Quinone-type end-group-based polycondensed-ring conjugated macromolecules and intermediates thereof, and their preparation methods and applications

Abstract

The present invention discloses polycyclic condensed-ring conjugated macromolecules based on quinone-type end groups, intermediates thereof, and methods for preparing and applying the same. The polycyclic condensed-ring conjugated macromolecules based on quinone-type end groups of the present invention are compounds represented by the following formula (1). The polycyclic condensed-ring conjugated macromolecules based on quinone-type end groups provided by the present invention have strong near-infrared light absorption and a suitable energy level structure, making them suitable for use as light detection materials or photovoltaic materials in the preparation of light detectors or solar cells. #imgabs0#

Description

Technical Field

[0001] The present invention relates to the field of organic solar cells and organic photodetectors, and in particular to a multi-condensed ring conjugated macromolecule based on quinone-type end groups and intermediates thereof, as well as preparation methods and applications thereof. Background Art

[0002] Organic solar cells have developed rapidly in recent years, garnering widespread attention from both academia and industry due to their advantages, including light weight, flexibility, simple processing, large-scale fabrication, and low cost. Organic photodetectors, as a new type of photodetector, are also a key area of ​​research in organic electronics. Currently, the photoelectric conversion efficiency of organic solar cells based on a blend of a polymer donor and a fullerene acceptor has exceeded 12%, demonstrating the enormous potential for organic solar cells. Polymer materials, due to their high molar extinction coefficients and broad solar spectrum absorption, offer high photoelectric conversion efficiencies in 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 and macromolecular semiconductor materials have a defined molecular structure and molecular weight, along with advantages such as batch stability, simple purification, and high purity, leading to increasing interest in organic fused-ring small and macromolecular solar cells.

[0003] Due to the advantages of fullerene derivatives such as large enough electron affinity, isotropic electron transport performance, and relatively matched electron energy levels, fullerene derivatives (PC 61 BM and PC 71 PCBM has become a star molecule in acceptor materials and has always held a dominant position. However, PCBM also has many disadvantages, such as weak visible light absorption, difficult energy level control, and complex purification processes. New organic polycyclic fused-ring macromolecules possess strong visible light absorption properties and are particularly suitable as photovoltaic materials for organic solar cells and photodetectors. Therefore, the synthesis of new acceptor materials remains highly desirable. Summary of the Invention

[0004] The present invention aims to provide polycyclic fused-ring conjugated macromolecules based on quinone-type end groups, intermediates thereof, and methods for preparing and applying the same. These polycyclic fused-ring conjugated macromolecules based on quinone-type end groups have good solubility, are easily processed into films, have ultra-narrow optical band gaps, and suitable electronic energy levels, and can be used as electron donors or electron acceptors in solar cells and photodetectors.

[0005] In order to achieve the above object, the present invention provides a poly-condensed ring conjugated macromolecule based on a quinone-type end group, wherein the conjugated macromolecule is a compound represented by the following formula (1):

[0006]

[0007] Wherein, each group Ar is independently selected from one of the groups shown in the following formula:

[0008]

[0009] The group D is selected from one of the groups shown in the following formula:

[0010]

[0011] Each group B is independently selected from the formula The groups shown;

[0012] wherein R1 is independently selected from H, fluorine, chlorine, bromine, trifluoromethyl, C1-C30 alkyl, C1-C30 alkoxy, and C1-C30 alkylthio;

[0013] Each group E independently represents a substituted or unsubstituted conjugated fused ring structure composed of 1-10 thiophenes, selenophenes, and pyrroles, and the substituents are independently selected from H, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio, and C6-C30 aryl;

[0014] Each R2 is independently selected from the formula The groups shown;

[0015] each X, each Y, and each Y' are each independently selected from O, S, and Se;

[0016] Each Z is independently selected from C, N and Si;

[0017] each R3, each R4, each R5 and each R6 are each independently selected from H, C1-C30 alkyl, C1-C30 alkoxy, C1-C30 alkylthio and C6-C30 aryl;

[0018] n is an integer from 0 to 6;

[0019] m is an integer from 0 to 6;

[0020] p is an integer from 0 to 6.

[0021] Preferably, R1 is independently selected from H, fluorine, chlorine, bromine, trifluoromethyl, C1-C10 alkyl, C1-C10 alkoxy, C1-C10 alkylthio; each group E is independently a substituted or unsubstituted conjugated fused ring structure composed of 1-5 thiophenes, selenophenes and pyrroles, and the substituents are independently selected from H, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio and C6-C20 aryl; each X, each Y and each Y' are each independently selected from O, S and Se; each Z is each independently selected from C, N and Si; each R3, each R4, each R5 and each R6 are each independently selected from H, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio and C6-C20 aryl; n is an integer from 0 to 4; m is an integer from 0 to 4; p is an integer from 0 to 4;

[0022] More preferably, R1 is independently selected from H, fluorine, chlorine, bromine, trifluoromethyl, C1-C5 alkyl, C1-C5 alkoxy, C1-C5 alkylthio; each group E is independently selected from H, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio; each group E is independently selected from H, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio; each group E is independently selected from H, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio; each group E is independently selected from H, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio; each group E is independently selected from H, C1-C20 alkyl, C1-C20 alkyl and C6-C12 aryl; each X, each Y and each Y' are each independently selected from S and Se; each Z is each independently selected from C, N and Si; each R3, each R4, each R5 and each R6 are each independently selected from H, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio and C6-C12 aryl; n is an integer from 0 to 4; m is an integer from 0 to 4; p is an integer from 0 to 4;

[0023] More preferably, R1 is independently selected from H, fluorine, C1-C5 alkyl (such as methyl), C1-C5 alkoxy (such as methoxy); each group E represents independently substituted or unsubstituted thiophene, selenophene, pyrrole, thiophene, pyrrole, selenophene, thienopyrrole, thienoselenophene, trithiophene, dithienopyrrole, and the substituents are independently selected from H, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio and C6-C12 aryl; each X, each Y and each Y' is independently selected from S and Se; each Z is independently selected from C, N and Si; each R3, each R4, each R5 and each R6 is independently selected from H, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio and C6-C12 aryl; n is 0 or 1; m is 0 or 1; p is 0 or 1.

[0024] The second aspect of the present invention is a quinone intermediate represented by formula (a),

[0025]

[0026] Wherein, each group Ar is independently selected from one of the groups shown in the following formula:

[0027]

[0028] Wherein, R1 is independently selected from H, fluorine, chlorine, bromine, trifluoromethyl, C1-C30 alkyl, C1-C30 alkoxy, and C1-C30 alkylthio.

[0029] Preferably, R1 is independently selected from H, fluorine, chlorine, bromine, trifluoromethyl, C1-C10 alkyl, C1-C10 alkoxy, C1-C10 alkylthio;

[0030] More preferably, R1 is independently selected from H, fluorine, chlorine, bromine, trifluoromethyl, C1-C5 alkyl, C1-C5 alkoxy, C1-C5 alkylthio;

[0031] More preferably, R1 is independently selected from H, fluorine, C1-C5 alkyl (such as methyl), C1-C5 alkoxy (such as methoxy).

[0032] Formula (a) can be specifically selected from one or more of the following compounds:

[0033]

[0034] The third aspect of the present invention provides a method for preparing the quinone intermediate, comprising the following steps:

[0035] Under the action of a catalyst, the compound represented by formula (b) reacts with malononitrile in an organic solvent through a Knoevenagel condensation reaction to obtain a quinone intermediate represented by formula (a);

[0036]

[0037] In formula (b), the group Ar is defined the same as in formula (a).

[0038] In the above preparation method, the molar ratio of the compound represented by formula (b), malononitrile and catalyst can be 1:(1-100):(1-100), preferably 1:(1-20):(1:50), such as 1:1:5;

[0039] The catalyst may be titanium tetrachloride and pyridine in a molar ratio of 1: (0.5-10);

[0040] The organic solvent can be dichloromethane, chloroform, etc.

[0041] The specific steps of the Knoevenagel condensation reaction may be as follows: mixing the compound represented by formula (b), malononitrile and an organic solvent and stirring at 0-100°C for 10 minutes to 12 hours, more preferably, the reaction temperature is 0-30°C and the time is 10 minutes to 1 hour; for example, the reaction temperature is 0°C and the time is 10 minutes; then adding titanium tetrachloride and stirring at 0-100°C for 0.5-12 hours, more preferably, the reaction temperature is 0-30°C and the time is 0.5-1 hour; for example, the reaction temperature is 0°C and the time is 0.5 hours; finally, adding pyridine and stirring at 0-100°C for 10 minutes to 12 hours, more preferably, the reaction temperature is 0-30°C and the time is 0.5-12 hours; for example, the reaction temperature is 0°C and the time is 0.5 hours.

[0042] After the condensation reaction is completed, the method further comprises the following step: using a silica gel column to separate the condensation reaction product by chromatography using a mixture of petroleum ether and dichloromethane in a volume ratio of 1:0.2-3 as an eluent to obtain a compound represented by formula (a).

[0043] The fourth aspect of the present invention provides a method for preparing the compound represented by formula (1), comprising the following steps:

[0044] In the presence of a palladium catalyst, the compound represented by formula (2) and the quinone intermediate represented by formula (a) undergo a coupling reaction in an organic solvent to obtain a compound represented by formula (1);

[0045]

[0046] In formula (2), the definitions of group D and group B are the same as those of formula (1);

[0047]

[0048] In formula (a), the group Ar is defined as in formula (1).

[0049] In the above preparation method, formula (a) can be specifically selected from one or more of the following compounds:

[0050]

[0051] In the above preparation method, the molar ratio of the compound represented by formula (2) to the compound represented by formula (a) can be 1:(2-100), preferably 1:(2-4), such as 1:3.

[0052] In the above preparation method, the coupling reaction temperature may be 20-110°C, and the time may be 10 minutes to 48 hours. More preferably, the Stille coupling reaction temperature is 80-110°C, and the time is 10-15 hours; for example, the Stille coupling reaction temperature is 110°C, and the time is 6 hours.

[0053] In the above preparation method, the palladium catalyst can be tetrakis(triphenylphosphine)palladium or palladium acetate; the molar ratio of the palladium catalyst to the compound represented by formula (2) can be (0.01-0.1):1, preferably (0.01-0.05):1, such as 0.05:1.

[0054] In the above preparation method, the organic solvent can be toluene or tetrahydrofuran; the volume ratio of the amount of the compound represented by formula (2) to the organic solvent is 1 mmol: (20-500) mL, preferably 1 mmol: (40-400) mL, such as 1 mmol: 300 mL.

[0055] In the above preparation method, the reaction is carried out under an inert atmosphere.

[0056] In the above-mentioned preparation method, after the coupling reaction is completed, the method further comprises the following steps: using a silica gel column to separate the coupling reaction product by chromatography using a mixture of petroleum ether and dichloromethane in a volume ratio of 1:0.2-3 as an eluent to obtain a compound represented by formula (1).

[0057] The fifth aspect of the present invention provides the use of the compound represented by formula (1) as an electron donor material and / or electron acceptor material in the preparation of solar cells; or the use of the compound represented by formula (1) as an electron donor material and / or electron acceptor material in the preparation of photodetectors.

[0058] In a sixth aspect, the present invention provides a photovoltaic material for preparing a solar cell or a photodetector, comprising the compound represented by formula (1) described in any one of the above.

[0059] Preferably, the photovoltaic material is a light-harvesting active layer material.

[0060] As an example, the photovoltaic material is composed of an electron donor polymer material PTB7-Th represented by formula (3) and a compound represented by formula (1) described above in a weight ratio of 0.5-4:1;

[0061]

[0062] A seventh aspect of the present invention provides a solar cell, wherein the photovoltaic material thereof contains the compound represented by formula (1) as described in any one of the above. Preferably, the solar cell includes a light-capturing active layer, wherein the electron donor material and / or electron acceptor material in the light-capturing active layer contains the compound represented by formula (1) as described in any one of the above.

[0063] An eighth aspect of the present invention provides a method for preparing a solar cell, comprising the following steps: disposing the compound represented by formula (1) described in any one of the above items in a layer containing a photovoltaic material to obtain the solar cell.

[0064] In a ninth aspect, the present invention provides a photodetector comprising a light-harvesting active layer, wherein the electron donor material and / or the electron acceptor material in the light-harvesting active layer contains the compound represented by formula (1) described in any one of the above items.

[0065] The tenth aspect of the present invention is a method for preparing a photodetector, comprising the steps of forming an active layer for light capture by an electron donor material and / or an electron acceptor material containing a compound represented by formula (1) described in any one of the above items to obtain the photodetector.

[0066] The poly-condensed ring conjugated macromolecule provided by the present invention has good solubility, is easy to process into a film, has strong near-infrared light absorption and a suitable electronic energy level, and is suitable for use as a photovoltaic material or light detection material in the preparation of solar cells or light detectors. BRIEF DESCRIPTION OF THE DRAWINGS

[0067] Figure 1 The UV-visible absorption spectrum of the polycyclic fused-ring conjugated macromolecule represented by formula (1-1) obtained in Example 1 of the present invention, wherein the solution refers to a solution prepared with chloroform as a solvent (10 -6 mol / L), and thin films refer to those obtained by spin coating from chloroform solution (100 nm thickness).

[0068] Figure 2 This is the cyclic voltammetry curve of the poly-fused-ring conjugated macromolecule represented by formula (1-1) obtained in Example 1 of the present invention.

[0069] Figure 3 The UV-visible absorption spectrum of the polycyclic fused-ring conjugated macromolecule of formula (1-2) obtained in Example 2 of the present invention, wherein the solution refers to a solution prepared with chloroform as a solvent (10 -6 mol / L), and thin films refer to those obtained by spin coating from chloroform solution (100 nm thickness).

[0070] Figure 4 This is the cyclic voltammetry curve of the poly-fused-ring conjugated macromolecule represented by formula (1-2) obtained in Example 2 of the present invention.

[0071] Figure 5 The UV-visible absorption spectrum of the polycyclic fused-ring conjugated macromolecule represented by formula (1-3) obtained in Example 3 of the present invention, wherein the solution refers to a solution prepared with chloroform as a solvent (10 -6 mol / L), and thin films refer to those obtained by spin coating from chloroform solution (100 nm thickness).

[0072] Figure 6 This is the cyclic voltammetry curve of the multi-ring fused conjugated macromolecule represented by formula (1-3) obtained in Example 3 of the present invention.

[0073] Figure 7 The UV-visible absorption spectrum of the polycyclic fused-ring conjugated macromolecule of formula (1-4) obtained in Example 4 of the present invention, wherein the solution refers to a solution prepared with chloroform as a solvent (10 -6 mol / L), and thin films refer to those obtained by spin coating from chloroform solution (100 nm thickness).

[0074] Figure 8 This is the cyclic voltammetry curve of the multi-ring fused conjugated macromolecule represented by formula (1-4) obtained in Example 4 of the present invention.

[0075] Figure 9 This is the IV curve (current-voltage curve) of the solar cell obtained in Example 5.

[0076] Figure 10 This is the IV curve of the photodetector obtained in Example 6.

[0077] Figure 11 This is the external quantum efficiency curve of the photodetector obtained in Example 6.

[0078] Figure 12 This is the responsivity curve of the photodetector obtained in Example 6.

[0079] Figure 13 This is the noise current curve of the photodetector obtained in Example 6.

[0080] Figure 14 This is the relative detectivity curve of the photodetector obtained in Example 6. DETAILED DESCRIPTION

[0081] The endpoints of the ranges and any values ​​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 endpoints of each range, the endpoints of each range and individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered to be specifically disclosed herein.

[0082] In the present invention, each group is independently selected to represent that when each group appears simultaneously and in multiple places in the compound, they are all independently selected and can be the same or different. For example, although The group shown has four R1s, but these four R1s can be independently selected and can be the same or different.

[0083] In the present invention, The dashed lines in structures with dashed linkers indicate the linking sites and represent the linkers; In structures with solid connecting bonds, solid lines outside the brackets that are not connected to any groups or atoms also indicate the connection site and represent the connecting bond.

[0084] In one aspect, the present invention provides a poly-condensed-ring conjugated macromolecule based on a quinone-type end group, wherein the conjugated macromolecule is a compound represented by the following formula (1):

[0085] Formula (1)

[0086] The various groups in formula (1) are as defined in the Summary of the Invention section.

[0087] According to the present invention, in order to obtain a conjugated molecule with stronger light absorption, higher charge transfer performance and more suitable electronic energy level, preferably, R1 is independently selected from H, fluorine, chlorine, bromine, trifluoromethyl, C1-C5 alkyl, C1-C5 alkoxy, C1-C5 alkylthio; each group E is independently selected from 1-5 substituted or unsubstituted conjugated fused ring structures composed of one or more of thiophene, selenophene and pyrrole, and the substituents are independently selected from H, C1-C20 alkyl, C each X, each Y and each Y' is independently selected from S and Se; each Z is independently selected from C, N and Si; each R3, each R4, each R5 and each R6 is independently selected from H, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio and C6-C12 aryl; n is an integer from 0 to 4; m is an integer from 0 to 4; p is an integer from 0 to 4;

[0088] More preferably, R1 is independently selected from H, fluorine, C1-C5 alkyl, C1-C5 alkoxy; each group E is independently selected from H, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio and C6-C12 aryl; each X, each Y and each Y' is independently selected from S and Se; each Z is independently selected from C, N and Si; each R3, each R4, each R5 and each R6 is independently selected from H, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio and C6-C12 aryl; n is 0 or 1; m is 0 or 1; p is 0 or 1;

[0089] More preferably, R1 is independently selected from H, fluorine, methyl, methoxy; each group E represents independently substituted or unsubstituted thiophene, selenophene, pyrrole, thiophene, pyrrole, selenophene, thienopyrrole, thienoselenophene, trithiophene, dithienopyrrole, and the substituents are independently selected from H, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio and C6-C12 aryl; each X, each Y and each each Y' is independently selected from S and Se; each Z is independently selected from C, N and Si; each R3, each R4, each R5 and each R6 is independently selected from H, n-butyl, n-pentyl, n-hexyl, n-octyl, 2-ethylhexyl, n-butoxy, n-pentyloxy, n-hexyloxy, n-octyloxy, 2-ethylhexyloxy, n-butylthio, n-pentylthio, n-hexylthio, n-octylthio and 2-ethylhexylthio; n is 0 or 1; m is 0 or 1; p is 0 or 1;

[0090] 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, and 2-ethylhexyl. Alkyl groups within other ranges of the present invention can also be selected from these specific examples as appropriate.

[0091] 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-decyloxy, and 2-ethylhexyloxy. Alkoxy groups within other scopes of the present invention can also be selected from these specific examples as appropriate.

[0092] 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, and 2-ethylhexylthio. Alkylthio groups within other scopes of the present invention can also be selected from these specific examples as appropriate.

[0093] Specific examples of C6-C12 aryl groups include phenyl, benzyl, p-tolyl, etc. Aryl groups within other scopes of the present invention can also be selected from these specific examples according to circumstances.

[0094] Wherein, the two groups E located on both sides of the structure of group D should be understood to constitute a conjugated structure together with the middle and two end structures of group D, wherein each group E independently represents a substituted or unsubstituted conjugated fused ring structure composed of one or more of 1-5 thiophenes, selenophenes and pyrroles, and the substituents are independently selected from H, C1-C20 alkyl, C1-C20 alkoxy, C1-C20 alkylthio and C6-C20 aryl. When group E is a thiophene conjugated fused ring structure or a selenophene conjugated fused ring structure or a pyrrole conjugated fused ring structure, in fact, there is a thiophene or selenophene or pyrrole group on each side to form the basic structure of the conjugated macromolecule with the middle structure and the two end structures; when group E is two or more thiophene conjugated fused ring structures, it can be understood as a normal thiophene structure 1 With anti-thiophene structure 2 Alternating conjugation, as shown in the structural formula The two carbon atoms connected by the dotted line are shared between the two rings to form the structural formula shown in For a fused ring structure consisting of two thiophenes, if there are three thiophene rings, the same method can be used to connect a second structure to the left of the first structure, or a first structure to the right of the second structure, forming a 1-2-1 thiophene conjugated fused ring structure with alternating positive and negative directions. A similar approach can be applied to conjugated fused ring structures consisting of multiple thiophenes, selenophenes, pyrroles, or any combination of two or three of these units.

[0095] According to the present invention, the group With strong electron pulling effect, the group Located at both ends of the fused ring unit, the resulting conjugated macromolecule has strong visible light absorption ability, high charge transfer performance and suitable electronic energy levels, making it suitable for use as a photovoltaic material in the preparation of organic solar cells; it is also suitable for use as a light detection material in light detectors.

[0096] Preferably, the group Ar is selected from one or more of the following groups Ar-1 to Ar-7:

[0097] Define the group Ar-1 as The group Ar-2 is The group Ar-3 is The group Ar-4 is The group Ar-5 is The group Ar-6 is The group Ar-7 is

[0098] The second aspect of the present invention provides a quinone intermediate represented by formula (a),

[0099]

[0100] Wherein, each group Ar is independently selected from one of the groups shown in the following formula:

[0101]

[0102] Wherein, R1 is independently selected from H, fluorine, chlorine, bromine, trifluoromethyl, C1-C30 alkyl, C1-C30 alkoxy, and C1-C30 alkylthio.

[0103] According to the present invention, preferably, R1 is independently selected from H, fluorine, chlorine, bromine, trifluoromethyl, C1-C10 alkyl, C1-C10 alkoxy, C1-C10 alkylthio;

[0104] More preferably, R1 is independently selected from H, fluorine, chlorine, bromine, trifluoromethyl, C1-C5 alkyl, C1-C5 alkoxy, C1-C5 alkylthio;

[0105] More preferably, R1 is independently selected from H, fluorine, C1-C5 alkyl (such as methyl), C1-C5 alkoxy (such as methoxy).

[0106] 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, and 2-ethylhexyl. Alkyl groups within other ranges of the present invention can also be selected from these specific examples as appropriate.

[0107] 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-decyloxy, and 2-ethylhexyloxy. Alkoxy groups within other scopes of the present invention can also be selected from these specific examples as appropriate.

[0108] 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, and 2-ethylhexylthio. Alkylthio groups within other scopes of the present invention can also be selected from these specific examples as appropriate.

[0109] Preferably, the group Ar is selected from one or more of the following groups Ar-1 to Ar-7:

[0110] Define the group Ar-1 as The group Ar-2 is The group Ar-3 is The group Ar-4 is The group Ar-5 is The group Ar-6 is The group Ar-7 is

[0111] The third aspect of the present invention provides a method for preparing a quinone intermediate represented by formula (a), comprising the following steps:

[0112] Under the action of a catalyst, the compound represented by formula (b) reacts with malononitrile in an organic solvent through a Knoevenagel condensation reaction to obtain a quinone intermediate represented by formula (a);

[0113]

[0114]

[0115] In formula (b), the group Ar is defined the same as in formula (a).

[0116] In this method, the group Ar is as described above, and the present invention will not elaborate on it here.

[0117] According to the present invention, the compound represented by formula (b) can undergo a Knoevenagel condensation reaction with malononitrile to form a quinone-type intermediate represented by formula (a), wherein there is no particular limitation on the amount of the compound represented by formula (b) and malononitrile used, as long as the quinone-type intermediate represented by formula (a) can be prepared. Preferably, the molar ratio of the compound represented by formula (b) to malononitrile is 1: (1 to 100), more preferably 1: (1 to 20), for example 1: 1.

[0118] According to the present invention, the reaction is carried out in the presence of a catalyst, and the molar ratio of the compound represented by formula (b) to the catalyst is preferably 1: (1 to 100), more preferably 1: (1 to 50), such as 1: 3. The catalyst can be titanium tetrachloride and pyridine, preferably titanium tetrachloride and pyridine in a molar ratio of 1: (0.5 to 10), such as 1: 0.5.

[0119] According to the present invention, the organic solvent is, for example, dichloromethane and / or chloroform.

[0120] According to the present invention, the Knoevenagel condensation reaction can be carried out in steps, such as: mixing the compound represented by formula (b), malononitrile and an organic solvent and stirring at 0-100°C for 10 minutes to 12 hours, more preferably at 0-30°C for 10 minutes to 1 hour, for example, stirring at 0°C for 10 minutes; then adding titanium tetrachloride and stirring at 0-100°C for 0.5-12 hours, more preferably at 0-30°C for 0.5-1 hour, for example, stirring at 0°C for 0.5 hours; finally, adding pyridine and stirring at 0-100°C for 10 minutes to 12 hours, more preferably at 0-30°C for 0.5-12 hours, for example, stirring at 0°C for 0.5 hours.

[0121] According to the present invention, in order to extract the compound represented by formula (a) from the reaction solution, the method further includes a post-treatment step, for example, using a silica gel column to separate the condensation reaction product by chromatography using a mixture of petroleum ether and dichloromethane in a volume ratio of 1:0.2-3 as an eluent to obtain the compound represented by formula (a).

[0122] A fourth aspect of the present invention provides a method for preparing the above-mentioned multi-fused-ring conjugated macromolecule, comprising the following steps:

[0123] In the presence of a palladium catalyst, the compound represented by formula (2) and the quinone intermediate represented by formula (a) undergo a coupling reaction in an organic solvent to obtain a compound represented by formula (1);

[0124]

[0125] In formula (2), the definitions of group D and group B are the same as those of formula (1);

[0126]

[0127] In formula (a), the group Ar is defined as in formula (1).

[0128] In this method, group B, group D, group Ar, etc. are as described above, and the present invention will not repeat them here.

[0129] The compound represented by formula (2) can be selected based on the structure of the poly-condensed ring conjugated macromolecule mentioned above.

[0130] According to the present invention, the compound represented by formula (2) can be a commercial product, or can be prepared by conventional methods in the art, for example, by reacting butyl lithium with trimethyltin.

[0131] According to the present invention, the compound represented by formula (a) can be appropriately selected. For example, specific examples of the compound represented by formula (a) may include:

[0132]

[0133] According to the present invention, the trimethyltin connected to both ends of the compound represented by formula (2) can undergo a Stille coupling reaction with the compound represented by formula (a), thereby forming a compound represented by formula (1), wherein 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 prepared. Preferably, the molar ratio of the compound represented by formula (2) to the compound represented by formula (a) is 1:2-100, more preferably 1:2-4.

[0134] According to the present invention, the reaction is carried out in the presence of a palladium catalyst, which may be tetrakis(triphenylphosphine)palladium or palladium acetate. The amount of the palladium catalyst used is 0.01-0.1 mmol, more preferably 0.01-0.05 mmol, relative to 1 mmol of the compound represented by formula (2). In the examples, 0.1 mmol is used.

[0135] According to the present invention, the organic solvent is, for example, toluene and / or tetrahydrofuran. The amount of the organic solvent used can be, for example, 20-500 mL (preferably 40-400 mL) relative to 1 mmol of the compound represented by formula (2).

[0136] According to the present invention, preferably, the conditions for the Stille coupling reaction include: a temperature of 20-110° C. (e.g., 80-110° C.) and a time of 10 min-48 h (e.g., 10-20 h). More preferably, the conditions for the Stille coupling reaction include: a temperature of 80-110° C. and a time of 10-15 h.

[0137] To ensure the smooth progress of the reaction, the method further includes maintaining the reaction system under an inert atmosphere before the reaction. For example, after all the raw materials are 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.

[0138] 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-treatment step, for example, the Stille coupling reaction product is subjected to chromatographic separation using a silica gel chromatography column (200-300 mesh silica gel can be used, and the eluent can be a mixture of petroleum ether and dichloromethane in a volume ratio of 1:0.2-3).

[0139] The fifth aspect of the present invention provides the use of the above-mentioned multi-condensed ring conjugated macromolecule based on quinone-type end groups as an electron donor material and / or electron acceptor material in the preparation of solar cells; or,

[0140] The application of the above-mentioned multi-condensed ring conjugated macromolecule based on quinone-type end groups as electron donor material and / or electron acceptor material in the preparation of photodetectors.

[0141] In a sixth aspect, the present invention provides a photovoltaic material containing the above-mentioned poly-condensed ring conjugated macromolecule based on quinone-type end groups for preparing solar cells or photodetectors.

[0142] According to the present invention, there is no particular limitation on photovoltaic materials, as long as they contain the above-mentioned polycyclic fused-ring conjugated macromolecules of the present invention. The photovoltaic material preferably refers to the electron donor material and / or electron acceptor material in the active layer of light capture in solar cells and photodetectors.

[0143] For example, the electron-donating polymer material PTB7-Th can be combined with the conjugated molecules provided herein in a weight ratio of 0.5-4:1 to form photovoltaic materials, particularly light-harvesting active layer materials for solar cells and photodetectors. The poly-fused-ring conjugated macromolecules provided herein are particularly preferred as electron acceptor materials. In this example, the electron-donating polymer material PTB7-Th and the conjugated molecules provided herein are combined in a weight ratio of 7:8.

[0144] Among them, the structural unit of the polymer material PTB7-Th is as follows:

[0145]

[0146] The preparation of the polymer material PTB7-Th can be carried out, for example, by referring to the method in the literature (Adv. Mater. 2013, 25, 4766-4771), which will not be described in detail in the present invention.

[0147] A seventh aspect of the present invention provides a solar cell, wherein the photovoltaic material in the solar cell contains the above-mentioned multi-ring fused conjugated macromolecule.

[0148] According to the present invention, there is no particular limitation on the structure of the solar cell. As long as the photovoltaic material used contains the poly-condensed ring conjugated macromolecule of the present invention, the photoelectric conversion efficiency of the solar cell can be effectively improved. For example, the solar cell is an organic solar cell.

[0149] Wherein, when the cell is an organic solar cell comprising 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 poly-condensed-ring conjugated macromolecules.

[0150] In particular, the conjugated molecules of the present invention are preferably used as electron acceptor materials in combination with other electron donor materials to form the light-harvesting active layer of a solar cell. Such an electron donor material may be, for example, the polymer material PTB7-Th, as defined above.

[0151] The polymer material PTB7-Th can be combined with the conjugated macromolecule provided by the present invention at a weight ratio of 0.5-4:1 to form a light-harvesting active layer. In the example, the polymer material PTB7-Th and the conjugated macromolecule provided by the present invention are combined at a weight ratio of 7:8 for illustration.

[0152] An eighth aspect of the present invention provides a method for preparing the above-mentioned solar cell, the method comprising: disposing the poly-condensed ring conjugated macromolecule in a layer containing a photovoltaic material.

[0153] According to the present invention, there is no particular limitation on the preparation process of the solar cell, and conventional methods in the art can be used. For organic solar cells, the layer containing the photovoltaic material can be an active layer for light capture.

[0154] According to the present invention, the preparation process of the organic solar cell may include, for example, the following: for an inverted structure device: coating a ZnO layer as a cathode modification layer (e.g., 20-50 nm thick) on a conductive glass (e.g., indium tin oxide glass, ITO) serving as a cathode; after drying, coating the ZnO layer with a mixture of a polymer material PTB7-Th and a conjugated macromolecule provided by the present invention as an active layer; after drying, vacuum evaporating molybdenum oxide (e.g., 5-10 nm thick) and Ag (e.g., 50-100 nm thick) as an anode. For a forward structure device: Unlike an inverted structure device, a polymer layer formed from a polymer combination of, for example, poly (3,4-ethylenedioxythiophene)-poly (styrene sulfonate), also known as PEDOT:PSS, is used in place of the ZnO layer; and PDINN, a derivative of perylene diimide, is used in place of molybdenum oxide.

[0155] The conjugated molecules provided by the present invention have a strong absorption peak in the near-infrared region, for example, a strong absorption peak in the wavelength range of 600-1600 nm; the conjugated molecules have good thermal stability and can withstand temperatures of around 340°C without decomposition; cyclic voltammetry test results show that their HOMO energy level and LUMO energy level can match the energy levels of most common electron donor materials, and they have good electron or hole acceptance capabilities, making them very suitable as photovoltaic materials for solar cells, especially electron acceptors and / or electron donor materials, and especially as electron acceptor materials.

[0156] A ninth aspect of the present invention provides a photodetector comprising a light-harvesting active layer, wherein the electron donor material and / or electron acceptor material in the light-harvesting active layer contains one or more of the above-mentioned poly-condensed-ring conjugated macromolecules.

[0157] The present invention has no particular limitation on the structure of the photodetector, and conventional structures in the art may be adopted, as long as it includes the above-mentioned poly-fused-ring conjugated macromolecule of the present invention, thereby achieving excellent photodetection effects.

[0158] The tenth aspect of the present invention provides a method for preparing a photodetector, wherein the method includes forming a light-capturing active layer with an electron donor material and / or an electron acceptor material containing one or more of the above-mentioned multi-condensed ring conjugated macromolecules.

[0159] The present invention has no particular limitation on the preparation process of the photodetector. The preparation process of the photodetector in this field can be adopted, as long as it includes the above-mentioned multi-ring conjugated macromolecule of the present invention, so that excellent light detection effect can be obtained.

[0160] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods. The materials, reagents, etc. used in the following examples, unless otherwise specified, can be obtained from commercial sources. 13 All are n-hexyl, -C4H9 are n-butyl, and -C2H5 are ethyl. 1H NMR was measured using a Bruker AVANCE400 / 300 nuclear magnetic resonance instrument. MS (MALDI) was measured using a Bruker Daltonics Biflex III MALDI-TOF Analyzer mass spectrometer, and MS (EI) was measured using an APEX II FT-ICR (Bruker Daltonics, Inc.) mass spectrometer. UV-visible absorption and visible light transmission spectra were measured using a UH4150 Spectrophotometer UV-visible spectrophotometer. Cyclic voltammetry was measured using a CHI660C electrochemical workstation cyclic voltammeter. IV curves were measured using a Keithley 2450 Source / Measure Unit. Parameters such as short-circuit current, open-circuit voltage, fill factor, and photoelectric conversion efficiency can be obtained from the IV curves. External quantum efficiency and responsivity curves were measured using a QE-R3011 (Enli Technology Co., Ltd.), and noise current was measured using a ProPlus 9812D wafer-level 1 / f noise characterization system. The polymer material PTB7-Th can be prepared, for example, according to the method described in the literature (Adv. Mater. 2013, 25, 4766-4771).

[0161] Preparation Example 1

[0162] This preparation example is used to illustrate the preparation method of the compound represented by the following formula (2-1). Group D is selected from Wherein E is a thiophene unit, Z is a carbon atom, R2 is a 2-ethylhexyl group; group B is Among them, the alkoxy group is on the side close to the D unit.

[0163]

[0164] As shown in the above reaction formula, the compound DTCP-2SnMe3 (146 mg, 0.2 mmol, purchased from Suzhou Nakai Technology Co., Ltd.), the compound OT-Br (128 mg, 0.44 mmol, purchased from Suzhou Nakai Technology Co., Ltd.), tetrakistriphenylphosphine palladium (25 mg, 0.022 mmol) and toluene (30 mL) were added to a reaction vessel, purged with argon for 25 minutes, and then refluxed at 110°C for 12 hours. After cooling to room temperature (about 25°C), the mixture was extracted with saturated brine and dichloromethane, dried over magnesium sulfate, and spin-dried. The resulting precipitate was chromatographed on a silica gel column (using 200-300 mesh silica gel and petroleum ether as eluent) to obtain an orange oily liquid (53 mg, 32% yield), which is compound COT. 1 H NMR (300MHz, CDCl3): δ7.08 (s, 2H), 7.00 (d, J = 5.4Hz, 2H), 6.86 (d, J = 5.4Hz, 2H), 4.04 (d, J = 6.0Hz, 4H), 1.9 6-1.76(m,6H),1.70-1.47(m,10H),1.39(m,8H),1.11-0.90(m,28H),0.83-0.71(m,6H),0.70-0.60(m,6H). 13 CNMR (75MHz, CDCl3): δ156.94,152.19,136.05,134.78,120.34,117.78,117.39,116.57,74.09,53.57,43.44,40.0 1,35.21,34.21,30.63,29.25,28.67,27.46,24.01,23.19,22.96,14.26,14.17,11.32,10.74.MS(MALDI-TOF):m / z 822.5(M + ).

[0165] As shown in the above reaction formula, the compound represented by formula COT (82 mg, 0.1 mmol) and tetrahydrofuran (20 mL) were added to a reaction vessel, purged with argon, and stirred at -78 ° C for 1 h. n-Butyl lithium (0.19 mL, 0.3 mmol, 1.6 M) was slowly added dropwise, stirred at -78 ° C for 2 h, trimethyltin chloride (0.5 mL, 0.5 mmol, 1 M) was added, and the reaction product was slowly returned to room temperature (about 25 ° C) and stirred overnight (about 12 h). Then, a saturated aqueous solution of potassium fluoride (1 mL) was added to quench the reaction, extracted with saturated brine and dichloromethane, dried over magnesium sulfate, and spin-dried. The resulting precipitate was poured into 100 mL of methanol and filtered to obtain a red solid (101 mg, yield 88%), which is the compound represented by formula (2-1). 1H NMR (400MHz, CDCl3): δ7.09(s,2H),6.91(s,2H),4.07(d,4H),1.86(m,6H),1.61(m ,10H),1.38(m,8H),0.98(m,28H),0.68(m,12H),0.38(s,18H).MS(MALDI-TOF):m / z 1149.1(M+).

[0166] Preparation Example 2

[0167] This preparation example is used to illustrate the preparation method of the compound represented by the following formula (2-3). Group D is selected from wherein the group E is X is a sulfur atom, Z is a nitrogen atom, R2 is a 2-ethylhexyl group; and group B does not exist.

[0168]

[0169] As shown in the above reaction formula, the compound represented by formula BTP (97 mg, 0.1 mmol; purchased from Suzhou Nakai Technology Co., Ltd.) and tetrahydrofuran (20 mL) were added to a reaction vessel, purged with argon, and stirred at -78°C for 1 hour. n-Butyl lithium (0.19 mL, 0.3 mmol, 1.6 M) was slowly added dropwise, and the mixture was stirred at -78°C for 2 hours. Trimethyltin chloride (0.5 mL, 0.5 mmol, 1 M) was added, and the reaction product was slowly returned to room temperature (about 25°C) and stirred overnight (about 12 hours). A saturated aqueous solution of potassium fluoride (1 mL) was then added to quench the mixture, and the mixture was extracted with saturated brine and dichloromethane, dried over magnesium sulfate, and spin-dried. The resulting precipitate was poured into 100 mL of methanol and filtered to obtain an orange-red solid (104 mg, 80% yield), which is the compound represented by formula (2-3). 1 H NMR (400MHz, CDCl3): δ4.62(m,4H),2.82(d,J=8.0Hz,4H),2.05(m,2H),1.84(m,4H),1.47-1.23( m,36H),1.02-0.83(m,18H),0.66-0.57(m,12H),0.49(s,18H).MS(MALDI-TOF):m / z1297.5(M+).

[0170] Preparation Example 3

[0171] This preparation example is used to illustrate the preparation method of the compound represented by the following formula (2-4). Group D is selected from wherein the group E is Z is a carbon atom, R2 is Group B is absent.

[0172]

[0173] As shown in the above reaction formula, the compound represented by Formula 3TT (108 mg, 0.1 mmol; purchased from Suzhou Nakai Technology Co., Ltd.) and tetrahydrofuran (20 mL) were added to a reaction vessel, purged with argon, and stirred at -78°C for 1 hour. n-Butyl lithium (0.19 mL, 0.3 mmol, 1.6 M) was slowly added dropwise, and the mixture was stirred at -78°C for 2 hours. Trimethyltin chloride (0.5 mL, 0.5 mmol, 1 M) was added, and the reaction product was slowly returned to room temperature (about 25°C) and stirred overnight (about 12 hours). A saturated aqueous solution of potassium fluoride (1 mL) was then added to quench the mixture, and the mixture was extracted with saturated brine and dichloromethane, dried over magnesium sulfate, and spin-dried. The resulting precipitate was poured into 100 mL of methanol and filtered to obtain a red solid (127 mg, 90% yield), which is the compound represented by Formula (2-4). 1 H NMR (400MHz, CD2Cl2): δ7.30(s,2H),7.10(d,J=8.4Hz,8H),7.08(d,J=8.4Hz,8H),2.53(t,J= 8.0Hz,8H),1.54(m,8H),1.33-1.22(m,24H),0.83(m,12H),0.36(s,18H).MS(MALDI-TOF):m / z 1408.1(M+).

[0174] Preparation Example 4

[0175] This preparation example is used to illustrate the preparation method of the compound represented by formula (a-1).

[0176]

[0177] As shown in the reaction formula above, 2-bromo-1,4-naphthoquinone (1.78 g, 7.5 mmol; purchased from Bidex Pharmaceuticals), malononitrile (500 mg, 7.5 mmol), and dichloromethane (30 mL) were added to a reaction vessel, purged with argon, and stirred at 0°C for 30 minutes. Titanium tetrachloride (7.5 mL, 7.5 mmol, 1 M) was slowly added, and the mixture was stirred at 0°C for 0.5 h. Pyridine (0.3 mL, 3.7 mmol) was slowly added, and the mixture was stirred at 0°C for 0.5 h. Water (40 mL) was added, and the mixture was stirred for 1.5 h. The mixture was extracted with saturated brine and dichloromethane, dried over magnesium sulfate, and spin-dried. The resulting precipitate was chromatographed on a silica gel column (200-300 mesh silica gel, eluent: petroleum ether / ethyl acetate (volume ratio: 25:1)) to yield a yellow solid (360 mg, 17% yield). 1H NMR (400MHz, CDCl3): δ8.82 (m, 1H), 8.36 (m, 2H), 7.83 (m, 2H). MS (EI): m / z 283.9 (M + ).

[0178] Example 1

[0179] This example is used to illustrate the conjugated macromolecule and its preparation method of the present invention.

[0180]

[0181] As shown in the above reaction formula, the compound represented by formula (2-1-8) obtained in the above Preparation Example 1 (115 mg, 0.1 mmol), the compound represented by formula (a-1) (86 mg, 0.3 mmol), tetrakis(triphenylphosphine)palladium (12 mg, 0.01 mmol) and toluene (30 mL) were added to a reaction vessel, purged with argon for 25 minutes, and then refluxed at 110°C for 6 hours. After cooling to room temperature (about 25°C), the mixture was extracted with saturated brine and dichloromethane, dried over magnesium sulfate, and spin-dried. The resulting precipitate was chromatographed on a silica gel column (using 200-300 mesh silica gel and an eluent of petroleum ether / dichloromethane with a volume ratio of 2:1) to obtain a black solid (64 mg, a yield of 52%), which is the poly- and fused-ring conjugated macromolecule represented by formula (1-1). 1 H NMR (400MHz, CDCl3): δ8.81(s,2H),8.31(s,2H),7.90(t,J=3.3Hz,2H),7.75(m,4H),7.60(t,J=3.8Hz,2H),7.44(t,J=3.0Hz,2H),4. 18(d,J=5.3Hz,4H),6.10(d,J=3.2Hz,2H),1.96(m,6H),1.64(m,10H),1.42(m,8H),0.98(m,28H),0.68(m,12H).MS(MALDI-TOF):m / z 1231.1(M+).

[0182] The UV-visible absorption spectrum of the polycyclic fused-ring conjugated macromolecule represented by formula (1-1) is as follows: Figure 1 As shown, it has a strong absorption peak in the wavelength range of 800-1400nm, and the maximum molar extinction coefficient is 8.2×10 4 M –1 cm –1 The film has the strongest absorption at around 1300nm; the maximum absorption peak of the film is red-shifted by 145nm compared with that in the solution.

[0183] Cyclic voltammetry curves such as Figure 2As shown, its HOMO energy level is -5.11eV, LUMO energy level is -4.19eV, and band gap is 0.92eV, indicating that the polycyclic fused-ring conjugated macromolecule shown in formula (1-1) has good electron-accepting ability and can match the energy levels of most common electron donor materials.

[0184] Example 2

[0185] This example is used to illustrate the conjugated macromolecule and its preparation method of the present invention.

[0186]

[0187] As shown in the above reaction formula, IDT-2SnMe3 (93 mg, 0.1 mmol; purchased from Suzhou Nakai Technology Co., Ltd.), the compound represented by formula (a-1) (86 mg, 0.3 mmol), tetrakis(triphenylphosphine)palladium (12 mg, 0.01 mmol) and toluene (30 mL) were added to a reaction vessel, purged with argon for 25 minutes, and then refluxed at 110°C for 6 hours. After cooling to room temperature (about 25°C), the mixture was extracted with saturated brine and dichloromethane, dried over magnesium sulfate, and spin-dried. The resulting precipitate was chromatographed on a silica gel column (using 200-300 mesh silica gel and an eluent of petroleum ether / dichloromethane with a volume ratio of 2:1) to obtain a green solid (69 mg, a yield of 66%), which is the poly-condensed ring conjugated macromolecule represented by formula (1-2). 1 H NMR (500MHz, CDCl3): δ8.85(m,2H),8.38(m,2H),8.13(s,2H),7.86(s,2H),7.80(m,4H),7.45(s,2H),2. 08(m,4H),1.96(m,4H),1.32-1.21(m,24H),0.90-0.82(m,8H),0.81-0.74(m,12H).MS(MALDI-TOF):m / z 1011.5(M + ).

[0188] The UV-visible absorption spectrum of the poly-fused ring conjugated macromolecule represented by formula (1-2) is as follows: Figure 3 As shown, it has a strong absorption peak in the wavelength range of 600-900 nm, and the maximum molar extinction coefficient is 5.3×10 4 M –1 cm –1 The film has the strongest absorption at around 832nm; the maximum absorption peak of the film is 20nm red-shifted than that of the solution.

[0189] Cyclic voltammetry curves such as Figure 4As shown, its HOMO energy level is -5.52eV, LUMO energy level is -4.18eV, and band gap is 1.34eV, indicating that the polycyclic fused-ring conjugated macromolecule shown in formula (1-2) has good electron-accepting ability and can match the energy levels of most common electron donor materials.

[0190] Example 3

[0191] This example is used to illustrate the conjugated macromolecule and its preparation method of the present invention.

[0192]

[0193] As shown in the above reaction formula, the compound represented by formula (2-3) obtained in the above Preparation Example 2 (130 mg, 0.1 mmol), the compound represented by formula (a-1) (86 mg, 0.3 mmol), tetrakis(triphenylphosphine)palladium (12 mg, 0.01 mmol) and toluene (30 mL) were added to a reaction vessel, purged with argon for 25 minutes, and then refluxed at 110° C. for 6 hours. After cooling to room temperature (about 25° C.), the mixture was extracted with saturated brine and dichloromethane, dried over magnesium sulfate, and spin-dried. The resulting precipitate was chromatographed on a silica gel column (using 200-300 mesh silica gel and an eluent of petroleum ether / dichloromethane with a volume ratio of 2:1) to obtain a brown solid (74 mg, a yield of 54%), which is the poly- and fused-ring conjugated macromolecule represented by formula (1-3). 1 H NMR (300MHz, CDCl3): δ8.84(m,2H),8.38(m,2H),7.81(s,2H),7.83(m,4H),4.69(d,J=6.0Hz,4H),3.09(t,J=9.0Hz ,4H),2.14-1.94(m,6H),1.46-1.21(m,28H),1.14-0.80(m,16H),0.74-0.60(m,12H).MS(MALDI-TOF):m / z1379.1(M + ).

[0194] The UV-visible absorption spectrum of the poly-fused ring conjugated macromolecule represented by formula (1-3) is as follows: Figure 5 As shown in Figure 2, it has a strong absorption peak in the wavelength range of 600-1000 nm, and the maximum molar extinction coefficient is 9.3×10 4 M –1 cm –1 The film has the strongest absorption at around 969nm; the maximum absorption peak of the film is red-shifted by 91nm compared with that in the solution.

[0195] Cyclic voltammetry curves such as Figure 6As shown, its HOMO energy level is -5.40eV, LUMO energy level is -4.13eV, and band gap is 1.27eV, indicating that the polycyclic fused-ring conjugated macromolecule shown in formula (1-3) has good electron-accepting ability and can match the energy levels of most common electron donor materials.

[0196] Example 4

[0197] This example is used to illustrate the conjugated macromolecule and its preparation method of the present invention.

[0198]

[0199] As shown in the above reaction formula, the compound represented by formula (2-4) obtained in the above Preparation Example 3 (141 mg, 0.1 mmol), the compound represented by formula (a-1) (86 mg, 0.3 mmol), tetrakis(triphenylphosphine)palladium (12 mg, 0.01 mmol) and toluene (30 mL) were added to a reaction vessel, purged with argon for 25 minutes, and then refluxed at 110° C. for 6 hours. After cooling to room temperature (about 25° C.), the mixture was extracted with saturated brine and dichloromethane, dried over magnesium sulfate, and spin-dried. The resulting precipitate was chromatographed on a silica gel column (using 200-300 mesh silica gel and an eluent of petroleum ether / dichloromethane with a volume ratio of 2:1) to obtain a brown solid (91 mg, a yield of 61%), which is the poly- and fused-ring conjugated macromolecule represented by formula (1-4). 1 H NMR (300MHz, CDCl3): δ8.82(m,2H),8.32(m,2H),8.24(s,2H),8.02(s,2H),7.77(m,4H),7.16(m,16H),2.57 (t,J=8.1Hz,8H),1.63-1.54(m,8H),1.36-1.22(m,24H),0.90-0.82(m,12H).MS(MALDI-TOF):m / z1490.1(M + ).

[0200] The UV-visible absorption spectrum of the poly-fused ring conjugated macromolecule represented by formula (1-4) is as follows: Figure 7 As shown, it has a strong absorption peak in the wavelength range of 700-1200 nm, and the maximum molar extinction coefficient is 7.2×10 4 M –1 cm –1 The film has the strongest absorption at around 988nm; the maximum absorption peak of the film is 30nm red-shifted than that of the solution.

[0201] Cyclic voltammetry curves such as Figure 8As shown, its HOMO energy level is -5.30eV, LUMO energy level is -4.16eV, and band gap is 1.14eV, indicating that the polycyclic fused-ring conjugated macromolecule shown in formula (1-4) has good electron-accepting ability and can match the energy levels of most common electron donor materials.

[0202] Example 5

[0203] This embodiment is used to illustrate the solar cell of the present invention.

[0204] The indium tin oxide (ITO) glass (purchased from Shenzhen CSG Float Glass Co., Ltd.) used as the cathode was first cleaned with detergent, then ultrasonically cleaned with deionized water, acetone, and isopropyl alcohol in sequence. After drying, a 30 nm thick ZnO cathode modification layer was spin-coated and dried at 200°C for 30 minutes for later use.

[0205] 0.8 mg of the polycyclic fused-ring conjugated macromolecule represented by the above formula (1-1) was mixed with 0.7 mg of the polymer donor material PTB7-Th in 0.1 mL of chloroform to obtain a mixed solution, which was then spin-coated on the above ZnO layer. After drying, a light-harvesting active layer (effective area of ​​4 mm2) was obtained. 2 ). Vacuum on the active layer (absolute pressure of 2×10 -5 MoO3 (purchased from J&K Technology Co., Ltd.) with a thickness of about 5 nm and metal Ag with a thickness of about 80 nm were evaporated as the anode of the solar cell.

[0206] A solar light source was simulated using an AM1.5 filter (model XES-70S1 from SAN-EI ELECTRIC Co., Ltd.) at 100 mW / cm 2 The photovoltaic performance of the device was tested under light intensity calibrated using a standard single-crystalline silicon solar cell (purchased from VLSI Standards Inc.). The resulting IV curve was measured using a Keithley 2450 Source-Measure Unit and controlled by a computer using Labview software.

[0207] The IV curve obtained is as follows Figure 9 As shown. Figure 9 The IV curve shown can be used to obtain the open circuit voltage V of the solar cell. OC is 0.499V, short-circuit current J SC 9.45 mA·cm -2 , the fill factor FF is 61.7% and the photoelectric conversion efficiency PCE is 2.91%.

[0208] Example 6

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

[0210] The indium tin oxide (ITO) glass (purchased from Shenzhen CSG Float Glass Co., Ltd.) used as the cathode was first cleaned with detergent, then ultrasonically cleaned with deionized water, acetone, and isopropyl alcohol in sequence. After drying, a 30 nm thick PEDOT:PSS anode modification layer was spin-coated and dried at 150°C for 15 minutes for later use.

[0211] 0.8 mg of the polycyclic fused-ring conjugated macromolecule represented by the above formula (1-3) was mixed with 0.7 mg of the polymer donor material PTB7-Th in 0.1 mL of chloroform to obtain a mixed solution, which was then spin-coated on the above PEDOT:PSS layer. After drying, a light-harvesting active layer (effective area of ​​4 mm2) was obtained. 2 A 5 nm thick PDINN cathode modification layer was spin-coated on the active layer and vacuum (absolute pressure of 2×10 -5 Pa) evaporated about 80nm of metal Ag as the cathode of the solar cell.

[0212] A solar light source was simulated using an AM1.5 filter (model XES-70S1 from SAN-EI ELECTRIC Co., Ltd.) at 100 mW / cm 2 The device was tested for photocurrent density under light intensity, which was calibrated using a standard single-crystal silicon solar cell (purchased from VLSI Standards Inc). The dark current density of the device was also measured in the dark state. The resulting IV curve was measured using a Keithley 2450 Source-Measure Unit and controlled by a computer using Labview software. The resulting IV curve is shown in Figure 1. Figure 10 As shown. Figure 10 The IV curve shown can be used to obtain the short-circuit current density J of the photodetector. SC 4.0 mA·cm -2 The dark current density at 0 bias is 3.2×10 -6 mA·cm -2 .

[0213] The device's external quantum efficiency and responsivity were measured using a QE-R3011 system (Enli Technology Co. Ltd). The light intensity at each wavelength was calibrated using a standard single-crystal silicon solar cell (purchased from VLSI Standards Inc). The resulting EQE curve is shown in Figure 1. Figure 11 As shown, the response curve is Figure 12 shown.

[0214] The noise current is measured using the ProPlus 9812D wafer-level 1 / f noise characterization system. The total noise current is as follows: Figure 13 As shown, the total noise current at 210Hz is 3.9×10 -13 A Hz -1 / 2 The device's specific detectivity is obtained as Figure 14 As shown, the highest specific detectivity in the near-infrared region can reach 2.8×10 10 Jones.

[0215] The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, various simple variations of the technical solution of the present invention may be made, including combining the various technical features in any other appropriate manner. These simple variations and combinations should also be regarded as disclosed in the present invention and fall within the scope of protection of the present invention.

Claims

1. A compound represented by formula (1), Formula (1) in, Each group Ar is independently selected from the group represented by the following formula: The group D is selected from one of the groups shown in the following formula: ； Each group B is independently selected from the formula The groups shown; wherein R1 is independently selected from H, fluorine, chlorine, bromine, methyl, and methoxy; Each group E independently represents a substituted or unsubstituted thienyl or ; The substituents are each independently selected from C1-C30 alkyl groups; Each R2 is independently selected from the formula or The groups shown; Y is S; Y' is S; R4 is H; Each X is independently selected from S and Se; R3 are each independently selected from H, C1-C30 alkyl, C1-C30 alkoxy; Each R5 and each R6 are independently selected from C1-C30 alkyl; n is 0 or 1; m is 0 or 1; p is 0 or 1.

2. The compound according to claim 1, characterized in that: Each R5 and each R6 is each independently selected from n-hexyl, n-octyl and 2-ethylhexyl.

3. Quinone intermediate represented by formula (a), Formula (a) in, Each group Ar is independently selected from the group represented by the following formula: Wherein, R1 is independently selected from H, fluorine, chlorine, bromine, methyl, and methoxy.

4. The quinone intermediate according to claim 3, characterized in that: R1 is independently selected from H, fluoro, methyl, methoxy.

5. The method for preparing the quinone intermediate according to claim 3 or 4, comprising the steps of: Under the action of a catalyst, the compound represented by formula (b) reacts with malononitrile in an organic solvent through a Knoevenagel condensation reaction to obtain a quinone intermediate represented by formula (a); Formula (b) In formula (b), the group Ar is as defined in formula (a).

6. The method according to claim 5, characterized in that: The molar ratio of the compound represented by formula (b), malononitrile and the catalyst is 1: (1-100): (1-100); The catalyst is titanium tetrachloride and pyridine in a molar ratio of 1: (0.5-10); The organic solvent is dichloromethane or chloroform; The Knoevenagel condensation reaction comprises the following steps: mixing the compound represented by formula (b), malononitrile and an organic solvent, stirring at 0-100° C. for 10 min-12 h, then adding titanium tetrachloride, stirring at 0-100° C. for 0.5-12 h, and finally adding pyridine, stirring at 0-100° C. for 10 min-12 h.

7. A method for preparing the compound of formula (1) according to any one of claims 1 to 2, comprising the following steps: In the presence of a palladium catalyst, the compound represented by formula (2) is subjected to a coupling reaction with the quinone intermediate represented by formula (a) according to claim 3 or 4 in an organic solvent to obtain a compound represented by formula (1); Formula (2) In formula (2), the group D and the group B are defined the same as in formula (1).

8. The preparation method according to claim 7, characterized in that: The molar ratio of the compound represented by formula (2) to the quinone intermediate represented by formula (a) is 1:(2-100); and / or, The coupling reaction temperature is 20-110°C and the reaction time is 10 min-48 h; and / or, The palladium catalyst is tetrakis(triphenylphosphine)palladium or palladium acetate; the molar ratio of the palladium catalyst to the compound represented by formula (2) is (0.01-0.1):1; and / or, The organic solvent is toluene or tetrahydrofuran.

9. Use of the compound represented by formula (1) according to any one of claims 1 to 2 as an electron donor material and / or electron acceptor material in the preparation of solar cells or photodetectors.

10. A photovoltaic material for preparing a solar cell or a photodetector, comprising the compound represented by formula (1) according to any one of claims 1 to 2.

11. A solar cell, wherein the photovoltaic material thereof contains the compound represented by formula (1) according to any one of claims 1 to 2.

12. The solar cell according to claim 11, wherein: The solar cell comprises a light-harvesting active layer, wherein the electron donor material and / or the electron acceptor material in the light-harvesting active layer contains the compound represented by formula (1) according to any one of claims 1 to 2.

13. A method for preparing a solar cell, comprising the following steps: placing the compound represented by formula (1) according to any one of claims 1 to 2 in a layer containing a photovoltaic material to obtain the solar cell.

14. A photodetector comprising a light-harvesting active layer, wherein the electron donor material and / or the electron acceptor material in the light-harvesting active layer comprises the compound represented by formula (1) according to any one of claims 1 to 2.

15. A method for preparing a photodetector, comprising the steps of forming an electron donor material and / or an electron acceptor material containing the compound represented by formula (1) according to any one of claims 1 to 2 into a light-harvesting active layer to obtain the photodetector.

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