compared to that in the solution.

[0169] Cyclic voltammetry measurements revealed that its HOMO level was -5.48 eV, its LUMO level was -3.82 eV, and its band gap was 1.48 eV, indicating that the multi-fused-ring conjugated macromolecule shown in formula (1-10-a-15) has good electron acceptance capability and can match the energy levels of most common electron donor materials.

[0170] Example 6

[0171] This embodiment is used to illustrate the conjugated macromolecule and its preparation method of the present invention.

[0172]

[0173] As shown in the reaction formula above, the compound (280 mg, 0.2 mmol) of formula (2-10-b-3) obtained in Preparation Example 3, the compound (166 mg, 0.72 mmol) of formula (a-2-4) obtained in Preparation Example 7, pyridine (0.8 mL, 0.96 mmol), and chloroform (30 mL) were added to the reaction vessel, purged with argon gas for 25 min, and then refluxed at 65 °C for 15 h. After cooling to room temperature (approximately 25 °C), the reaction product was poured into 200 mL of methanol and filtered. The resulting precipitate was separated by chromatography using a silica gel column (200-300 mesh silica gel, eluent of petroleum ether / dichloromethane at a volume ratio of 1:2) to obtain a blue solid (318 mg, yield 87%), which is the polycyclic fused-ring conjugated macromolecule of formula (1-10-b-15). 1 H NMR (300MHz, CDCl3): δ8.83(s,2H),8.53(m,2H),7.76(s,2H),7.67(m,4H),7.31(d,J=7.5Hz,8H),7.12 (d,J=7.2Hz,8H),2.57(m,12H),1.54(m,12H),1.28(m,36H),0.87(m,18H).MS(MALDI):m / z1830.1(M+).

[0174] The UV-Vis absorption spectrum of the multi-ring conjugated macromolecule shown in equation (1-10-b-15) indicates that it has a strong absorption peak in the wavelength range of 600-900 nm, and the maximum molar extinction coefficient is 3.0 × 10⁻⁶. 5 M –1 ·cm –1 The film absorbs most strongly at around 766 nm; the maximum absorption peak of the film is redshifted by 28 nm compared to that in the solution.

[0175] Cyclic voltammetry measurements revealed that its HOMO level was -5.49 eV, its LUMO level was -3.82 eV, and its band gap was 1.47 eV, indicating that the multi-fused-ring conjugated macromolecule shown in formula (1-10-b-15) has good electron acceptance capability and can match the energy levels of most commonly used electron donor materials.

[0176] Example 7

[0177] This embodiment is used to illustrate the conjugated macromolecule and its preparation method of the present invention.

[0178]

[0179] As shown in the reaction formula above, the compound (303 mg, 0.2 mmol) of formula (2-12-b-3) obtained in Preparation Example 4, the compound (166 mg, 0.72 mmol) of formula (a-2-4) obtained in Preparation Example 7, pyridine (0.8 mL, 0.96 mmol), and chloroform (30 mL) were added to the reaction vessel, purged with argon gas for 25 min, and then refluxed at 65 °C for 15 h. After cooling to room temperature (approximately 25 °C), the reaction product was poured into 200 mL of methanol and filtered. The resulting precipitate was separated by chromatography using a silica gel column (200-300 mesh silica gel, eluent of petroleum ether / dichloromethane at a volume ratio of 1:2) to obtain a blue solid (342 mg, yield 88%), which is the polycyclic fused-ring conjugated macromolecule of formula (1-12-b-15). 1 H NMR (300MHz, CDCl3): δ8.77(s,2H),8.55(m,2H),7.72(s,2H),7.67(m,2H),7.32(d,J=7.5Hz,8H),7.13 (d,J=7.2Hz,8H),2.57(m,12H),1.55(m,12H),1.23(m,36H),0.88(m,18H).MS(MALDI):m / z1941.5(M+).

[0180] The UV-Vis absorption spectrum of the multi-ring conjugated macromolecule shown in equation (1-12-b-15) indicates that it has a strong absorption peak in the wavelength range of 600-900 nm, and the maximum molar extinction coefficient is 3.3 × 10⁻⁶. 5 M –1 ·cm –1 The film absorbs most strongly at around 788 nm; the maximum absorption peak of the film is redshifted by 30 nm compared to that in the solution.

[0181] Cyclic voltammetry measurements revealed a HOMO energy level of -5.45 eV, a LUMO energy level of -3.78 eV, and a band gap of 1.45 eV, indicating that the multi-fused-ring conjugated macromolecule shown in formula (1-12-b-15) has good electron acceptance capabilities and can match the energy levels of most commonly used electron donor materials.

[0182] Example 8

[0183] This embodiment is used to illustrate the solar cell of the present invention.

[0184] The indium tin oxide (ITO) glass used as the cathode (purchased from Shenzhen Nanbo Float Glass Co., Ltd.) was first cleaned with detergent, then ultrasonically cleaned with deionized water, acetone, and isopropanol in sequence. After drying, a 30nm thick ZnO cathode modification layer was spin-coated and dried at 200℃ for 30 minutes for later use.

[0185] 1.5 mg of the multi-fused-ring conjugated macromolecule shown in formula (1-8-a-3) was mixed with 1 mg of polymer donor material PBnDT-FTAZ in 0.1 mL of chloroform to obtain a mixture, which was then spin-coated onto the ZnO layer. After drying, a light-harvesting active layer (effective area of ​​4 mm²) was obtained. 2 Vacuum (absolute pressure 2 × 10⁻⁶) is applied to the active layer. -5 MoO3 (purchased from Bailingwei Technology Co., Ltd.) with a vapor deposition thickness of about 5 nm and metallic Ag with a thickness of about 80 nm were used as the anode of the solar cell.

[0186] A simulated solar light source was used with an AM1.5 filter (SAN-EI ELECTRIC Co., Ltd. model XES-70S1), at 100mW / cm². 2 The photovoltaic performance of the device was tested under varying light intensity, calibrated using a standard monocrystalline silicon solar cell (purchased from VLSI Standards Inc.). The resulting IV curves were measured using a B2912A Precision Source / Measure Unit (Agilent Technologies), controlled by a computer via LabVIEW software.

[0187] The resulting IV curve is as follows Figure 3 As shown. (Through) Figure 3 The open-circuit voltage V of the solar cell can be obtained from the IV curve shown. OC The voltage is 0.97V, and the short-circuit current J is... SC 14.45 mA·cm -2 The fill factor (FF) is 72%, and the photoelectric conversion efficiency (PCE) is 10.09%.

[0188] Example 9

[0189] This embodiment is used to illustrate the solar cell of the present invention.

[0190] The method described in Example 8 differs in that a mixture of 1.5 mg of the polycyclic fused ring conjugated macromolecules of formula (1-8-a-19) is used instead of the polycyclic fused ring conjugated macromolecules of formula (1-8-a-3) to finally prepare and test a solar cell.

[0191] The resulting IV curve is as follows Figure 4 As shown. (Through) Figure 4 The open-circuit voltage V of the solar cell can be obtained from the IV curve shown. OC The voltage is 0.96V, and the short-circuit current J is... SC 15.34 mA·cm -2The fill factor (FF) is 66%, and the photoelectric conversion efficiency (PCE) is 9.71%.

[0192] Example 10

[0193] This embodiment is used to illustrate the solar cell of the present invention.

[0194] The method described in Example 8 differs in that 1.5 mg of the polycyclic fused ring conjugated macromolecule of formula (1-8-a-F1) is used instead of the polycyclic fused ring conjugated macromolecule of formula (1-8-a-3) to finally prepare a solar cell and test it.

[0195] The resulting IV curve is as follows Figure 5 As shown. (Through) Figure 5 The open-circuit voltage V of the solar cell can be obtained from the IV curve shown. OC The voltage is 0.96V, and the short-circuit current J is... SC 16.46 mA·cm -2 The fill factor (FF) is 72%, and the photoelectric conversion efficiency (PCE) is 11.37%.

[0196] Example 11

[0197] This embodiment is used to illustrate the solar cell of the present invention.

[0198] The method described in Example 8 differs in that 1.5 mg of the polycyclic fused ring conjugated macromolecule of formula (1-8-a-15) is used instead of the polycyclic fused ring conjugated macromolecule of formula (1-8-a-3) to finally prepare and test a solar cell.

[0199] The resulting IV curve is as follows Figure 6 As shown. (Through) Figure 6 The open-circuit voltage V of the solar cell can be obtained from the IV curve shown. OC The voltage is 0.90V, and the short-circuit current is J. SC 19.65 mA·cm -2 The fill factor (FF) is 70%, and the photoelectric conversion efficiency (PCE) is 12.37%.

[0200] Example 12

[0201] This embodiment is used to illustrate the solar cell of the present invention.

[0202] The method described in Example 8 differs in that a mixture of three polycyclic fused ring conjugated macromolecules of formula (1-10-a-15) is used instead of the polycyclic fused ring conjugated macromolecule of formula (1-8-a-3) to finally prepare and test a solar cell.

[0203] The resulting IV curve is as follows Figure 7 As shown. (Through) Figure 7 The open-circuit voltage V of the solar cell can be obtained from the IV curve shown. OC The voltage is 0.94V, and the short-circuit current J is... SC 20.26 mA·cm -2 The fill factor (FF) is 68%, and the photoelectric conversion efficiency (PCE) is 12.95%.

[0204] Example 13

[0205] This embodiment is used to illustrate the solar cell of the present invention.

[0206] The method described in Example 8 differs in that 1.5 mg of the polycyclic fused ring conjugated macromolecule of formula (1-10-b-15) is used instead of the polycyclic fused ring conjugated macromolecule of formula (1-8-a-3) to finally prepare and test a solar cell.

[0207] The resulting IV curve is as follows Figure 8 As shown. (Through) Figure 8 The open-circuit voltage V of the solar cell can be obtained from the IV curve shown. OC The voltage is 0.93V, and the short-circuit current J is... SC 20.64 mA·cm -2 The fill factor (FF) is 67%, and the photoelectric conversion efficiency (PCE) is 12.86%.

[0208] Example 14

[0209] This embodiment is used to illustrate the solar cell of the present invention.

[0210] The method described in Example 8 differs in that 1.5 mg of the polycyclic fused ring conjugated macromolecule of formula (1-12-b-15) is used instead of the polycyclic fused ring conjugated macromolecule of formula (1-8-a-3) to finally prepare and test a solar cell.

[0211] The resulting IV curve is as follows Figure 9 As shown. (Through) Figure 9 The open-circuit voltage V of the solar cell can be obtained from the IV curve shown. OC The voltage is 0.99V, and the short-circuit current J is... SC 21.37 mA·cm -2 The fill factor (FF) is 62%, and the photoelectric conversion efficiency (PCE) is 13.08%.

[0212] Example 15

[0213] This embodiment is used to illustrate the perovskite solar cell of the present invention.

[0214] The indium tin oxide (ITO) glass (purchased from Shenzhen Nanbo Float Glass Co., Ltd.) used as the cathode was first cleaned with detergent, and then ultrasonically cleaned with deionized water, acetone and isopropanol in sequence. After drying, a 30nm thick SnO2 electron transport layer was spin-coated and annealed at 150℃ for 30 minutes for later use.

[0215] 0.25 mg of the polycyclic fused-ring conjugated macromolecule (1-8-a-3) shown above was dissolved in 1 mL of DMF, and then 500 mg of PbI2 was added. The homogeneous solution was then spin-coated onto the electron transport layer and annealed at 70 °C for 20 minutes. After cooling, a 2:1 mixture of formamidine iodophor (FAI) and methylamine iodophor (MAI) was spin-coated onto the layer and annealed at 150 °C for 15 minutes to obtain the perovskite layer doped with the polycyclic fused-ring conjugated macromolecule (1-8-a-3). Finally, an 80 mg / mL solution of 2,2',7,7'-tetratetra[N,N-di(4-methoxyphenyl)amino]-9,9'-spirodifluorene (spiro-OMeTAD) was spin-coated as the hole transport layer. A vacuum (absolute pressure 2 × 10⁻⁶) was applied to the active layer. -5 A metallic Ag with a vapor deposition thickness of approximately 150 nm is used as the anode of a solar cell.

[0216] A simulated solar light source was used with an AM1.5 filter (SAN-EI ELECTRIC Co., Ltd. model XES-70S1), at 100mW / cm². 2 The photovoltaic performance of the device was tested under varying light intensity, calibrated using a standard monocrystalline silicon solar cell (purchased from VLSI Standards Inc.). The resulting IV curves were measured using a B2912A Precision Source / Measure Unit (Agilent Technologies), controlled by a computer via LabVIEW software.

[0217] The resulting IV curve is as follows Figure 10 Shown. Through Figure 10 The open-circuit voltage V of the solar cell can be obtained from the IV curve shown. OC The voltage is 1.004V, and the short-circuit current is J. SC 23.58 mA·cm -2 The fill factor (FF) is 80.7%, and the photoelectric conversion efficiency (PCE) is 19.11%.

[0218] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A multi-fused-ring conjugated macromolecule, characterized in that, The conjugated macromolecule is a compound represented by formula (1): Equation (1) , In this system, groups B, C, and D form a conjugated system; each group B independently represents 1-3 thiophene conjugated fused ring structures; each group C independently represents 1-3 thiophene conjugated fused ring structures; group D represents a substituted or unsubstituted naphthalene ring structure; and when both groups B are 1 thiophene structure, C is not always 0. For group D, its naphthalene ring structure forms a fused ring structure with group C shown in formula (1), and the naphthalene ring structure is shown in the following formula: , The two groups A are each independently selected from the following structures: ； Each R1 is selected independently from the formula. or The groups shown; each R2 is independently selected from the formula or The indicated groups; Each Z is independently selected from C, N, Si, and Ge; Each X, each X', and each Y is independently selected from O, S, or Se; m is an integer between 0 and 6; n is an integer between 0 and 6; p is an integer between 0 and 6; q is an integer between 0 and 6; Each of R3-R9 is independently selected from H, halogen, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio, and C6-C24 aryl; Among them, each R 10 and each R 11 Each is independently selected from H, halogen, C1-C30 alkyl, C1-C30 alkoxy and C1-C30 alkylthio groups.

2. The multi-fused-ring conjugated macromolecule according to claim 1, wherein, Each Z is independently selected from C, N, and Si; each X, each X', and each Y is independently selected from O or S; m is an integer from 0 to 4; n is an integer from 0 to 4; p is an integer from 0 to 4; q is an integer from 0 to 4.

3. The multi-fused-ring conjugated macromolecule according to claim 2, wherein, Each of R3-R5 and each of R7-R8 is independently selected from H, halogen, C1-C10 alkyl, C1-C10 alkoxy, C1-C10 alkylthio, and C6-C12 aryl; each of R6 and each of R9 is independently selected from H, halogen, C4-C15 alkyl, C4-C15 alkoxy, C4-C15 alkylthio, and C6-C12 aryl.

4. The multi-fused-ring conjugated macromolecule according to claim 3, wherein, Each Z is selected from C; each R3-R5 and each R7-R8 is independently selected from H, F, Cl, Br, I, methyl, ethyl, n-propyl, n-butyl, methoxy, ethoxy, n-propoxy, n-butoxy, methylthio, ethylthio, n-propylthio, and n-butylthio; each R6 and each R9 is independently selected from H, n-butyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-butoxy, n-pentoxy, n-hexoxy, n-octyloxy, 2-ethylhexoxy, n-butylthio, n-pentylthio, n-hexylthio, n-octylthio, and 2-ethylhexylthio.

5. The multi-fused-ring conjugated macromolecule according to any one of claims 1-3, wherein, This multi-fused-ring conjugated macromolecule is one of the compounds shown in the following formula: Equation (1-8-a) ; Equation (1-10-a) ; Equation (1-10-b) ; Equation (1-12-b) .

6. The multi-fused-ring conjugated macromolecule according to claim 5, wherein, Each R 10 and each R 11 Each is independently selected from H, halogen, C1-C20 alkyl, C1-C20 alkoxy and C1-C20 alkylthio groups.

7. The multi-fused-ring conjugated macromolecule according to claim 6, wherein, Each R 10 and each R 11 Each is independently selected from H, halogen, C4-C15 alkyl, C4-C15 alkoxy and C4-C15 alkylthio groups.

8. The multi-fused-ring conjugated macromolecule according to claim 7, wherein, Each R 10 and each R 11 Each is independently selected from H, n-butyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-butoxy, n-pentoxy, n-hexoxy, n-octyloxy, 2-ethylhexoxy, n-butylthio, n-pentylthio, n-hexylthio, n-octylthio, and 2-ethylhexylthio.

9. The multi-fused-ring conjugated macromolecule according to claim 5, wherein, Definition: Group A-1 is Group A-2 is Group A-3 is Group A-4 is Group A-5 is Group A-6 is , The multi-fused-ring conjugated macromolecule is one of the compounds shown in the following formula: Formula (1-8-a-1): In formula (1-8-a), Z is always C, A is always group A-1, R2 does not exist, R 10 and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-8-a-2): In formula (1-8-a), Z is always C, A is always group A-1, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-8-a-3): In formula (1-8-a), Z is always C, A is always group A-1, R2 does not exist, R 10 All are hexyl and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-8-a-4): In formula (1-8-a), Z is always C, A is always group A-1, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-8-a-5): In formula (1-8-a), Z is always C, A is always the group A-2, R2 does not exist, R 10 and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-8-a-6): In formula (1-8-a), Z is always C, A is always the group A-2, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-8-a-7): In formula (1-8-a), Z is always C, A is always the group A-2, R2 does not exist, R 10 All are hexyl and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-8-a-8): In formula (1-8-a), Z is always C, A is always the group A-2, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-8-a-9): In formula (1-8-a), Z is always C, A is always the group A-3, R2 does not exist, R 10 and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-8-a-10): In formula (1-8-a), Z is always C, A is always the group A-3, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-8-a-11): In formula (1-8-a), Z is always C, A is always the group A-3, R2 does not exist, R 10 All are hexyl and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-8-a-12): In formula (1-8-a), Z is always C, A is always the group A-3, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-8-a-13): In formula (1-8-a), Z is always C, A is always the group A-4, R2 does not exist, R 10 and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-8-a-14): In formula (1-8-a), Z is always C, A is always the group A-4, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-8-a-15): In formula (1-8-a), Z is always C, A is always the group A-4, R2 does not exist, R 10 All are hexyl and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-8-a-16): In formula (1-8-a), Z is always C, A is always the group A-4, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-8-a-17): In formula (1-8-a), Z is always C, A is always the group A-5, R2 does not exist, R 10 and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-8-a-18): In formula (1-8-a), Z is always C, A is always the group A-5, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-8-a-19): In formula (1-8-a), Z is always C, A is always the group A-5, R2 does not exist, R 10 All are hexyl and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-8-a-20): In formula (1-8-a), Z is always C, A is always the group A-5, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-8-a-21): In formula (1-8-a), Z is always C, A is always the group A-6, R2 does not exist, R 10 and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-8-a-22): In formula (1-8-a), Z is always C, A is always the group A-6, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-8-a-23): In formula (1-8-a), Z is always C, A is always the group A-6, R2 does not exist, R 10 All are hexyl and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-8-a-24): In formula (1-8-a), Z is always C, A is always the group A-6, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-8-a-25): In formula (1-8-a), Z is always C, one A is always group A-2, the other A is always group A-3, R2 does not exist, R 10 and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-8-a-26): In formula (1-8-a), Z is always C, one A is always group A-2, the other A is always group A-3, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-8-a-27): In formula (1-8-a), Z is always C, one A is always group A-2, the other A is always group A-3, R2 does not exist, R 10 All are hexyl and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-8-a-28): In formula (1-8-a), Z is always C, one A is always group A-2, the other A is always group A-3, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-10-a-1): In formula (1-10-a), Z is always C, A is always the group A-1, R2 does not exist, R 10 and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-10-a-2): In formula (1-10-a), Z is always C, A is always group A-1, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-10-a-3): In formula (1-10-a), Z is always C, A is always group A-1, R2 does not exist, R 10 All are hexyl and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-10-a-4): In formula (1-10-a), Z is always C, A is always group A-1, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-10-a-5): In formula (1-10-a), Z is always C, A is always the group A-2, R2 does not exist, R 10 and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-10-a-6): In formula (1-10-a), Z is always C, A is always the group A-2, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-10-a-7): In formula (1-10-a), Z is always C, A is always the group A-2, R2 does not exist, R 10 All are hexyl and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-10-a-8): In formula (1-10-a), Z is always C, A is always the group A-2, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-10-a-9): In formula (1-10-a), Z is always C, A is always the group A-3, R2 does not exist, R 10 and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-10-a-10): In formula (1-10-a), Z is always C, A is always the group A-3, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-10-a-11): In formula (1-10-a), Z is always C, A is always the group A-3, R2 does not exist, R 10 All are hexyl and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-10-a-12): In formula (1-10-a), Z is always C, A is always the group A-3, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-10-a-13): In formula (1-10-a), Z is always C, A is always the group A-4, R2 does not exist, R 10 and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-10-a-14): In formula (1-10-a), Z is always C, A is always the group A-4, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-10-a-15): In formula (1-10-a), Z is always C, A is always the group A-4, R2 does not exist, R 10 All are hexyl and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-10-a-16): In formula (1-10-a), Z is always C, A is always the group A-4, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-10-a-17): In formula (1-10-a), Z is always C, A is always the group A-5, R2 does not exist, R 10 and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-10-a-18): In formula (1-10-a), Z is always C, A is always the group A-5, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-10-a-19): In formula (1-10-a), Z is always C, A is always the group A-5, R2 does not exist, R 10 All are hexyl and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-10-a-20): In formula (1-10-a), Z is always C, A is always the group A-5, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-10-a-21): In formula (1-10-a), Z is always C, A is always the group A-6, R2 does not exist, R 10 and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-10-a-22): In formula (1-10-a), Z is always C, A is always the group A-6, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-10-a-23): In formula (1-10-a), Z is always C, A is always the group A-6, R2 does not exist, R 10 All are hexyl and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-10-a-24): In formula (1-10-a), Z is always C, A is always the group A-6, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-10-a-25): In formula (1-10-a), Z is always C, one A is always group A-2, the other A is always group A-3, R2 does not exist, R 10 and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-10-a-26): In formula (1-10-a), Z is always C, one A is always group A-2, the other A is always group A-3, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-10-a-27): In formula (1-10-a), Z is always C, one A is always group A-2, the other A is always group A-3, R2 does not exist, R 10 All are hexyl and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-10-a-28): In formula (1-10-a), Z is always C, one A is always group A-2, the other A is always group A-3, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-10-b-1): In formula (1-10-b), Z is always C, A is always the group A-1, R2 does not exist, and R 10 and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-10-b-2): In formula (1-10-b), Z is always C, A is always group A-1, R2 does not exist, and R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-10-b-3): In formula (1-10-b), Z is always C, A is always group A-1, R2 does not exist, and R 10 All are hexyl and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-10-b-4): In formula (1-10-b), Z is always C, A is always group A-1, R2 does not exist, and R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-10-b-5): In formula (1-10-b), Z is always C, A is always the group A-2, R2 does not exist, and R 10 and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-10-b-6): In formula (1-10-b), Z is always C, A is always the group A-2, R2 does not exist, and R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-10-b-7): In formula (1-10-b), Z is always C, A is always the group A-2, R2 does not exist, and R 10 All are hexyl and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-10-b-8): In formula (1-10-b), Z is always C, A is always the group A-2, R2 does not exist, and R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-10-b-9): In formula (1-10-b), Z is always C, A is always the group A-3, R2 does not exist, and R 10 and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-10-b-10): In formula (1-10-b), Z is always C, A is always the group A-3, R2 does not exist, and R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-10-b-11): In formula (1-10-b), Z is always C, A is always the group A-3, R2 does not exist, and R 10 All are hexyl and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-10-b-12): In formula (1-10-b), Z is always C, A is always the group A-3, R2 does not exist, and R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-10-b-13): In formula (1-10-b), Z is always C, A is always the group A-4, R2 does not exist, and R 10 and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-10-b-14): In formula (1-10-b), Z is always C, A is always the group A-4, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-10-b-15): In formula (1-10-b), Z is always C, A is always the group A-4, R2 does not exist, and R 10 All are hexyl and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-10-b-16): In formula (1-10-b), Z is always C, A is always the group A-4, R2 does not exist, and R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-10-b-17): In formula (1-10-b), Z is always C, A is always the group A-5, R2 does not exist, and R 10 and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-10-b-18): In formula (1-10-b), Z is always C, A is always the group A-5, R2 does not exist, and R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-10-b-19): In formula (1-10-b), Z is always C, A is always the group A-5, R2 does not exist, and R 10 All are hexyl and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-10-b-20): In formula (1-10-b), Z is always C, A is always the group A-5, R2 does not exist, and R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-10-b-21): In formula (1-10-b), Z is always C, A is always the group A-6, R2 does not exist, and R 10 and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-10-b-22): In formula (1-10-b), Z is always C, A is always the group A-6, R2 does not exist, and R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-10-b-23): In formula (1-10-b), Z is always C, A is always the group A-6, R2 does not exist, and R 10 All are hexyl and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-10-b-24): In formula (1-10-b), Z is always C, A is always the group A-6, R2 does not exist, and R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-10-b-25): In formula (1-10-b), Z is always C, one A is always group A-2, the other A is always group A-3, R2 does not exist, R 10 and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-10-b-26): In formula (1-10-b), Z is always C, one A is always group A-2, the other A is always group A-3, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-10-b-27): In formula (1-10-b), Z is always C, one A is always group A-2, the other A is always group A-3, R2 does not exist, R 10 All are hexyl and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-10-b-28): In formula (1-10-b), Z is always C, one A is always group A-2, the other A is always group A-3, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-12-b-1): In formula (1-12-b), Z is always C, A is always group A-1, R2 does not exist, and R 10 and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-12-b-2): In formula (1-12-b), Z is always C, A is always group A-1, R2 does not exist, and R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-12-b-3): In formula (1-12-b), Z is always C, A is always group A-1, R2 does not exist, and R 10 All are hexyl and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-12-b-4): In formula (1-12-b), Z is always C, A is always group A-1, R2 does not exist, and R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-12-b-5): In formula (1-12-b), Z is always C, A is always the group A-2, R2 does not exist, and R 10 and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-12-b-6): In formula (1-12-b), Z is always C, A is always the group A-2, R2 does not exist, and R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-12-b-7): In formula (1-12-b), Z is always C, A is always the group A-2, R2 does not exist, and R 10 All are hexyl and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-12-b-8): In formula (1-12-b), Z is always C, A is always the group A-2, R2 does not exist, and R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-12-b-9): In formula (1-12-b), Z is always C, A is always the group A-3, R2 does not exist, and R 10 and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-12-b-10): In formula (1-12-b), Z is always C, A is always the group A-3, R2 does not exist, and R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-12-b-11): In formula (1-12-b), Z is always C, A is always the group A-3, R2 does not exist, and R 10 All are hexyl and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-12-b-12): In formula (1-12-b), Z is always C, A is always the group A-3, R2 does not exist, and R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-12-b-13): In formula (1-12-b), Z is always C, A is always the group A-4, R2 does not exist, and R 10 and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-12-b-14): In formula (1-12-b), Z is always C, A is always the group A-4, R2 does not exist, and R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-12-b-15): In formula (1-12-b), Z is always C, A is always the group A-4, R2 does not exist, and R 10 All are hexyl and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-12-b-16): In formula (1-12-b), Z is always C, A is always the group A-4, R2 does not exist, and R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-12-b-17): In formula (1-12-b), Z is always C, A is always the group A-5, R2 does not exist, and R 10 and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-12-b-18): In formula (1-12-b), Z is always C, A is always the group A-5, R2 does not exist, and R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-12-b-19): In formula (1-12-b), Z is always C, A is always the group A-5, R2 does not exist, and R 10 All are hexyl and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-12-b-20): In formula (1-12-b), Z is always C, A is always the group A-5, R2 does not exist, and R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-12-b-21): In formula (1-12-b), Z is always C, A is always the group A-6, R2 does not exist, and R 10 and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-12-b-22): In formula (1-12-b), Z is always C, A is always the group A-6, R2 does not exist, and R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-12-b-23): In formula (1-12-b), Z is always C, A is always the group A-6, R2 does not exist, and R 10 All are hexyl and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-12-b-24): In formula (1-12-b), Z is always C, A is always the group A-6, R2 does not exist, and R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl; Formula (1-12-b-25): In formula (1-12-b), Z is always C, one A is always group A-2, the other A is always group A-3, R2 does not exist, R 10 and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-12-b-26): In formula (1-12-b), Z is always C, one A is always group A-2, the other A is always group A-3, R2 does not exist, R 10 and R 11 All are H, and R1 is n-hexyl; Formula (1-12-b-27): In formula (1-12-b), Z is always C, one A is always group A-2, the other A is always group A-3, R2 does not exist, R 10 All are hexyl and R 11 Both are H, and R1 is also H. Furthermore, R9 is a positive hexyl group; Formula (1-12-b-28): In formula (1-12-b), Z is always C, one A is always group A-2, the other A is always group A-3, R2 does not exist, R 10 All are hexyl and R 11 All are H, and R1 is n-hexyl.

10. A method for preparing the multi-fused-ring conjugated macromolecule according to any one of claims 1-9, the method comprising: In the presence of a basic compound and in an organic solvent, the compound shown in formula (2) is subjected to a dehydration condensation reaction with the compound shown in formula (a) to obtain the compound shown in formula (1); wherein, Equation (2) ; Formula (a) is selected from one or more of the following compounds: 。 11. The method according to claim 10, wherein, The molar ratio of the compound shown in formula (2) to the compound shown in formula (a) is 1:2-100.

12. The method according to claim 10 or 11, wherein, The conditions for the dehydration condensation reaction include: a temperature of 20-100℃ and a time of 10 min-48 h.

13. The method according to claim 10, wherein, The basic compound is one or more of piperidine, pyridine, and triethylamine.

14. The method according to claim 13, wherein, The amount of the basic compound used is 0.1-1000 mmol relative to 1 mmol of the compound shown in formula (2).

15. The method according to claim 13, wherein, The organic solvent is chloroform and / or dichloromethane.

16. A photovoltaic material or photodetector material comprising one or more of the multi-fused-ring conjugated macromolecules as described in any one of claims 1-9.

17. A solar cell, wherein the photovoltaic material in the cell contains the multi-fused-ring conjugated macromolecule as described in any one of claims 1-9.

18. The solar cell according to claim 17, wherein, When the cell is an organic solar cell including a light-harvesting active layer, the electron donor material and / or electron acceptor material in the light-harvesting active layer contains one or more of the polycyclic fused ring conjugated macromolecules; When the cell is a perovskite solar cell comprising an electron transport layer, a perovskite light-harvesting layer, and a modification layer, the light-harvesting layer and / or the electron transport layer and / or the modification layer contains one or more of the multi-fused-ring conjugated macromolecules.

19. A method for preparing a solar cell according to claim 17 or 18, the method comprising: The multi-fused-ring conjugated macromolecules are configured in a light-harvesting layer and / or an electron transport layer and / or a modification layer.

20. The method according to claim 19, wherein, For organic solar cells, the layer containing photovoltaic materials is the active layer for light trapping; For perovskite solar cells, the photovoltaic material-containing layer is a light-harvesting layer and / or an electron transport layer and / or a modification layer.

21. A photodetector comprising an active layer for light trapping, wherein, The electron donor material and / or electron acceptor material in the light-harvesting active layer contains one or more of the multi-fused-ring conjugated macromolecules described in any one of claims 1-9.

22. A method for fabricating a photodetector, wherein, The method includes using one or more electron donor materials and / or electron acceptor materials containing any one of the polycyclic fused ring conjugated macromolecules of claims 1-9 to form an active layer for light trapping.

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