Resonant boron-nitrogen bond compound, preparation method thereof and photoelectric detector

Abstract

The invention relates to the field of organic short-wave infrared electronic materials and organic short-wave infrared dyes, in particular to a resonance boron-nitrogen bond compound, a preparation method thereof and a photoelectric detector. The invention solves the problems of few construction units and single strategy in the molecular structures of the existing organic short-wave infrared photoelectric material and organic short-wave infrared dye. Compared with the prior art, the resonance boron-nitrogen bond compound provided by the invention has the advantages that (1) the structural unit has the properties of high electron affinity, planar molecular skeleton, narrow optical band gap and the like; and (2) small molecules and high molecules based on the structural unit have the characteristics of strong short-wave infrared absorption and low LUMO energy level, and are applied to an organic short-wave infrared detector to realize excellent detection performance. (3) according to the receptor structure unit based on the resonance boron-nitrogen bond and the small molecule and the high molecule based on the receptor structure unit, the preparation method is simple, the reaction yield is high, the expandable structure is rich, and the photoelectric property is greatly adjustable.

Description

Technical Field

[0001] The present invention relates to the fields of organic short-wave infrared optoelectronic materials and organic short-wave infrared dyes, and specifically to resonance boron-nitrogen bond compounds, their preparation methods, and photodetectors. Background Art

[0002] Light with a wavelength range in the 1000nm - 3000nm band that is invisible to the naked eye is called short-wave infrared light, which has the characteristics of little harm to the human eye, good penetrability, excellent recognition ability, etc. Short-wave infrared light detection has great potential in industrial, national defense, and scientific research applications, such as optoelectronic communication, aerospace, environmental monitoring, and biomedicine. Currently, the realization of short-wave infrared light detection mainly relies on epitaxially grown single-crystalline inorganic semiconductors, such as germanium (Ge) and indium gallium arsenide (InGaAs), which usually have high external quantum efficiency (EQE) and responsivity (R). However, due to the need for a strict crystal growth environment and lattice matching with the substrate material, the production cost of these inorganic photodetectors is high, and low-temperature conditions are required to suppress dark current to achieve a high specific detectivity (D*). Organic semiconductors exhibit characteristics such as adjustable bandgap, low cost, low power consumption, and the ability to achieve solution processing and fabricate flexible devices, while organic photodetectors can achieve flexible wearable and room-temperature operation, etc., and have broad application prospects in low-cost civilian fields.

[0003] However, the development of short-wave infrared-responsive organic conjugated materials with an absorption spectrum exceeding 1000nm is currently relatively lagging, which limits the range of material selection and the improvement of device performance. The currently commonly used design strategy is to adopt a quinone structure and combine the intramolecular D-A effect to reduce the bandgap. In addition, the exciton dissociation, charge generation, and collection efficiencies of existing photodiodes have not reached the optimal level, resulting in a still significant gap in the values of responsivity (R) and specific detectivity (D*) compared with traditional visible light detectors, making it difficult to be widely applied in complex scenarios. Therefore, achieving high-sensitivity short-wave infrared detection has become one of the urgent problems to be solved in this field. Summary of the Invention

[0004] In view of this, the technical problem to be solved by the present invention is to provide resonance boron-nitrogen bond compounds, their preparation methods, and photodetectors. The resonance boron-nitrogen bond compounds provided by the present invention have an absorption spectrum exceeding 1000nm and exhibit excellent infrared detection performance when applied to photodetectors.

[0005] The present invention provides resonance boron-nitrogen bond compounds, which have a structure of Formula 1 or Formula 2;

[0006]

[0007] wherein, n is an integer from 2 to 200;

[0008] R1 and R2 are independently selected from self-dissolving groups;

[0009] R3 is selected from a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a cyano group, a p-trifluoromethylphenyl group, a p-2,4,6-tris(trifluoromethyl)phenyl group, a pentafluorophenyl group, and a phenyl group substituted with a C2-C 20 alkyl group; or R3 and B where it is located together form a boron fluorene group or an oxa-boron fluorene group;

[0010] A1 is selected from a substituted or unsubstituted C4-C 300 aryl group or a substituted or unsubstituted C4-C 300 heteroaryl group; preferably, A1 is selected from a substituted or unsubstituted C4-C 274 aryl group or a substituted or unsubstituted C4-C 274 heteroaryl group; more preferably, A1 is selected from a substituted or unsubstituted C4-C 20 aryl group or a substituted or unsubstituted C4-C 20 heteroaryl group;

[0011] A2 is selected from a substituted or unsubstituted C8-C 200 aryl group with an electron-donating ability or a substituted or unsubstituted C6-C 200 heteroaryl group with an electron-donating ability; preferably, A2 is selected from a substituted or unsubstituted C8-C 158 aryl group with an electron-donating ability or a substituted or unsubstituted C6-C 158 heteroaryl group with an electron-donating ability; more preferably, A2 is selected from a substituted or unsubstituted C8-C 62 aryl group with an electron-donating ability or a substituted or unsubstituted C6-C 62 heteroaryl group;

[0012] A3 is selected from a substituted or unsubstituted C3-C5 hydrocarbon group with an electron-withdrawing ability, a substituted or unsubstituted C6-C 150 aryl group with an electron-withdrawing ability or a substituted or unsubstituted C6-C 150 heteroaryl group with an electron-withdrawing ability; preferably, A3 is selected from a substituted or unsubstituted C3-C5 hydrocarbon group with an electron-withdrawing ability, a substituted or unsubstituted C6-C 112 aryl group with an electron-withdrawing ability or a substituted or unsubstituted C6-C 112 heteroaryl group with an electron-withdrawing ability; more preferably, A3 is selected from a substituted or unsubstituted C3-C5 hydrocarbon group with an electron-withdrawing ability, a substituted or unsubstituted C6-C 15 aryl group with an electron-withdrawing ability or a substituted or unsubstituted C6-C 15 heteroaryl group;

[0013] A4 is selected from a substituted or unsubstituted C6-C250 aryl or substituted or unsubstituted C6-C 250 heteroaryl; preferably, A4 is selected from substituted or unsubstituted C6-C 210 aryl or substituted or unsubstituted C6-C 210 heteroaryl; more preferably, A4 is selected from substituted or unsubstituted C6-C 64 aryl or substituted or unsubstituted C6-C 64 heteroaryl.

[0014] Introducing resonance boron-nitrogen bonds into organic conjugated materials is an effective method to achieve ultra-narrow bandgaps and strong short-wave infrared absorption. Resonance boron-nitrogen bonds refer to boron-nitrogen covalent bonds and boron-nitrogen coordination bonds with equal lengths that can be converted into each other. The introduction of resonance boron-nitrogen bonds can enhance the effective conjugation degree within and between molecules, and reduce the bandgap by significantly lowering the LUMO energy level and slightly increasing the HOMO energy level. The resonance boron-nitrogen bond compounds provided in this application achieve high charge affinity through the introduction of resonance boron-nitrogen bonds and the design of a planar molecular backbone, have an extremely low lowest unoccupied molecular orbital (LUMO) energy level, an ultra-narrow optical bandgap, and strong short-wave infrared absorption, and have excellent infrared detection performance in organic short-wave infrared photodetectors; at the same time, they have the advantages of short reaction steps, high reaction yields, rich expandable structures, and significantly adjustable optoelectronic properties.

[0015] Among the resonance boron-nitrogen bond compounds provided by the present invention, the resonance boron-nitrogen bond compound with the structure shown in Formula 1 is a receptor small molecule based on a resonance boron-nitrogen unit, and the resonance boron-nitrogen bond compound with the structure shown in Formula 2 is a conjugated polymer based on a resonance boron-nitrogen unit. The structures of Formula 1 and Formula 2 both have groups A1, R1, R2, and R3. Among them, A1 is one of the groups constituting the backbone of the resonance boron-nitrogen bond compound with the structure shown in Formula 1 or Formula 2. R1 and R2 are independently selected from solubilizing groups, and R1 and R2 can be selected with different lengths as solubilizing side chains. R3, as a substituent group on boron, is selected from a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a phenyl group, a cyano group, a p-trifluoromethylphenyl group, a p-2,4,6-tris(trifluoromethyl)phenyl group, a pentafluorophenyl group, C2-C 20 alkyl-substituted phenyl; or R3 and the B where it is located together form a boron fluorene group or an oxa-boron fluorene group. All possible substitution sites in the resonance boron-nitrogen bond compounds provided by the present invention can be substituted.

[0016] Preferably, A1 is selected from one of the groups with the structures shown in Formula A1-1 to Formula A1-35;

[0017]

[0018]

[0019] In Formulae A1-1 to A1-35, the R e and R f are independently selected from hydrogen, fluorine, chlorine, bromine, -CN, -NO2, substituted or unsubstituted C1-C 32 alkyl, substituted or unsubstituted C1-C 32 alkoxy, substituted or unsubstituted C6-C 28 aryl, substituted or unsubstituted C3-C 28 heteroaryl, and X is an integer from 1 to 28. In particular, the shown in the formula represents the substitution site where the group to which it belongs is linked to other groups.

[0020] Preferably, the R1 and R2 are independently selected from one of Formulae R-1 to R-27:

[0021]

[0022] wherein m, j, x, and y are independently integers from 1 to 28, and p is an integer from 1 to 20. In particular, the shown in the formula represents the substitution site where the group to which it belongs is linked to other groups.

[0023] In the resonance boron-nitrogen bond compound provided by the present invention, A2 and A3 are groups constituting the resonance boron-nitrogen bond compound having the structure shown in Formula 1, wherein A2 has a structure of an electron-donating substituent group, and A3 has a structure of a terminal electron-withdrawing group. Preferably, A2 is selected from one of the groups having the structures shown in Formulae A2-1 to A2-22;

[0024]

[0025] In Formulae A2-1 to A2-22, the R g is selected from substituted or unsubstituted C1-C 32 alkyl, substituted or unsubstituted C1-C 32 alkoxy, substituted or unsubstituted C6-C 28 aryl, substituted or unsubstituted C3-C 28 heteroaryl; X is an integer from 1 to 28; and R4 is selected from solubilizing groups. In particular, the shown in the formula represents the substitution site where the group to which it belongs is linked to other groups.

[0026] A3 is selected from one of the groups having the structures shown in Formulae A3-1 to A3-15;

[0027]

[0028] In Formulae A3-1 to A3-15, the Rh , R i and R j are independently selected from hydrogen, fluorine, chlorine, bromine, -CN, -NO2, substituted or unsubstituted C1-C 32 alkyl, substituted or unsubstituted C1-C 32 alkoxy, substituted or unsubstituted C6-C 28 aryl, substituted or unsubstituted C3-C 28 heteroaryl. In particular, the shown in the formula represents the substitution site where the group to which it belongs is linked to other groups.

[0029] In the resonance boron-nitrogen bond compound provided by the present invention, the A4 is a group constituting the resonance boron-nitrogen bond compound having the structure shown in Formula 2, and the A4 is preferably selected from one of the groups having the structures shown in Formula A4-1 to Formula A4-30;

[0030]

[0031]

[0032] In Formula A4-1 to Formula A4-30, the R k and R l are independently selected from hydrogen, fluorine, chlorine, bromine, -CN, -NO2, substituted or unsubstituted C1-C 32 alkyl, substituted or unsubstituted C1-C 32 alkoxy, substituted or unsubstituted C6-C 28 aryl, substituted or unsubstituted C6-C 28 heteroaryl. In particular, the shown in the formula represents the substitution site where the group to which it belongs is linked to other groups.

[0033] In the resonance boron-nitrogen bond compound provided by the present invention, the resonance boron-nitrogen bond compound having the structure shown in Formula 1 is preferably a compound having the structures shown in Formula 1-1 to Formula 1-39;

[0034]

[0035]

[0036]

[0037]

[0038]

[0039] Among the resonance boron-nitrogen bond compounds provided by the present invention, the resonance boron-nitrogen bond compounds with the structure shown in Formula 2 are preferably the compounds with the structures shown in Formula 2-1 to Formula 2-12;

[0040]

[0041]

[0042] The present invention also provides a preparation method of the resonance boron-nitrogen bond compound according to any one of the above technical solutions, including the following steps:

[0043] React the compound with the structure shown in Formula a and the compound with the structure shown in Formula b, and then react the obtained product of the reaction with the compound with the structure shown in Formula c to obtain the resonance boron-nitrogen bond compound with the structure shown in Formula 1;

[0044] OHC-A2-CHO Formula b; H-A3 Formula c;

[0045] Or,

[0046] React the compound with the structure shown in Formula a and the compound with the structure shown in Formula d to obtain the resonance boron-nitrogen bond compound with the structure shown in Formula 1;

[0047] OHC-A2-A3 Formula d;

[0048] Or,

[0049] React the compound with the structure shown in Formula a and the compound with the structure shown in Formula e, and then subject the obtained product of the reaction to self-polymerization to obtain the resonance boron-nitrogen bond compound with the structure shown in Formula 2;

[0050] OHC-A4-X a Formula e;

[0051] In Formula e, the indicated X a is selected from halogens; preferably, the said X a is Br.

[0052] In Formulas a to e, the said R1, R2, R3, A1, A2, A3, A4 are the same as above and will not be elaborated herein.

[0053] In the first aspect of the present invention, a compound having the structure shown in formula a and a compound having the structure shown in formula b can be reacted, and then the reaction product obtained is reacted with a compound having the structure shown in formula c to obtain a resonance boron-nitrogen bond compound having the structure shown in formula 1. Specifically, under the action of piperidine and acetic acid, the compound having the structure shown in formula a and the compound having the structure shown in formula b are reacted in an organic solvent, and then under the action of pyridine, the reaction product obtained is reacted with the compound having the structure shown in formula c in an organic solvent to obtain a resonance boron-nitrogen bond compound having the structure shown in formula 1. In certain embodiments of the present invention, the synthesis of the resonance boron-nitrogen bond compound having the structure shown in formula 1 is carried out according to the following reaction formula:

[0054]

[0055] The specific process of the above reaction formula includes: under the protection of an inert atmosphere, the compound having the structure shown in formula a and the compound having the structure shown in formula b are dissolved in a rectified organic solvent, and a Knoevenagel condensation reaction is carried out under the action of piperidine and acetic acid to obtain a precursor Pr-1 molecule; this precursor will be used in the synthesis of a small molecule acceptor with an electron-withdrawing end group connected by a double bond. Specifically, the precursor Pr-1 molecule and the compound having the structure shown in formula c are subjected to a Knoevenagel condensation reaction in an organic solvent under the action of pyridine, and then separated and purified by column chromatography to obtain a resonance boron-nitrogen bond compound having the structure shown in formula 1.

[0056] Preferably, the water content of the rectified organic solvent is 20 ppm to 500 ppm. Preferably, the organic solvents are each selected from one of dichloromethane, chloroform, tetrahydrofuran, toluene, benzene, o-dichlorobenzene, and 1,4-dioxane. Preferably, the temperature for the reaction of the compound having the structure shown in formula a and the compound having the structure shown in formula b in the present invention is 80 °C to 140 °C, and the time is 1 h to 8 h; the temperature for the reaction of the reaction product obtained and the compound having the structure shown in formula c is 55 °C to 120 °C, and the reaction time is 8 h to 24 h.

[0057] Preferably, the molar ratio of the compound having the structure shown in formula a and the compound having the structure shown in formula b in the present invention is 1:(4 to 10); the molar ratio of the compound having the structure shown in formula a and piperidine is 1:(2 to 6); the molar ratio of piperidine and acetic acid is 1:(1 to 5). Preferably, the molar ratio of the reaction product obtained and the compound having the structure shown in formula c is 1:(3 to 8); the molar ratio of the reaction product obtained and pyridine is 1:(10 to 50). Preferably, the molar concentration of each raw material in its respective reaction solution is 0.0002 M to 0.001 M.

[0058] In the second aspect of the present invention, the compound of the structure shown by formula a and the compound of the structure shown by formula d can also be reacted to obtain the resonance boron-nitrogen bond compound of the structure shown by formula 1. Specifically, under the action of piperidine and acetic acid, the compound of the structure shown by formula a and the compound of the structure shown by formula d are reacted in an organic solvent to obtain the resonance boron-nitrogen bond compound of the structure shown by formula 1. In certain embodiments of the present invention, the synthesis of the resonance boron-nitrogen bond compound of the structure shown by formula 1 is carried out according to the following reaction formula:

[0059]

[0060] The specific process of the above reaction formula includes: under the protection of an inert atmosphere, the compound of the structure shown by formula a and the compound of the structure shown by formula d are dissolved in a rectified organic solvent, and a Knoevenagel condensation reaction is carried out under the action of piperidine and acetic acid, and then separated and purified by column chromatography to obtain the resonance boron-nitrogen bond compound of the structure shown by formula 1.

[0061] Preferably, the water content of the rectified organic solvent is 20 ppm to 500 ppm. Preferably, the organic solvent is selected from one of dichloromethane, chloroform, tetrahydrofuran, toluene, benzene, o-dichlorobenzene, and 1,4-dioxane. Preferably, the temperature for reacting the compound of the structure shown by formula a and the compound of the structure shown by formula d in the present invention is 80 °C to 140 °C, and the time is 1 h to 8 h.

[0062] Preferably, the molar ratio of the compound of the structure shown by formula a to the compound of the structure shown by formula d in the present invention is 1:(3 to 10); the molar ratio of the compound of the structure shown by formula a to piperidine is 1:(3 to 8); the molar ratio of piperidine to acetic acid is 1:(1 to 5). Preferably, the molar concentration of each raw material in the reaction solution where it is located is 0.0002 M to 0.001 M.

[0063] In the third aspect of the present invention, the compound of the structure shown by formula a and the compound of the structure shown by formula e can be reacted, and then the reaction product is subjected to self-polymerization to obtain the resonance boron-nitrogen bond compound of the structure shown by formula 2. Specifically, under the action of piperidine and acetic acid, the compound of the structure shown by formula a and the compound of the structure shown by formula e are reacted in an organic solvent, and then the reaction product and an alkylbisstannane salt and a Stille polymerization catalyst are subjected to a Stille polymerization reaction, or the reaction product and a Yamamoto polymerization catalyst are subjected to a Yamamoto polymerization reaction to obtain the resonance boron-nitrogen bond compound of the structure shown by formula 2. In certain embodiments of the present invention, the synthesis of the resonance boron-nitrogen bond compound of the structure shown by formula 2 is carried out according to the following reaction formula:

[0064]

[0065] The specific process of the above reaction formula includes: under the protection of an inert atmosphere, dissolving the compound with the structure shown in formula a and the compound with the structure shown in formula e in a rectified organic solvent, and carrying out a Knoevenagel condensation reaction under the action of piperidine and acetic acid to obtain monomer m-1 molecules; under the protection of an inert atmosphere, dissolving the monomer m-1 molecules, an alkyl bisstannane salt and a catalyst in a rectified organic solvent, and carrying out a Stille polymerization reaction under the conditions of avoiding light and heating under reflux. After the reaction is completed, a homopolymer based on a resonance boron-nitrogen unit, that is, a resonance boron-nitrogen compound with the structure shown in formula 2, is obtained by purification; alternatively, under the protection of an inert atmosphere, dissolving the monomer m-1 molecules and a catalyst in a rectified organic solvent, and carrying out a Yamamoto polymerization reaction under the conditions of avoiding light and heating under reflux. After the reaction, purification is carried out to obtain a homopolymer based on a resonance boron-nitrogen unit, that is, a resonance boron-nitrogen compound with the structure shown in formula 2.

[0066] Preferably, the water content of the rectified organic solvent is 20 ppm to 500 ppm. Preferably, the organic solvents are each independently selected from one of dichloromethane, chloroform, tetrahydrofuran, toluene, benzene, o-dichlorobenzene, and 1,4-dioxane. Preferably, the Stille polymerization catalyst is selected from one or more of tris(dibenzylideneacetone)dipalladium, tris(o-methylphenyl)phosphine, or tetrakis(triphenylphosphine)palladium; the Yamamoto polymerization catalyst is selected from one or more of Ni(COD)2, bipyridine, or cyclooctadiene. Preferably, the alkyl bisstannane salt is hexanorbutylditin, and its structure is

[0067] Preferably, in the present invention, the temperature for reacting the compound with the structure shown in formula a and the compound with the structure shown in formula e is 80 °C to 140 °C, and the time is 1 h to 8 h; the temperature for the self-polymerization of the reaction product is 55 °C to 140 °C, and the reaction time is 1 h to 48 h; if the self-polymerization is a Stille polymerization reaction, the temperature for the self-polymerization is 80 °C to 140 °C, and the reaction time is 1 h to 48 h; if the self-polymerization is a Yamamoto polymerization reaction, the temperature for the self-polymerization is 55 °C to 140 °C, and the reaction time is 1 h to 48 h.

[0068] Preferably, the molar ratio of the compound of the structure shown by formula a to the compound of the structure shown by formula e is 1:(2 - 6); the molar ratio of the compound of the structure shown by formula a to piperidine is 1:(2 - 6); the molar ratio of piperidine to acetic acid is 1:(1 - 5). If the Stille polymerization reaction is carried out in the present invention, the molar ratio of the compound of the structure shown by formula a, alkyl bisstannane, and Stille polymerization catalyst is 1:(1 - 1.05):(0.05 - 0.25). In an embodiment of the present invention, the Stille polymerization reaction is carried out, and the molar ratio of the compound of the structure shown by formula a, alkyl bisstannane, tris(dibenzylideneacetone)dipalladium, and tris(o-tolyl)phosphine is 1:(1 - 1.05):(0.01 - 0.05):(0.04 - 0.2). In another embodiment of the present invention, the Stille polymerization reaction is carried out, and the molar ratio of the compound of the structure shown by formula a, alkyl bisstannane, and tetrakis(triphenylphosphine)palladium is 1:(1 - 1.05):(0.01 - 0.05). If the Yamamoto polymerization reaction is carried out in the present invention, the molar ratio of the compound of the structure shown by formula a to the Yamamoto polymerization catalyst is 1:(9 - 15). In another embodiment of the present invention, the Yamamoto polymerization reaction is carried out, and the molar ratio of the compound of the structure shown by formula a, Ni(COD)2, bipyridine, and cyclooctadiene is 1:(3 - 5):(3 - 5):(3 - 5), preferably 1:4:4:4. Preferably, the molar concentration of each raw material in the reaction solution where it is located is 0.0002M - 0.001M.

[0069] The compound of the structure shown by formula a in the present invention is also called dimethyl BIP monomer, and it can be obtained by carrying out a borane reaction on a borane precursor, and the structure of the borane precursor is Specifically, the borane reaction is carried out on the borane precursor, an oxidant, and a borane reagent to obtain the compound of the structure shown by formula a. In some embodiments of the present invention, the synthesis of the compound of the structure shown by formula a is carried out according to the following reaction formula:

[0070]

[0071] The specific process of the above reaction formula includes: under the protection of an inert atmosphere, dissolving the borane precursor in a rectified organic solvent, then successively adding an oxidant and a borane reagent, carrying out a borane reaction under heating conditions, and then separating and purifying by column chromatography to obtain the compound of the structure shown by formula a.

[0072] Preferably, the organic solvent is one of dichloromethane, tetrahydrofuran, toluene, o-dichlorobenzene, and 1,4-dioxane. Preferably, the water content of the rectified organic solvent is 20 ppm to 500 ppm. The borane reagent of the present invention can be conventionally selected according to the structure of the R3 group. Preferably, the borane reagent is selected from the mixture of boron trifluoride etherate and an organic base, boron trichloride, boron tribromide, boron triiodide, triphenylboron, the mixture of trimethylsilyl cyanide and tin tetrachloride, tris(trifluoromethylphenyl)boron, tris(2,4,6-tris(trifluoromethyl)phenyl)boron, tris(pentafluorophenyl)boron, 5-chloro-5H-dibenzo[b,d]borole, and 10-chloro-10H-dibenzo[b,e][1,4]oxaborole. Preferably, the oxidant is 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ). Preferably, the reaction temperature of the borane reaction is 20°C to 30°C, preferably 25°C, and the reaction time is 12 h to 24 h.

[0073] The present invention also provides an application of the resonance boron-nitrogen bond compound according to any one of the above technical solutions in the preparation of a photodetector. Specifically, the present invention provides a photodetector, which is an organic photovoltaic type short-wave infrared detector or an organic optoelectronic transistor type short-wave infrared detector;

[0074] The organic photovoltaic type short-wave infrared detector of the present invention includes: a cathode, a cathode interface layer disposed on the cathode, an active layer disposed on the cathode interface layer, an anode interface layer disposed on the active layer, and an anode disposed on the anode interface layer. The active layer is composed of a donor material and the resonance boron-nitrogen bond compound according to any one of the above technical solutions; the resonance boron-nitrogen bond compound serves as an electron acceptor material in the organic optoelectronic transistor type short-wave infrared detector, and is preferably a resonance boron-nitrogen bond compound having the structure shown in Formula 1. The organic photovoltaic type short-wave infrared detector of the present invention further includes a substrate. If the organic photovoltaic type short-wave infrared detector is an inverted device structure, its cathode is disposed on the substrate; if the organic photovoltaic type short-wave infrared detector is a normal device structure, its anode is disposed on the substrate. Specifically, the active layer of the present invention is composed of a donor material and the resonance boron-nitrogen bond compound in a mass ratio of (1 to 10):(1 to 10), and the thickness can be 30 nm to 600 nm; preferably, the donor material is one or more of P3HT, PTB7-Th, PBDB-T, or PM6. Preferably, the cathode is ITO; the cathode interface layer is ZnO with a thickness of 10 nm to 40 nm; the anode interface layer is MoO3 with a thickness of 10 nm to 40 nm; the anode is Al with a thickness of 60 nm to 140 nm.

[0075] If the organic photovoltaic short-wave infrared detector of the present invention is an inverted device structure, it can be prepared by the following steps: First, clean the substrate and the cathode, set the cathode on the substrate, then coat the cathode interface layer on the cathode, and then spin-coat the active layer material dissolved in the processing solvent on the cathode interface layer. After post-treatment, an active layer is formed. Finally, an anode interface layer and an anode are sequentially covered on the active layer to obtain an organic photovoltaic short-wave infrared detector with an inverted device structure. Preferably, the processing solvent is chloroform, chlorobenzene, o-dichlorobenzene, toluene or tetrahydrofuran, and the total concentration of the dissolved donor material and acceptor material is 5 mg / mL to 40 mg / mL. Preferably, the post-treatment includes one or more of thermal annealing or solvent vapor annealing; the temperature of the thermal annealing is 60°C to 220°C, and the time of the thermal annealing is 1 min to 120 min; the solvent for the solvent vapor annealing is one or more of dichloromethane, chloroform, ether or toluene, and the time of the solvent vapor annealing is 0.1 min to 10 min. The active layer material dissolved in the processing solvent of the present invention may also contain additives, and the additives include but are not limited to one or more of 1-chloronaphthalene, 1,8-diiodooctane, 1-phenylnaphthalene, 1,3,5-tribromobenzene or diiodomethane, etc.; the introduction of the additives can regulate the film morphology and improve the device performance.

[0076] If the organic photovoltaic short-wave infrared detector of the present invention is a normal device structure, it can be prepared by the following steps: First, clean the substrate and the anode, set the anode on the substrate, coat the anode interface layer on the anode, and then spin-coat the active layer material dissolved in the processing solvent on the anode interface layer. After post-treatment, an active layer is formed. Finally, a cathode interface layer and a cathode are sequentially covered on the active layer to obtain an organic photovoltaic short-wave infrared detector with a normal device structure. Preferably, the processing solvent is chloroform, chlorobenzene, o-dichlorobenzene, toluene or tetrahydrofuran, and the total concentration of the dissolved donor material and acceptor material is 5 mg / mL to 40 mg / mL. Preferably, the post-treatment includes one or more of thermal annealing or solvent vapor annealing; the temperature of the thermal annealing is 60°C to 220°C, and the time of the thermal annealing is 1 min to 120 min; the solvent for the solvent vapor annealing is one or more of dichloromethane, chloroform, ether or toluene, and the time of the solvent vapor annealing is 0.1 min to 10 min. The active layer material dissolved in the processing solvent of the present invention may also contain additives, and the additives include but are not limited to one or more of 1-chloronaphthalene, 1,8-diiodooctane, 1-phenylnaphthalene, 1,3,5-tribromobenzene or diiodomethane, etc.; the introduction of the additives can regulate the film morphology and improve the device performance.

[0077] The organic optoelectronic transistor type short-wave infrared detector of the present invention is preferably a bottom-gate top-contact structure, which sequentially includes, from top to bottom: heavily doped silicon, silicon dioxide provided on the heavily doped silicon, a charge transport layer provided on the silicon dioxide, an electrode provided on the charge transport layer, and a polymer light-absorbing layer provided on the electrode. The polymer light-absorbing layer is composed of the resonance boron-nitrogen bond compound described in any of the above technical solutions; the resonance boron-nitrogen bond compound serves as an electron acceptor and an infrared photon absorption material in the organic optoelectronic transistor type short-wave infrared detector, and is preferably selected from the resonance boron-nitrogen bond compounds having the structure shown in Formula 2. Preferably, the concentration of the polymer light-absorbing layer of the present invention is 3 mg / mL to 20 mg / mL; the thickness of the silicon dioxide is 100 nm to 500 nm; the charge transport layer is graphene with a thickness of 1 nm to 20 nm; the electrode is a co-evaporated alloy of titanium and gold, wherein the thickness of titanium is 5 nm to 30 nm, and the thickness of gold is 40 nm to 200 nm.

[0078] The organic optoelectronic transistor type short-wave infrared detector of the present invention is prepared by the following steps: silicon dioxide is provided on heavily doped silicon to obtain a substrate; after cleaning the obtained substrate, the charge transport layer is transferred onto the substrate so that the charge transport layer is provided on the silicon dioxide, then an electrode is covered on the charge transport layer, and finally the resonance boron-nitrogen bond compound is dissolved by a processing solvent and coated on the charge transport layer as an electron acceptor and an infrared photon absorption material, and a polymer light-absorbing layer is formed through post-treatment to obtain a final device. Preferably, the processing solvent is selected from dichloromethane, chloroform, chlorobenzene, o-dichlorobenzene, toluene or tetrahydrofuran. Preferably, the post-treatment includes one or more of thermal annealing or solvent vapor annealing; the temperature of the thermal annealing is 60 °C to 220 °C, and the time of the thermal annealing is 1 min to 120 min; the solvent for the solvent vapor annealing is one or more of dichloromethane, chloroform, diethyl ether or toluene, and the time of the solvent vapor annealing is 0.1 min to 10 min.

[0079] The present invention provides a resonance boron-nitrogen bond compound, a preparation method thereof, and a photodetector. The present invention develops and designs an organic structural unit based on a resonance boron-nitrogen bond, as well as a small molecule resonance boron-nitrogen bond compound and a polymer resonance boron-nitrogen bond compound based on this unit, solving the problems of few building units and single strategy in the existing organic short-wave infrared optoelectronic materials and organic short-wave infrared dye molecular structures. Compared with the prior art, the resonance boron-nitrogen bond compound provided by the present invention has the following advantages: (1) This structural unit has properties such as high electron affinity, a planar molecular skeleton, and a narrow optical band gap. (2) Small molecules and polymers based on this structural unit have strong absorption in the short-wave infrared region and low LUMO energy levels, and excellent detection performance is achieved when applied to organic short-wave infrared detectors. (3) The receptor structural unit based on the resonance boron-nitrogen bond in the present invention, as well as small molecules and polymers based on this unit, have a simple preparation method, high reaction yields, rich expandable structures, and greatly adjustable optoelectronic properties. Experiments show that the absorption spectrum of the resonance boron-nitrogen bond compound provided by the present invention exceeds 1000 nm, and it has excellent infrared detection performance when applied to a photodetector. Description of the Drawings

[0080] Figure 1 It is the film-state ultraviolet-visible short-wave infrared absorption spectrum diagram of small molecules L1, L4, and L5 based on the resonance boron-nitrogen unit BIP;

[0081] Figure 2 It is the film-state ultraviolet-visible short-wave infrared absorption spectrum diagram of small molecules L6, L8, and L12 based on the resonance boron-nitrogen unit BIP;

[0082] Figure 3 It is the film-state ultraviolet-visible short-wave infrared absorption spectrum diagram of small molecules L13, L14, and L16 based on the resonance boron-nitrogen unit BIP;

[0083] Figure 4 It is the film-state ultraviolet-visible short-wave infrared absorption spectrum diagram of polymers L25, L26, L29, and L31 based on the resonance boron-nitrogen unit BIP;

[0084] Figure 5 It is the device structure schematic diagram of the photovoltaic detector described in the present invention;

[0085] Figure 6 It is the EQE curve diagram of an inverted organic photovoltaic detector based on resonance boron-nitrogen small molecules L1, L4, L5, L6, and L8;

[0086] Figure 7 It is the EQE curve diagram of an inverted organic photovoltaic detector based on resonance boron-nitrogen small molecules L12, L13, L14, and L16;

[0087] Figure 8Responsivity curves of organic photovoltaic detectors based on resonance boron-nitrogen small molecules L1, L4, L5, L6 and L8;

[0088] Figure 9 Responsivity curves of organic photovoltaic detectors based on resonance boron-nitrogen small molecules L12, L13, L14 and L16;

[0089] Figure 10 Dark current curves of organic photovoltaic detectors based on resonance boron-nitrogen small molecules L1, L4, L5, L6 and L8;

[0090] Figure 11 Dark current curves of organic photovoltaic detectors based on resonance boron-nitrogen small molecules L12, L13, L14 and L16;

[0091] Figure 12 Schematic diagram of the device structure of the phototransistor detector described in the present invention;

[0092] Figure 13 Responsivity curves of organic phototransistor detectors based on resonance boron-nitrogen polymers L25, L26, L29 and L31;

[0093] Figure 14 Noise current density curves of organic phototransistor detectors based on resonance boron-nitrogen polymers L25, L26, L29 and L31;

[0094] Figure 15 Film-state ultraviolet-visible short-wave infrared absorption spectra of small molecules R35, R36 and R37 based on resonance boron-nitrogen unit BODIPY;

[0095] Figure 16 Film-state ultraviolet-visible short-wave infrared absorption spectra of polymers R38, R39 and R40 based on resonance boron-nitrogen unit BODIPY. Detailed implementation manners

[0096] The present invention discloses resonance boron-nitrogen bond compounds, their preparation methods and photodetectors. Those skilled in the art can draw on the content of this article and appropriately modify the process parameters to achieve. It should be particularly noted that all similar substitutions and modifications are obvious to those skilled in the art, and they are all regarded as included in the present invention. The methods and applications of the present invention have been described through preferred embodiments, and those skilled in the art can obviously make changes or appropriate modifications and combinations to the methods and applications in this article without departing from the content, spirit and scope of the present invention to implement and apply the technology of the present invention.

[0097] The following further elaborates on the present invention in conjunction with embodiments:

[0098] Example 1

[0099] A unit small molecule acceptor L1 based on a resonance boron-nitrogen bond, and its structural formula is as shown in formula L1:

[0100]

[0101] Its synthetic route is as follows:

[0102]

[0103] Synthesis of compound 1-1:

[0104] Under an argon atmosphere, add ultradry dichloromethane (20.0 mL) to a 100 mL round-bottom flask containing the boron precursor (0.40 g, 1.38 mmol). Dissolve 0.35 g of DDQ (1.1 eq) in 6 mL of toluene, and add it dropwise to the reaction system. Rinse the remaining DDQ in the syringe with ultradry dichloromethane, and react for 3 h. At -78 °C, slowly add 6.19 mL (30 eq.) of DBU and 7.35 mL (40 eq.) of BF3·Et2O dropwise in sequence. After reacting for 5 min, restore to room temperature and react for 5 h. After the reaction system is cooled to room temperature, concentrate it, and purify the crude product by column chromatography to obtain 0.27 g of a dark red liquid with a yield of 33%.

[0105] Synthesis of compound 1-2:

[0106] Add 24 mg (1.0 eq) of compound 1-1, 165 mg (6.0 eq) of CPDT dialdehyde, and 200 mg of molecular sieve into a polymerization tube. Add 20 mL of ultradry toluene under an argon atmosphere. After fully dissolving, add 89 μL of piperidine and 69 μL of glacial acetic acid. Subsequently, react at 85 °C for 1 h. After the system is cooled, extract twice with dichloromethane / water, dry and rotary evaporate. Separate and obtain 36 mg of a pure brown-green product by column chromatography with a yield of 46%.

[0107] Synthesis of compound L1:

[0108] Add 63 mg (1.0 eq) of compound 1-2 and 57 mg (5.0 eq) of 2F-IC into a polymerization tube, and add 20 mL of ultradry chloroform. Add 0.15 mL of pyridine under an argon atmosphere, and then react at 70 °C overnight. The next day, the color of the solution changes from green to brown-blue. After the system is cooled, rotary evaporate and add it to methanol for reverse sedimentation to remove 2F-IC. Subsequently, obtain a solid and separate it by column chromatography to obtain 52 mg with a yield of 62%.

[0109] Elemental analysis structure (C 96 H 90(B2F8N8O2S4): Theoretical values: C, 68.24; H, 5.37; B, 1.28; F, 9.00; N, 6.63; O, 1.89; S, 7.59. Test values: C, 68.26; H, 5.31; N, 6.65.

[0110] MALDI-TOF analysis, theoretical value: 1688.61; experimental value: 1688.6.

[0111] Example 2

[0112] A small molecule acceptor L2 based on a unit with a resonant boron-nitrogen bond, the structural formula is shown as formula L2:

[0113]

[0114] Its synthetic route is as follows:

[0115]

[0116] Synthesis of compound 2-1:

[0117] The synthesis steps and experimental conditions of 2-1 are the same as those of 1-1, only the raw materials are changed.

[0118] Synthesis of compound 1-2:

[0119] Add 58 mg (1.0 eq) of compound 2-1, 275 mg (6.0 eq) of CPDT dialdehyde, 200 mg of molecular sieve into a polymerization tube. Add 20 mL of super-dry toluene under an argon atmosphere. After complete dissolution, add 176 μL of piperidine and 138 μL of glacial acetic acid. Subsequently, react at 85 °C for 1 h. After the system cools down, extract twice with dichloromethane / water, dry and rotary evaporate. The pure product of 73 mg with a yield of 50% is obtained by column chromatography separation.

[0120] Synthesis of compound L2:

[0121] Add 73 mg (1.0 eq) of compound 2-2 and 58 mg (5.0 eq) of 2F-IC into a polymerization tube, and 20 mL of super-dry chloroform. Add 0.16 mL of pyridine under an argon atmosphere, and then react at 70 °C for 18 h. The next day, the color of the solution changes from green to brownish blue. After the system cools down, rotary evaporate and then add it to methanol for anti-sedimentation to remove 2F-IC. Subsequently, the obtained solid is separated by column chromatography to obtain 62 mg of dark red solid with a yield of 65%.

[0122] Elemental analysis structure (C 106 H 110(B2F8N8O6S4): Theoretical values: C, 67.22; H, 5.85; B, 1.14; F, 8.02; N, 5.92; O, 5.07; S, 6.77. Test values: C, 67.35; H, 5.80; N, 5.85.

[0123] MALDI-TOF analysis, theoretical value: 1892.75; experimental value: 1892.8.

[0124] Example 3

[0125] A small molecule acceptor L3 based on a unit with a resonance boron-nitrogen bond, and its structural formula is as shown in formula L3:

[0126]

[0127] Its synthetic route is as follows:

[0128]

[0129] Synthesis of compound 3-1:

[0130] The synthesis steps and experimental conditions of 3-1 are the same as those of 1-1, only the raw materials are changed.

[0131] Synthesis of compound 3-2:

[0132] Add 68 mg (1.0 eq) of compound 3-1, 194 mg (6.0 eq) of alkoxythiophene dialdehyde, and 200 mg of molecular sieve into a polymerization tube. Add 20 mL of ultradry toluene under an argon atmosphere. After complete dissolution, add 176 μL of piperidine and 138 μL of glacial acetic acid. Then react at 75 °C for 1 h. After the system cools down, extract twice with dichloromethane / water, dry and rotary evaporate. Obtain 58 mg of a pure brown-green product by column chromatography, with a yield of 45%.

[0133] Synthesis of compound L3:

[0134] Add 58 mg (1.0 eq) of compound 3-2 and 52 mg (5.0 eq) of 2F-IC into a polymerization tube, and 20 mL of ultradry chloroform. Add 0.13 mL of pyridine under an argon atmosphere, and then react at 60 °C for 14 h. The next day, the color of the solution changes from green to brown-blue. After the system cools down, rotary evaporate and then add it to methanol for reverse sedimentation to remove 2F-IC. Then obtain a solid by column chromatography to obtain 50 mg of a black solid, with a yield of 65%.

[0135] Elemental analysis structure (C 98 H 90(B2F8N8O6S2): Theoretical values: C, 68.69; H, 5.29; B, 1.26; F, 8.87; N, 6.54; O, 5.60; S, 3.74. Test values: C, 68.63; H, 5.25; N, 6.60.

[0136] MALDI-TOF analysis, theoretical value: 1712.65; experimental value: 1712.7.

[0137] Example 4

[0138] A small molecule acceptor L4 based on a unit with a resonant boron-nitrogen bond, and its structural formula is as shown in formula L4:

[0139]

[0140] Its synthetic route is as follows:

[0141]

[0142] Synthesis of compound 4-1:

[0143] The synthesis steps and experimental conditions of 4-1 are the same as those of 1-1, only the raw materials are changed.

[0144] Synthesis of compound 4-2:

[0145] Add 56 mg (1.0 eq) of compound 4-1, 229 mg (5.0 eq) of CPDT dialdehyde, and 200 mg of molecular sieve into a polymerization tube. Add 15 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, add 176 μL of piperidine and 138 μL of glacial acetic acid. Then react at 85 °C for 1 h. After the system cools down, extract twice with dichloromethane / water, dry and rotary evaporate. The pure product of 61 mg with a yield of 42% is obtained by column chromatography.

[0146] Synthesis of compound L4:

[0147] Add 61 mg (1.0 eq) of compound 4-2 and 55 mg (5.0 eq) of 2Cl-IC into a polymerization tube, and 20 mL of ultra-dry chloroform. Add 0.15 mL of pyridine under an argon atmosphere, and then react at 65 °C for 12 h. The next day, the color of the solution changes from green to blue. After the system cools down, rotary evaporate and then add it to methanol for reverse sedimentation to remove 2Cl-IC. The resulting solid is separated by column chromatography to obtain 56 mg of a black-red solid with a yield of 68%.

[0148] Elemental analysis structure (C 110 H 98 B2C l4(F4N8O2S4): Theoretical values: C, 68.40; H, 5.11; B, 1.12; Cl, 7.34; F, 3.93; N, 5.80; O, 1.66; S, 6.64. Test values: C, 68.25; H, 5.10; N, 5.76.

[0149] MALDI-TOF analysis, theoretical value: 1928.56; experimental value: 1928.6.

[0150] Example 5

[0151] A small molecule acceptor L5 based on a unit with a resonant boron-nitrogen bond, and its structural formula is as shown in formula L5:

[0152]

[0153] Its synthetic route is as follows:

[0154]

[0155] Synthesis of compound 5-1:

[0156] The synthesis steps and experimental conditions of 5-1 are the same as those of 1-1, only the raw materials are changed.

[0157] Synthesis of compound 5-2:

[0158] Add 44 mg (1.0 eq) of compound 5-1, 284 mg (5.0 eq) of CPDT dialdehyde, and 200 mg of molecular sieve into a polymerization tube. Add 15 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, add 176 μL of piperidine and 138 μL of glacial acetic acid. Then react at 85 °C for 1 h. After the system cools down, extract with dichloromethane / water twice, dry and rotary evaporate. The pure product is obtained by column chromatography separation, 64 mg, with a yield of 42%.

[0159] Synthesis of compound L5:

[0160] Add 64 mg (1.0 eq) of compound 5-2 and 65 mg (6.0 eq) of 2Cl-IC into a polymerization tube, and 20 mL of ultra-dry chloroform. Add 0.15 mL of pyridine under an argon atmosphere, and then react at 65 °C for 12 h. The next day, the color of the solution changes from green to blue. After the system cools down, rotary evaporate and then add it to methanol for reverse sedimentation to remove 2Cl-IC. The resulting solid is separated by column chromatography to obtain 56 mg of black solid, with a yield of 66%.

[0161] Elemental analysis structure (C 114 H 88 B2C l4 F4N 12O2S4): Theoretical values: C, 67.59; H, 4.38; B, 1.07; Cl, 7.00; F, 3.75; N, 8.30; O, 1.58; S, 6.33. Test values: C, 67.60; H, 4.35; N, 8.25.

[0162] MALDI-TOF analysis, theoretical value: 2022.49; experimental value: 2022.5.

[0163] Example 6

[0164] A small molecule acceptor L6 based on a unit with a resonance boron-nitrogen bond, and its structural formula is as shown in formula L6:

[0165]

[0166] Its synthetic route is as follows:

[0167]

[0168] Synthesis of compound 6-1:

[0169] The synthesis steps and experimental conditions of 6-1 are the same as those of 1-1, only the raw materials and reactants are changed.

[0170] Synthesis of compound 6-2:

[0171] Add 134 mg (1.0 eq) of compound 6-1, 229 mg (5.0 eq) of CPDT dialdehyde, and 200 mg of molecular sieve into a polymerization tube. Add 15 mL of super-dry toluene under an argon atmosphere. After complete dissolution, add 176 μL of piperidine and 138 μL of glacial acetic acid. Then react at 85 °C for 1 h. After the system cools down, extract twice with dichloromethane / water, dry and rotary evaporate. The pure product of 94 mg is obtained by column chromatography separation, with a yield of 42%.

[0172] Synthesis of compound L6:

[0173] Add 94 mg (1.0 eq) of compound 6-2 and 66 mg (6.0 eq) of 2Cl-IC into a polymerization tube, and 20 mL of super-dry chloroform. Add 0.15 mL of pyridine under an argon atmosphere, and then react at 65 °C for 12 h. The next day, the color of the solution changes from green to blue. After the system cools down, rotary evaporate and then add it to methanol for reverse sedimentation to remove 2Cl-IC. The resulting solid is separated by column chromatography to obtain 77 mg of black solid, with a yield of 67%.

[0174] Elemental analysis structure (C 168 H 204 B2Cl4N 10O2S5): Theoretical values: C, 74.21; H, 7.56; B, 0.80; Cl, 5.21; N, 5.15; O, 1.18; S, 5.89. Test values: C, 74.18; H, 7.42; N, 5.17.

[0175] MALDI-TOF analysis, theoretical value: 2715.37; experimental value: 2715.4.

[0176] Example 7

[0177] A small molecule acceptor L7 based on a unit with a resonant boron-nitrogen bond, and its structural formula is as shown in formula L7:

[0178]

[0179] Its synthetic route is as follows:

[0180]

[0181] Synthesis of compound 7-1:

[0182] The synthesis steps and experimental conditions of 7-1 are the same as those of 1-1, only the raw materials and reactants are changed.

[0183] Synthesis of compound 7-2:

[0184] Add 48 mg (1.0 eq) of compound 7-1, 335 mg (6.0 eq) of bithiophene dialdehyde, and 200 mg of molecular sieve into a polymerization tube. Add 15 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, add 180 μL of piperidine and 140 μL of glacial acetic acid. Then react at 85 °C for 1 h. After the system cools down, extract twice with dichloromethane / water, dry and rotary evaporate. The brown-green pure product (68 mg) is obtained by column chromatography separation, and the yield is 43%.

[0185] Synthesis of compound L7:

[0186] Add 68 mg (1.0 eq) of compound 7-2 and 58 mg (6.0 eq) of 2F-IC into a polymerization tube, and 18 mL of ultra-dry chloroform. Add 0.15 mL of pyridine under an argon atmosphere, and then react at 65 °C for 16 h. The next day, the color of the solution changes from green to blue. After the system cools down, rotary evaporate and then add it to methanol for reverse sedimentation to remove 2F-IC. Then the obtained solid is separated by column chromatography to obtain 59 mg of black solid, and the yield is 71%.

[0187] Elemental analysis structure (C 118 H 126(B2F8N8O2S4): Theoretical values: C, 71.21; H, 6.38; B, 1.09; F, 7.64; N, 5.63; O, 1.61; S, 6.44. Test values: C, 71.20; H, 6.35; N, 5.60.

[0188] MALDI-TOF analysis, theoretical value: 1988.89; experimental value: 1988.9.

[0189] Example 8

[0190] A small molecule acceptor L8 based on a unit with a resonant boron-nitrogen bond, the structural formula is as shown in formula L8:

[0191]

[0192] Its synthetic route is as follows:

[0193]

[0194] Synthesis of compound 8-1:

[0195] The synthesis steps and experimental conditions of 8-1 are the same as those of 1-1, only the raw materials are changed.

[0196] Synthesis of compound 8-2:

[0197] Add 76 mg (1.0 eq) of compound 8-1, 386 mg (6.0 eq) of CPDT dialdehyde, and 200 mg of molecular sieve into a polymerization tube. Add 15 mL of super-dry toluene under an argon atmosphere. After complete dissolution, add 190 μL of piperidine and 150 μL of glacial acetic acid. Then react at 85 °C for 2 h. After the system cools down, extract with dichloromethane / water twice, dry and rotary evaporate. The pure product of 73 mg is obtained by column chromatography separation, with a yield of 36%.

[0198] Synthesis of compound L8:

[0199] Add 73 mg (1.0 eq) of compound 8-2 and 50 mg (6.0 eq) of 2F-IC into a polymerization tube, and 18 mL of super-dry chloroform. Add 0.15 mL of pyridine under an argon atmosphere, and then react at 65 °C for 16 h. The next day, the color of the solution changes from green to blue. After the system cools down, rotary evaporate and then add it to methanol for reverse sedimentation. The resulting solid is separated by column chromatography to obtain 53 mg of a black solid, with a yield of 60%.

[0200] Elemental analysis structure (C 152 H 136 B2F8N 10O2S4): Theoretical values: C, 74.92; H, 5.63; B, 0.89; F, 6.24; N, 5.75; O, 1.31; S, 5.26. Test values: C, 74.90; H, 5.60; N, 5.72.

[0201] MALDI-TOF analysis, theoretical value: 2434.98; experimental value: 2435.0.

[0202] Example 9

[0203] A small molecule acceptor L9 based on a unit with a resonant boron-nitrogen bond, and its structural formula is as shown in formula L9:

[0204]

[0205] Its synthesis route is as follows:

[0206]

[0207] Synthesis of compound 9-1:

[0208] The synthesis steps and experimental conditions of 9-1 are the same as those of 1-1, only the raw materials are changed.

[0209] Synthesis of compound 9-2:

[0210] Add 75 mg (1.0 eq) of compound 9-1, 185 mg (6.0 eq) of CPDT dialdehyde, and 200 mg of molecular sieve into a polymerization tube. Add 15 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, add 190 μL of piperidine and 150 μL of glacial acetic acid. Then react at 85 °C for 2 h. After the system cools down, extract twice with dichloromethane / water, dry and rotary evaporate. The pure product of 40 mg in brown-green color is obtained by column chromatography separation, and the yield is 30%.

[0211] Synthesis of compound L9:

[0212] Add 40 mg (1.0 eq) of compound 9-2 and 42 mg (6.0 eq) of 2F-IC into a polymerization tube, and 18 mL of ultra-dry chloroform. Add 0.15 mL of pyridine under an argon atmosphere, and then react at 65 °C for 16 h. The next day, the color of the solution changes from green to blue. After the system cools down, rotary evaporate and then add it to methanol for reverse sedimentation. The solid obtained is separated by column chromatography to obtain 35 mg of black-purple solid, and the yield is 67%.

[0213] Elemental analysis structure (C 102 H 118(B2F8N8O4S2): Theoretical values: C, 69.69; H, 6.77; B, 1.23; F, 8.65; N, 6.37; O, 3.64; S, 3.65. Test values: C, 69.70; H, 6.56; N, 6.30.

[0214] MALDI-TOF analysis, theoretical value: 1756.88; experimental value: 1756.9.

[0215] Example 10

[0216] A small molecule acceptor L10 based on a unit with a resonance boron-nitrogen bond, and its structural formula is as shown in formula L10:

[0217]

[0218] Its synthetic route is as follows:

[0219]

[0220] Synthesis of compound 10-1:

[0221] The synthesis steps and experimental conditions of 10-1 are the same as those of 1-1, only the raw materials are changed.

[0222] Synthesis of compound 10-2:

[0223] Add 55 mg (1.0 eq) of compound 10-1, 274 mg (6.0 eq) of CPDT dialdehyde, and 200 mg of molecular sieve into a polymerization tube. Add 15 mL of super-dry toluene under an argon atmosphere. After complete dissolution, add 190 μL of piperidine and 150 μL of glacial acetic acid. Then react at 85 °C for 2 h. After the system cools down, extract with dichloromethane / water twice, dry and rotary evaporate. The pure product with a brownish-green color, 57 mg, is obtained by column chromatography separation, with a yield of 40%.

[0224] Synthesis of compound L10:

[0225] Add 57 mg (1.0 eq) of compound 10-2 and 55 mg (6.0 eq) of 2F-IC into a polymerization tube, and 18 mL of super-dry chloroform. Add 0.15 mL of pyridine under an argon atmosphere, and then react at 65 °C for 13 h. The next day, the color of the solution changes from green to blue. After the system cools down, rotary evaporate and then add it to methanol for reverse sedimentation. The resulting solid is separated by column chromatography to obtain 48 mg of a black solid, with a yield of 65%.

[0226] Elemental analysis structure (C 104 H 90 B2F 10N8O4S4): Theoretical values: C, 67.31; H, 4.89; B, 1.17; F, 10.24; N, 6.04; O, 3.45; S, 6.91. Test values: C, 67.25; H, 4.80; N, 6.10.

[0227] MALDI-TOF analysis, theoretical value: 1854.60; experimental value: 1854.6.

[0228] Example 11

[0229] A small molecule acceptor L11 based on a unit with a resonance boron-nitrogen bond, and its structural formula is as shown in formula L11:

[0230]

[0231] Its synthetic route is as follows:

[0232]

[0233] Synthesis of compound 11-1:

[0234] The synthesis steps and experimental conditions of 11-1 are the same as those of 1-1, only the raw materials are changed.

[0235] Synthesis of compound 11-2:

[0236] Add 46 mg (1.0 eq) of compound 11-1, 234 mg (6.0 eq) of carbazole dialdehyde, and 200 mg of molecular sieve into a polymerization tube. Add 15 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, add 178 μL of piperidine and 132 μL of glacial acetic acid. Subsequently, react at 85 °C for 3 h. After the system cools down, extract twice with dichloromethane / water, dry and rotary evaporate. The light green pure product (42 mg, yield 35%) is obtained by column chromatography separation.

[0237] Synthesis of compound L11:

[0238] Add 42 mg (1.0 eq) of compound 11-2 and 48 mg (6.0 eq) of 2F-IC into a polymerization tube, and 18 mL of ultra-dry chloroform. Add 0.15 mL of pyridine under an argon atmosphere, and then react at 65 °C for 13 h. The next day, the color of the solution changes from green to blue. After the system cools down, rotary evaporate and then add it to methanol for reverse precipitation. The resulting solid is separated by column chromatography to obtain 41 mg of a black solid with a yield of 72%.

[0239] Elemental analysis structure (C 98 H 80 B2F8N 10O4): Theoretical values: C, 71.98; H, 4.93; B, 1.32; F, 9.29; N, 8.56; O, 3.91. Test values: C, 71.80; H, 4.99; N, 8.50.

[0240] MALDI-TOF analysis, theoretical value: 1634.64; experimental value: 1634.6.

[0241] Example 12

[0242] A small molecule acceptor L12 based on a unit with a resonance boron-nitrogen bond, and its structural formula is as shown in formula L12:

[0243]

[0244] Its synthesis route is as follows:

[0245]

[0246] Synthesis of compound 12-1:

[0247] The synthesis steps and experimental conditions of 12-1 are the same as those of 1-1, only the raw materials are changed.

[0248] Synthesis of compound 12-2:

[0249] Add 128 mg (1.0 eq) of compound 12-1, 275 mg (6.0 eq) of CPDT dialdehyde, and 200 mg of molecular sieve into a polymerization tube. Add 15 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, add 178 μL of piperidine and 132 μL of glacial acetic acid. Then react at 85 °C for 3 h. After the system cools down, extract with dichloromethane / water twice, dry and rotary evaporate. The light green pure product of 87 mg is obtained by column chromatography separation, with a yield of 40%.

[0250] Synthesis of compound L12:

[0251] Add 42 mg (1.0 eq) of compound 12-2 and 63 mg (6.0 eq) of 2Cl-IC into a polymerization tube, and 18 mL of ultra-dry chloroform. Add 0.15 mL of pyridine under an argon atmosphere, and then react at 65 °C for 13 h. The next day, the color of the solution changes from green to blue. After the system cools down, rotary evaporate and then add it to methanol for reverse sedimentation. The resulting solid is separated by column chromatography to obtain 74 mg of black solid, with a yield of 70%.

[0252] Elemental analysis structure (C 168 H 202 B2C l4N8O2S4): Theoretical values: C, 75.94; H, 7.66; B, 0.81; Cl, 5.34; N, 4.22; O, 1.20; S, 4.83. Test values: C, 75.90; H, 7.59; N, 4.13.

[0253] MALDI-TOF analysis, theoretical value: 2653.38; experimental value: 2653.4.

[0254] Example 13

[0255] A small molecule acceptor L13 based on a unit with a resonant boron-nitrogen bond, and its structural formula is as shown in formula L13:

[0256]

[0257] Its synthesis route is as follows:

[0258]

[0259] Synthesis of compound 13-1:

[0260] The synthesis steps and experimental conditions of 13-1 are the same as those of 1-1, only the raw materials are changed.

[0261] Synthesis of compound 13-2:

[0262] Add 62 mg (1.0 eq) of compound 13-1, 275 mg (6.0 eq) of CPDT dialdehyde, and 200 mg of molecular sieve into a polymerization tube. Add 15 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, add 178 μL of piperidine and 132 μL of glacial acetic acid. Then react at 85 °C for 3 h. After the system cools down, extract twice with dichloromethane / water, dry and rotary evaporate. The light green pure product (56 mg, yield 37%) is obtained by column chromatography separation.

[0263] Synthesis of compound L13:

[0264] Add 56 mg (1.0 eq) of compound 13-2 and 51 mg (6.0 eq) of 2F-IC into a polymerization tube, and 18 mL of ultra-dry chloroform. Add 0.15 mL of pyridine under an argon atmosphere, and then react at 65 °C for 13 h. The next day, the color of the solution changes from green to blue. After the system cools down, rotary evaporate and add it to methanol for reverse sedimentation. The resulting solid is separated by column chromatography to obtain 44 mg of black solid, with a yield of 62%.

[0265] Elemental analysis structure (C 110 H 113(B2F8N9O4S4): Theoretical values: C, 68.56; H, 5.91; B, 1.12; F, 7.89; N, 6.54; O, 3.32; S, 6.65. Test values: C, 68.59; H, 5.90; N, 6.35.

[0266] MALDI-TOF analysis, theoretical value: 1925.79; experimental value: 1925.8.

[0267] Example 14

[0268] A small molecule acceptor L14 based on a unit with a resonance boron-nitrogen bond, and its structural formula is as shown in formula L14:

[0269]

[0270] Its synthesis route is as follows:

[0271]

[0272] Synthesis of compound 14-1:

[0273] The synthesis steps and experimental conditions of 14-1 are the same as those of 1-1, only the raw materials are changed.

[0274] Synthesis of compound 14-2:

[0275] Add 89 mg (1.0 eq) of compound 14-1, 275 mg (6.0 eq) of CPDT dialdehyde, and 200 mg of molecular sieve into a polymerization tube. Add 16 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, add 150 μL of piperidine and 115 μL of glacial acetic acid. Then react at 85 °C for 3 h. After the system cools down, extract with dichloromethane / water twice, dry and rotary evaporate. The light green pure product (56 mg) is obtained by column chromatography separation, and the yield is 32%.

[0276] Synthesis of compound L14:

[0277] Add 56 mg (1.0 eq) of compound 14-2 and 50 mg (6.0 eq) of 2Cl-IC into a polymerization tube, and 12 mL of ultra-dry chloroform. Add 0.12 mL of pyridine under an argon atmosphere, and then react at 65 °C for 13 h. The next day, the color of the solution changes from green to blue. After the system cools down, rotary evaporate and then add it to methanol for reverse sedimentation. The resulting solid is separated by column chromatography to obtain 45 mg of a black-red solid, and the yield is 63%.

[0278] Elemental analysis structure (C 124 H 108 B2Cl4F 12N8O2S4): Theoretical values: C, 65.85; H, 4.81; B, 0.96; Cl, 6.27; F, 10.08; N, 4.95; O, 1.41; S, 5.67. Test values: C, 65.82; H, 4.79; N, 4.90.

[0279] MALDI-TOF analysis, theoretical value: 2258.62; experimental value: 2258.6.

[0280] Example 15

[0281] A small molecule acceptor L15 based on a unit with a resonant boron-nitrogen bond, and its structural formula is as shown in formula L15:

[0282]

[0283] Its synthetic route is as follows:

[0284]

[0285] Synthesis of compound 15-1:

[0286] The synthesis steps and experimental conditions of 15-1 are the same as those of 1-1, only the raw materials are changed.

[0287] Synthesis of compound 15-2:

[0288] Add 65 mg (1.0 eq) of compound 15-1, 275 mg (6.0 eq) of CPDT dialdehyde, and 200 mg of molecular sieve into a polymerization tube. Add 14 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, add 160 μL of piperidine and 118 μL of glacial acetic acid. Then react at 85 °C for 3 h. After the system cools down, extract twice with dichloromethane / water, dry and rotary evaporate. The green pure product (54 mg) is obtained by column chromatography separation, with a yield of 35%.

[0289] Synthesis of compound L15:

[0290] Add 54 mg (1.0 eq) of compound 15-2 and 55 mg (6.0 eq) of 2Cl-IC into a polymerization tube, and 12 mL of ultra-dry chloroform. Add 0.12 mL of pyridine under an argon atmosphere, and then react at 65 °C for 13 h. The next day, the color of the solution changes from green to blue. After the system cools down, rotary evaporate and then add it to methanol for reverse sedimentation. The resulting solid is separated by column chromatography to obtain 49 mg of a black-red solid, with a yield of 69%.

[0291] Elemental analysis structure (C 120 H 106(B2Cl4N8O4S4): Theoretical values: C, 71.50; H, 5.30; B, 1.07; Cl, 7.03; N, 5.56; O, 3.17; S, 6.36. Test values: C, 71.45; H, 5.45; N, 5.60.

[0292] MALDI-TOF analysis, theoretical value: 2012.62; experimental value: 2012.6.

[0293] Example 16

[0294] A small molecule acceptor L16 based on a unit with resonance boron-nitrogen bonds, and its structural formula is as shown in formula L16:

[0295]

[0296] Its synthetic route is as follows:

[0297]

[0298] Synthesis of compound 16-1:

[0299] The synthesis steps and experimental conditions of 16-1 are the same as those of 1-1, only the raw materials are changed.

[0300] Synthesis of compound 16-2:

[0301] Add 56 mg (1.0 eq) of compound 16-1, 395 mg (6.0 eq) of CPDT dialdehyde, and 200 mg of molecular sieve into a polymerization tube. Add 14 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, add 160 μL of piperidine and 118 μL of glacial acetic acid. Then react at 85 °C for 3 h. After the system cools down, extract twice with dichloromethane / water, dry and rotary evaporate. The light green pure product (74 mg) is obtained by column chromatography separation, with a yield of 40%.

[0302] Synthesis of compound L16:

[0303] Add 74 mg (1.0 eq) of compound 16-2 and 52 mg (5.0 eq) of 2Cl-IC into a polymerization tube, and 12 mL of ultra-dry chloroform. Add 0.12 mL of pyridine under an argon atmosphere, and then react at 65 °C for 13 h. The next day, the color of the solution changes from green to blue. After the system cools down, rotary evaporate and then add it to methanol for reverse sedimentation. The resulting solid is separated by column chromatography to obtain 62 mg of a black-red solid, with a yield of 66%.

[0304] Elemental analysis structure (C 140 H 138(B2Cl4F4N8O2S4): Theoretical values: C, 72.10; H, 5.96; B, 0.93; Cl, 6.08; F, 3.26; N, 4.80; O, 1.37; S, 5.50. Test values: C, 72.05; H, 5.90; N, 4.77.

[0305] MALDI-TOF analysis, theoretical value: 2328.87; experimental value: 2328.9.

[0306] Example 17

[0307] A small molecule acceptor L17 based on a unit with a resonant boron-nitrogen bond, and its structural formula is as shown in formula L17:

[0308]

[0309] Its synthetic route is as follows:

[0310]

[0311] Synthesis of compound 17-1:

[0312] The synthesis steps and experimental conditions of 17-1 are the same as those of 1-1, only the raw materials are changed.

[0313] Synthesis of compound 17-2:

[0314] Add 56 mg (1.0 eq) of compound 17-1 and 319 mg (6.0 eq) of thiophene dialdehyde to a polymerization tube, 200 mg of molecular sieve. Add 16 mL of ultradry toluene under an argon atmosphere. After complete dissolution, add 160 μL of piperidine and 118 μL of glacial acetic acid. Then react at 85 °C for 3 h. After the system cools down, extract twice with dichloromethane / water, dry and rotary evaporate. The yellow pure product (57 mg) is obtained by column chromatography separation, and the yield is 36%.

[0315] Synthesis of compound L17:

[0316] Add 57 mg (1.0 eq) of compound 17-2 and 57 mg (6.0 eq) of 2Cl-IC to a polymerization tube, and 12 mL of ultradry chloroform. Add 0.13 mL of pyridine under an argon atmosphere, and then react at 65 °C for 13 h. The next day, the color of the solution changes from yellow to blue. After the system cools down, rotary evaporate and add it to methanol for reverse sedimentation. The resulting solid is separated by column chromatography to obtain 52 mg of a black-red solid, and the yield is 70%.

[0317] Elemental analysis structure (C 120 H 126(B2Cl4F4N8O2S4): Theoretical values: C, 69.29; H, 6.11; B, 1.04; Cl, 6.82; F, 3.65; N, 5.39; O, 1.54; S, 6.17. Test values: C, 69.25; H, 6.01; N, 5.39.

[0318] MALDI-TOF analysis, theoretical value: 2076.78; experimental value: 2076.8.

[0319] Example 18

[0320] A small molecule acceptor L18 based on a unit with a resonant boron-nitrogen bond, and its structural formula is as shown in formula L18:

[0321]

[0322] Its synthesis route is as follows:

[0323]

[0324] Synthesis of compound 18-1:

[0325] The synthesis steps and experimental conditions of 18-1 are the same as those of 1-1, only the raw materials are changed.

[0326] Synthesis of compound 18-2:

[0327] Add 56 mg (1.0 eq) of compound 18-1 and 596 mg (6.0 eq) of thiophene dialdehyde into a polymerization tube, 200 mg of molecular sieve. Add 16 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, add 160 μL of piperidine and 118 μL of glacial acetic acid. Subsequently, react at 85 °C for 3 h. After the system cools down, extract twice with dichloromethane / water, dry and rotary evaporate. The yellow pure product of 82 mg is obtained by column chromatography separation, and the yield is 33%.

[0328] Synthesis of compound L18:

[0329] Add 82 mg (1.0 eq) of compound 18-2 and 52 mg (6.0 eq) of 2Cl-IC into a polymerization tube, and 12 mL of ultra-dry chloroform. Add 0.13 mL of pyridine under an argon atmosphere, and then react at 65 °C for 13 h. The next day, the color of the solution changes from yellow to blue. After the system cools down, rotary evaporate and then add it to methanol for reverse sedimentation. Subsequently, the obtained solid is separated by column chromatography to obtain 58 mg of black-red solid, and the yield is 66%.

[0330] Elemental analysis structure (C 184 H 194 B2Cl4F4N 12O2S4): Theoretical values: C, 74.33; H, 6.58; B, 0.73; Cl, 4.77; F, 2.56; N, 5.65; O, 1.08; S, 4.31. Test values: C, 74.30; H, 6.52; N, 5.61.

[0331] MALDI-TOF analysis, theoretical value: 2969.32; experimental value: 2969.3.

[0332] Example 19

[0333] A small molecule acceptor L19 based on a unit with a resonant boron-nitrogen bond, and its structural formula is as shown in formula L19:

[0334]

[0335] Its synthetic route is as follows:

[0336]

[0337] Synthesis of compound 19-1:

[0338] The synthesis steps and experimental conditions of 19-1 are the same as those of 1-1, only the raw materials are changed.

[0339] Synthesis of compound 19-2:

[0340] Add 56 mg (1.0 eq) of compound 19-1, 597 mg (6.0 eq) of benzodindeno[1,2-b:2',1'-d]thiophene bisaldehyde, 200 mg of molecular sieve into a polymerization tube. Add 16 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, add 160 μL of piperidine and 118 μL of glacial acetic acid. Then react at 85 °C for 3 h. After the system cools down, extract twice with dichloromethane / water, dry and rotary evaporate. The green pure product (98 mg, yield 39%) is obtained by column chromatography separation.

[0341] Synthesis of compound L19:

[0342] Add 98 mg (1.0 eq) of compound 19-2 and 61 mg (6.0 eq) of 2Cl-IC into a polymerization tube, and 12 mL of ultra-dry chloroform. Add 0.13 mL of pyridine under an argon atmosphere, and then react at 65 °C for 13 h. The next day, the color of the solution changes from green to blue. After the system cools down, rotary evaporate and then add it to methanol for reverse sedimentation. The resulting solid is separated by column chromatography to obtain 78 mg of a black-red solid with a yield of 67%.

[0343] Elemental analysis structure (C 184 H 194 B2Cl4F4N 12O2S4): Theoretical values: C, 74.33; H, 6.58; B, 0.73; Cl, 4.77; F, 2.56; N, 5.65; O, 1.08; S, 4.31. Test values: C, 74.30; H, 6.52; N, 5.61.

[0344] MALDI-TOF analysis, theoretical value: 2969.32; experimental value: 2969.3.

[0345] Example 20

[0346] A small molecule acceptor L20 based on a unit with a resonant boron-nitrogen bond, and its structural formula is as shown in formula L20:

[0347]

[0348] Its synthetic route is as follows:

[0349]

[0350] Synthesis of compound 20-1:

[0351] The synthesis steps and experimental conditions of 20-1 are the same as those of 1-1, only the raw materials are changed.

[0352] Synthesis of compound 20-2:

[0353] Add 56 mg (1.0 eq) of compound 20-1, 335 mg (6.0 eq) of fluorene dialdehyde, and 200 mg of molecular sieve into a polymerization tube. Add 16 mL of super-dry toluene under an argon atmosphere. After complete dissolution, add 160 μL of piperidine and 118 μL of glacial acetic acid. Then react at 85 °C for 3 h. After the system cools down, extract with dichloromethane / water twice, dry and rotary evaporate. The yellow pure product of 66 mg is obtained by column chromatography separation, and the yield is 40%.

[0354] Synthesis of compound L20:

[0355] Add 82 mg (1.0 eq) of compound 20-2 and 63 mg (6.0 eq) of 2Cl-IC into a polymerization tube, and 15 mL of super-dry chloroform. Add 0.16 mL of pyridine under an argon atmosphere, and then react at 65 °C for 13 h. The next day, the color of the solution changes from yellow to blue. After the system cools down, rotary evaporate and then add it to methanol for reverse sedimentation. The resulting solid is separated by column chromatography to obtain 53 mg of a black-red solid, and the yield is 62%.

[0356] Elemental analysis structure (C 134 H 138(B2Cl4F4N8O2): Theoretical values: C, 75.49; H, 6.52; B, 1.01; Cl, 6.65; F, 3.56; N, 5.26; O, 1.50. Measured values: C, 75.52; H, 6.43; N, 5.23.

[0357] MALDI-TOF analysis, theoretical value: 2128.98; experimental value: 2129.0.

[0358] Example 21

[0359] A small molecule acceptor L21 based on a unit with a resonance boron-nitrogen bond, and its structural formula is as shown in formula L21:

[0360]

[0361] Its synthetic route is as follows:

[0362]

[0363] Synthesis of compound 21-1:

[0364] The synthesis steps and experimental conditions of 21-1 are the same as those of 1-1, only the raw materials are changed.

[0365] Synthesis of compound 21-2:

[0366] Add 56 mg (1.0 eq) of compound 21-1, 275 mg (6.0 eq) of CPDT dialdehyde, and 200 mg of molecular sieve into a polymerization tube. Add 16 mL of super-dry toluene under an argon atmosphere. After complete dissolution, add 160 μL of piperidine and 118 μL of glacial acetic acid. Then react at 85 °C for 3 h. After the system cools down, extract twice with dichloromethane / water, dry and rotary evaporate. The green pure product (50 mg, yield 40%) is obtained by column chromatography.

[0367] Synthesis of compound L21:

[0368] Add 50 mg (1.0 eq) of compound 21-2 and 75 mg (6.0 eq) of 21-3 into a polymerization tube, and add 15 mL of super-dry chloroform. Add 0.16 mL of pyridine under an argon atmosphere, and then react at 65 °C for 13 h. The next day, the color of the solution changes from yellow to blue. After the system cools down, rotary evaporate and then add it to methanol for reverse sedimentation. The resulting solid is separated by column chromatography to obtain 55 mg of a black-red solid with a yield of 68%.

[0369] Elemental analysis structure (C 118 H 102(B2Cl4F4N8O2S4): Theoretical values: C, 69.76; H, 5.06; B, 1.06; Cl, 6.98; F, 3.74; N, 5.52; O, 1.57; S, 6.31. Test values: C, 69.77; H, 5.04; N, 5.46.

[0370] MALDI-TOF analysis, theoretical value: 2028.59; experimental value: 2028.6.

[0371] Example 22

[0372] A small molecule acceptor L22 based on a unit with a resonant boron-nitrogen bond, and its structural formula is as shown in formula L22:

[0373]

[0374] Its synthetic route is as follows:

[0375]

[0376] Synthesis of compound 22-1:

[0377] The synthesis steps and experimental conditions of 22-1 are the same as those of 1-1, only the raw materials are changed.

[0378] Synthesis of compound 22-2:

[0379] Add 56 mg (1.0 eq) of compound 22-1, 275 mg (6.0 eq) of CPDT dialdehyde, and 200 mg of molecular sieve into a polymerization tube. Add 16 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, add 160 μL of piperidine and 118 μL of glacial acetic acid. Then react at 85 °C for 3 h. After the system cools down, extract twice with dichloromethane / water, dry and rotary evaporate. The green pure product (50 mg, yield 40%) is obtained by column chromatography separation.

[0380] Synthesis of compound L22:

[0381] Add 50 mg (1.0 eq) of compound 21-2 and 75 mg (6.0 eq) of 22-3 into a polymerization tube, and 15 mL of ultra-dry chloroform. Add 0.16 mL of pyridine under an argon atmosphere, and then react at 65 °C for 13 h. The next day, the color of the solution changes from yellow to blue. After the system cools down, rotary evaporate and then add it to methanol for reverse sedimentation. The resulting solid is separated by column chromatography to obtain 58 mg of a black-red solid with a yield of 70%.

[0382] Elemental analysis structure (C 118 H 102(B2Cl4F4N8O2S4): Theoretical values: C, 69.76; H, 5.06; B, 1.06; Cl, 6.98; F, 3.74; N, 5.52; O, 1.57; S, 6.31. Test values: C, 69.77; H, 5.03; N, 5.55.

[0383] MALDI-TOF analysis, theoretical value: 2028.59; experimental value: 2028.6.

[0384] Example 23

[0385] A small molecule acceptor L23 based on a unit with resonance boron-nitrogen bonds, the structural formula is as shown in formula L23:

[0386]

[0387] Its synthesis route is as follows:

[0388]

[0389] Synthesis of compound 23-1:

[0390] The synthesis steps and experimental conditions of 23-1 are the same as those of 1-1, only the raw materials are changed.

[0391] Synthesis of compound L23:

[0392] Add 56 mg (1.0 eq) of compound 23-1, 219 mg (3.0 eq) of 23-2, 200 mg of molecular sieve into a polymerization tube. Under an argon atmosphere, add 16 mL of ultra-dry toluene. After complete dissolution, add 160 μL of piperidine and 118 μL of glacial acetic acid. Subsequently, react at 120 °C for 5 h. After the system cools down, extract twice with dichloromethane / water, dry and rotary evaporate. 119 mg of black pure product is obtained by column chromatography separation, and the yield is 60%.

[0393] Elemental analysis structure (C 112 H 98 (B2Cl4F4N8S6): Theoretical values: C, 67.67; H, 4.97; B, 1.09; Cl, 7.13; F, 3.82; N, 5.64; S, 9.68. Test values: C, 67.60; H, 5.00; N, 5.62.

[0394] MALDI-TOF analysis, theoretical value: 1984.51; experimental value: 1984.5.

[0395] Example 24

[0396] A small molecule acceptor L24 based on a unit with resonance boron-nitrogen bonds, the structural formula is as follows:

[0397]

[0398] The synthetic route is as follows:

[0399]

[0400] Synthesis of compound 24-1:

[0401] The synthesis steps and experimental conditions of 24-1 are the same as those of 1-1, only the raw materials are changed.

[0402] Synthesis of compound L24:

[0403] Add 56 mg (1.0 eq) of compound 24-1, 234 mg (3.0 eq) of 24-2, and 200 mg of molecular sieve into a polymerization tube. Add 16 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, add 160 μL of piperidine and 118 μL of glacial acetic acid. Subsequently, react at 120 °C for 5 h. After the system cools down, extract twice with dichloromethane / water, dry, and evaporate to dryness. Obtain 131 mg of a pure black product by column chromatography separation, with a yield of 63%.

[0404] Elemental analysis results (C 120 H 102 B2Cl4F4N8S6): Theoretical values: C, 69.03; H, 4.92; B, 1.04; Cl, 6.79; F, 3.64; N, 5.37; S, 9.21. Measured values: C, 69.00; H, 4.90; N, 5.30.

[0405] MALDI-TOF analysis, theoretical value: 2084.54; experimental value: 2084.5.

[0406] Example 25

[0407] A polymer L25 based on a resonance boron-nitrogen bond unit, with the structural formula shown as formula L25:

[0408]

[0409] The synthetic route is as follows:

[0410]

[0411] Synthesis of compound 25-1:

[0412] The synthesis steps and experimental conditions of 25-1 are the same as those of 1-1, only the raw materials are changed.

[0413] Synthesis of compound 25-3:

[0414] In a polymerization tube, 56 mg (1.0 eq) of compound 25-1 and 153 mg (3.0 eq) of 25-2 were added, along with 200 mg of molecular sieve. 16 mL of ultra-dry toluene was added under an argon atmosphere. After complete dissolution, 160 μL of piperidine and 118 μL of glacial acetic acid were added. Subsequently, the reaction was carried out at 85 °C for 1 h. After the system cooled, extraction was performed twice with dichloromethane / water, followed by drying and rotary evaporation. 108 mg of a green pure product was obtained by column chromatography separation, with a yield of 70%.

[0415] Synthesis of compound L25:

[0416] In a polymerization tube, 77 mg (1.0 eq) of compound 25-3, 29 mg (1.0 eq) of hexabutylditin, 0.9 mg (0.02 eq) of tris(dibenzylideneacetone)dipalladium(0) and 2.4 mg (0.16 eq) of tris(o-tolyl)phosphine were added. 2.5 mL of ultra-dry toluene was added under an argon atmosphere, and then the reaction was carried out at 120 °C for 12 h in the dark. After the reaction, the reaction system was precipitated in methanol, and the polymer precipitated out. The precipitate was successively Soxhlet extracted with acetone, n-hexane, and chloroform to obtain 66 mg of the final product, with a yield of 95%.

[0417] Elemental analysis theoretical values for the structure: C, 72.92; H, 6.70; B, 1.56; F, 5.49; N, 4.05; S, 9.27. Measured values: C, 72.88; H, 6.68; N, 4.01.

[0418] The obtained product was analyzed by gel permeation chromatography (GPC, trichlorobenzene, using polystyrene as the standard, at 150 °C), and the results were: M n = 20152, PDI = 2.21.

[0419] Example 26

[0420] A polymer L26 based on a resonance boron-nitrogen bond unit, with the structural formula shown as formula L26:

[0421]

[0422] Its synthetic route is as follows:

[0423]

[0424] Synthesis of compound 26-1:

[0425] The synthesis steps and experimental conditions of 26-1 are the same as those of 1-1, except for the raw materials.

[0426] Synthesis of compound 26-3:

[0427] In a polymerization tube, 146 mg (1.0 eq) of compound 26-1 and 149 mg (3.0 eq) of 26-2 were added. 200 mg of molecular sieve was added. Under an argon atmosphere, 16 mL of ultra-dry toluene was added. After complete dissolution, 200 μL of piperidine and 140 μL of glacial acetic acid were added. Subsequently, the reaction was carried out at 85 °C for 1 h. After the system cooled down, extraction was performed twice with dichloromethane / water, followed by drying and rotary evaporation. 164 mg of a green pure product was obtained by column chromatography separation, with a yield of 68%.

[0428] Synthesis of compound L26:

[0429] In a polymerization tube, 121 mg (1.0 eq) of compound 26-3, 29 mg (1.0 eq) of hexabutylditin, 0.9 mg (0.02 eq) of tris(dibenzylideneacetone)dipalladium(0) and 2.4 mg (0.16 eq) of tris(o-tolyl)phosphine were added. Under an argon atmosphere, 2.5 mL of ultra-dry toluene was added, and then the reaction was carried out at 120 °C for 12 h in the dark. After the reaction ended, the reaction system was precipitated in methanol, and the polymer precipitated out. The precipitate was successively Soxhlet extracted with acetone, n-hexane, and chloroform to obtain 105 mg of the final product, with a yield of 93%.

[0430] Theoretical values of elemental analysis structure: C, 86.96; H, 9.61; B, 0.95; N, 2.47. Measured values: C, 86.99; H, 9.57; N, 2.45.

[0431] The obtained product was analyzed by gel permeation chromatography (GPC, trichlorobenzene, using polystyrene as the standard, at 150 °C), and the results were as follows: M n = 18326, PDI = 2.35.

[0432] Example 27

[0433] A polymer L27 based on a resonance boron-nitrogen bond unit, with the structural formula shown as formula L27:

[0434]

[0435] Its synthesis route is as follows:

[0436]

[0437] Synthesis of compound 27-1:

[0438] The synthesis steps and experimental conditions of 27-1 are the same as those of 1-1, only the raw materials are changed.

[0439] Synthesis of compound 27-3:

[0440] In a polymerization tube, 56 mg (1.0 eq) of compound 27-1 and 182 mg (3.0 eq) of 27-2 were added, along with 200 mg of molecular sieve. 13 mL of ultra-dry toluene was added under an argon atmosphere. After complete dissolution, 200 μL of piperidine and 140 μL of glacial acetic acid were added. Subsequently, the reaction was carried out at 85 °C for 1 h. After the system cooled down, extraction was performed twice with dichloromethane / water, followed by drying and rotary evaporation. 115 mg of a green pure product was obtained by column chromatography separation, with a yield of 66%.

[0441] Synthesis of compound L27:

[0442] In a polymerization tube, 87 mg (1.0 eq) of compound 27-3, 29 mg (1.0 eq) of hexabutylditin, 0.9 mg (0.02 eq) of tris(dibenzylideneacetone)dipalladium(0) and 2.4 mg (0.16 eq) of tris(o-tolyl)phosphine were added. 2.2 mL of ultra-dry toluene was added under an argon atmosphere, and then the reaction was carried out at 120 °C for 12 h in the dark. After the reaction ended, the reaction system was precipitated in methanol, and the polymer precipitated out. The precipitate was successively Soxhlet extracted with acetone, n-hexane, and chloroform to obtain 71 mg of the final product, with a yield of 90%.

[0443] Theoretical values of elemental analysis structure: C, 74.31; H, 7.89; B, 1.36; F, 4.80; N, 3.54; S, 8.10. Measured values: C, 74.30; H, 7.85; N, 3.56.

[0444] The obtained product was analyzed by gel permeation chromatography (GPC, trichlorobenzene, using polystyrene as the standard, at 150 °C), and the results were: M n = 26535, PDI = 2.30.

[0445] Example 28

[0446] A polymer L28 based on a resonance boron-nitrogen bond unit, with the structural formula shown as formula L28:

[0447]

[0448] Its synthetic route is as follows:

[0449]

[0450] Synthesis of compound 28-1:

[0451] The synthesis steps and experimental conditions of 28-1 are the same as those of 1-1.

[0452] Synthesis of compound 28-3:

[0453] Add 38 mg (1.0 eq) of compound 28-1 and 112 mg (3.0 eq) of 28-2 into a polymerization tube. Add 200 mg of molecular sieve. Under an argon atmosphere, add 13 mL of ultra-dry toluene. After complete dissolution, add 200 μL of piperidine and 140 μL of glacial acetic acid. Subsequently, react at 85 °C for 1 h. After the system cools down, extract with dichloromethane / water twice, dry, and rotary evaporate to dryness. Purify the product by column chromatography to obtain 69 mg of green pure product with a yield of 63%.

[0454] Synthesis of compound L28:

[0455] Add Ni(COD)2 (55 mg, 4.0 eq), 2,2'-bipyridine (31 mg, 4.0 eq), cyclooctadiene (22 mg, 4.0 eq) and 6.0 mL of toluene into a polymerization tube, stir and activate at 80 °C for 30 min. Dissolve compound 28-3 (55 mg, 1.0 eq) in anhydrous toluene (10 mL), and add it dropwise to the catalyst solution. React in the dark at 80 °C for 24 h. After the reaction, precipitate the reaction system in methanol, and the polymer precipitates. Soxhlet extract the precipitate with acetone, n-hexane, and chloroform successively to obtain 45 mg of the final product with a yield of 95%.

[0456] Theoretical values of elemental analysis: C, 66.53; H, 6.87; B, 2.30; F, 8.09; N, 5.97; O, 3.41; S, 6.83. Measured values: C, 66.45; H, 6.77; N, 5.88.

[0457] Analyze the obtained product by gel permeation chromatography (GPC, trichlorobenzene, polystyrene as standard, 150 °C), and obtain: M n = 28176, PDI = 2.40.

[0458] Example 29

[0459] A polymer L29 based on a resonance boron-nitrogen bond unit, the structural formula is shown as formula L29:

[0460]

[0461] Its synthetic route is as follows:

[0462]

[0463] Synthesis of compound 29-1:

[0464] The synthesis steps and experimental conditions of 29-1 are the same as those of 1-1, only the raw materials are changed.

[0465] Synthesis of compound 29-3:

[0466] In a polymerization tube, 56 mg (1.0 eq) of compound 29-1 and 308 mg (3.0 eq) of 29-2 were added, along with 200 mg of molecular sieve. 13 mL of ultra-dry toluene was added under an argon atmosphere. After complete dissolution, 200 μL of piperidine and 140 μL of glacial acetic acid were added. Subsequently, the reaction was carried out at 85 °C for 1 h. After the system cooled, extraction was performed twice with dichloromethane / water, followed by drying and rotary evaporation. 144 mg of a green pure product was obtained by column chromatography separation, with a yield of 58%.

[0467] Synthesis of compound L29:

[0468] In a polymerization tube, 124 mg (1.0 eq) of compound 29-3, 29 mg (1.0 eq) of hexakis(n-butyl) distannane, 0.9 mg (0.02 eq) of tris(dibenzylideneacetone) dipalladium(0) and 2.4 mg (0.16 eq) of tris(o-tolyl)phosphine were added. 2.5 mL of ultra-dry toluene was added under an argon atmosphere, and then the reaction was carried out at 120 °C for 12 h in the dark. After the reaction was completed, the reaction system was precipitated in methanol, and the polymer precipitated out. The precipitate was successively extracted by Soxhlet extraction with acetone, n-hexane, and chloroform to obtain 106 mg of the final product, with a yield of 88%.

[0469] Elemental analysis theoretical values: C, 78.25; H, 7.81; B, 0.89; F, 3.13; N, 4.62; S, 5.29. Measured values: C, 78.30; H, 7.82; N, 4.61.

[0470] The obtained product was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene as the standard, 150 °C), and the results were as follows: M n = 18625, PDI = 2.55.

[0471] Example 30

[0472] A polymer L30 based on a resonance boron-nitrogen bond unit, with the structural formula shown as formula L30:

[0473]

[0474] Its synthetic route is as follows:

[0475]

[0476] Synthesis of compound 30-1

[0477] The synthesis steps and experimental conditions of 30-1 are the same as those of 1-1.

[0478] Synthesis of compound 30-3:

[0479] Add 38 mg (1.0 eq) of compound 30-1 and 313 mg (3.0 eq) of compound 30-2 into a polymerization tube. Add 200 mg of molecular sieve. Under an argon atmosphere, add 13 mL of ultradry toluene. After complete dissolution, add 200 μL of piperidine and 140 μL of glacial acetic acid. Subsequently, react at 85 °C for 1 h. After the system cools down, extract twice with dichloromethane / water, dry, and evaporate to dryness. Purify the green product (151 mg) by column chromatography with a yield of 62%.

[0480] Synthesis of compound L30:

[0481] Add 122 mg (1.0 eq) of compound 30-3, 29 mg (1.0 eq) of hexabutylditin, 0.9 mg (0.02 eq) of tris(dibenzylideneacetone)dipalladium(0) and 2.4 mg (0.16 eq) of tris(o-tolyl)phosphine into a polymerization tube. Under an argon atmosphere, add 2.5 mL of ultradry toluene, and then react at 120 °C for 12 h in the dark. After the reaction, precipitate the reaction system in methanol to precipitate the polymer. Soxhlet extract the precipitate with acetone, n-hexane, and chloroform successively to obtain 103 mg of the final product with a yield of 90%.

[0482] Elemental analysis: theoretical values: C, 77.92; H, 9.72; B, 0.95; F, 3.33; N, 2.46; S, 5.62. Measured values: C, 77.90; H, 9.66; N, 2.44.

[0483] Analyze the obtained product by gel permeation chromatography (GPC, trichlorobenzene, polystyrene as the standard, 150 °C) to obtain: M n = 32158, PDI = 2.66.

[0484] Example 31

[0485] A polymer L31 based on a resonance boron-nitrogen bond unit, with the structural formula shown in Formula L31:

[0486]

[0487] Its synthetic route is as follows:

[0488]

[0489] Synthesis of compound 31-1:

[0490] The synthesis steps and experimental conditions of 31-1 are the same as those of 1-1, except that the raw materials are changed.

[0491] Synthesis of compound 31-3:

[0492] In a polymerization tube, 56 mg (1.0 eq) of compound 31-1 and 107 mg (3.0 eq) of 31-2 were added, along with 200 mg of molecular sieve. 13 mL of ultra-dry toluene was added under an argon atmosphere. After complete dissolution, 175 μL of piperidine and 115 μL of glacial acetic acid were added. Subsequently, the reaction was carried out at 85 °C for 2 h. After the system cooled down, extraction was performed twice with dichloromethane / water, followed by drying and rotary evaporation. 82 mg of a green pure product was obtained by column chromatography separation, with a yield of 66%.

[0493] Synthesis of compound L31:

[0494] In a polymerization tube, 74 mg (1.0 eq) of compound 31-3, 35 mg (1.0 eq) of hexabutylditin, 1.1 mg (0.02 eq) of tris(dibenzylideneacetone)dipalladium, and 2.9 mg (0.16 eq) of tris(o-tolyl)phosphine were added. 3.0 mL of ultra-dry toluene was added under an argon atmosphere, and then the reaction was carried out at 120 °C for 12 h in the dark. After the reaction ended, the reaction system was precipitated in methanol, and the polymer precipitated out. The precipitate was successively extracted by Soxhlet extraction with acetone, n-hexane, and chloroform to obtain 103 mg of the final product, with a yield of 90%.

[0495] Theoretical values for elemental analysis structure: C, 73.19; H, 6.70; B, 2.00; F, 7.02; N, 5.17; S, 5.92. Measured values: C, 73.18; H, 6.72; N, 5.19.

[0496] The obtained product was analyzed by gel permeation chromatography (GPC, trichlorobenzene, using polystyrene as the standard, at 150 °C), and the results were: M n = 29138, PDI = 2.45.

[0497] Example 32

[0498] A polymer L32 based on a resonance boron-nitrogen bond unit, with the structural formula shown as formula L32:

[0499]

[0500] Its synthetic route is as follows:

[0501]

[0502] Synthesis of compound 32-1:

[0503] The synthesis steps and experimental conditions of 31-1 are the same as those of 1-1, except that the raw materials are changed.

[0504] Synthesis of compound 32-3:

[0505] In a polymerization tube, 129 mg (1.0 eq) of compound 32-1 and 107 mg (3.0 eq) of 32-2 were added. 200 mg of molecular sieve was added. Under an argon atmosphere, 13 mL of ultradry toluene was added. After complete dissolution, 175 μL of piperidine and 115 μL of glacial acetic acid were added. Subsequently, the reaction was carried out at 85 °C for 1 h. After the system cooled down, extraction was performed twice with dichloromethane / water, followed by drying and rotary evaporation. 116 mg of a green pure product was obtained by column chromatography separation, with a yield of 59%.

[0506] Synthesis of compound L32:

[0507] In a polymerization tube, Ni(COD)2 (33 mg, 4.0 eq), 2,2'-bipyridine (19 mg, 4.0 eq), cyclooctadiene (13 mg, 4.0 eq) and 4.0 mL of toluene were added. The mixture was stirred and activated at 80 °C for 30 min. Compound 32-3 (59 mg, 1.0 eq) was dissolved in anhydrous toluene (7 mL) and added dropwise to the catalyst solution. The reaction was carried out at 80 °C in the dark for 24 h. After the reaction, the reaction system was precipitated in methanol, and the polymer precipitated out. The precipitate was successively Soxhlet extracted with acetone, n-hexane and chloroform to obtain 51 mg of the final product, with a yield of 94%.

[0508] Theoretical values of elemental analysis structure: C, 82.35; H, 9.81; B, 1.20; N, 3.10; S, 3.55. Measured values: C, 82.32; H, 9.81; N, 3.11.

[0509] The obtained product was analyzed by gel permeation chromatography (GPC, trichlorobenzene, using polystyrene as the standard, 150 °C), and the results were as follows: M n = 14328, PDI = 2.50.

[0510] Example 33

[0511] A polymer L33 based on a resonance boron-nitrogen bond unit has the structural formula shown in Formula L33:

[0512]

[0513] Its synthetic route is as follows:

[0514]

[0515] Synthesis of compound 33-1:

[0516] The synthesis steps and experimental conditions of 33-1 are the same as those of 1-1, except that the raw materials are changed.

[0517] Synthesis of compound 33-3:

[0518] In a polymerization tube, 56 mg (1.0 eq) of compound 33-1 and 212 mg (3.0 eq) of 33-2 were added, along with 200 mg of molecular sieve. 13 mL of ultra-dry toluene was added under an argon atmosphere. After complete dissolution, 175 μL of piperidine and 115 μL of glacial acetic acid were added. Subsequently, the reaction was carried out at 85 °C for 1 h. After the reaction system cooled down, it was extracted twice with dichloromethane / water, dried, and concentrated by rotary evaporation. 109 mg of a green pure product was obtained by column chromatography separation, with a yield of 56%.

[0519] Synthesis of compound L33:

[0520] In a polymerization tube, 78 mg (1.0 eq) of compound 33-3, 23 mg (1.0 eq) of hexabutylditin, 0.7 mg (0.02 eq) of tris(dibenzylideneacetone)dipalladium(0) and 1.9 mg (0.16 eq) of tris(o-tolyl)phosphine were added. 3.0 mL of ultra-dry toluene was added under an argon atmosphere, and then the reaction was carried out at 120 °C for 12 h in the dark. After the reaction was completed, the reaction system was precipitated in methanol, and the polymer precipitated out. The precipitate was successively extracted by Soxhlet extraction with acetone, n-hexane, and chloroform to obtain 66 mg of the final product, with a yield of 93%.

[0521] Theoretical values for elemental analysis of the structure: C, 76.74; H, 7.46; B, 1.21; F, 4.26; N, 3.14; S, 7.19. Measured values: C, 76.73; H, 7.44; N, 3.07.

[0522] The obtained product was analyzed by gel permeation chromatography (GPC, trichlorobenzene, using polystyrene as the standard, at 150 °C), and the results were: M n = 41225, PDI = 2.36.

[0523] Example 34

[0524] A polymer L34 based on a resonance boron-nitrogen bond unit, with the structural formula shown as formula L34:

[0525]

[0526] Its synthetic route is as follows:

[0527]

[0528] Synthesis of compound 34-1:

[0529] The synthesis steps and experimental conditions of 34-1 are the same as those of 1-1, except that the raw materials are changed.

[0530] Synthesis of compound 34-3:

[0531] Add 56 mg (1.0 eq) of compound 34-1, 240 mg (3.0 eq) of 34-2 into a polymerization tube. Add 200 mg of molecular sieve. Under an argon atmosphere, add 15 mL of super-dry toluene. After complete dissolution, add 175 μL of piperidine and 115 μL of glacial acetic acid. Subsequently, react at 85 °C for 1 h. After the system cools down, extract twice with dichloromethane / water, dry and rotary evaporate to dryness. Separate by column chromatography to obtain 131 mg of green pure product with a yield of 62%.

[0532] Synthesis of compound L34:

[0533] Add 106 mg (1.0 eq) of compound 34-3, 29 mg (1.0 eq) of hexabutylditin, 0.9 mg (0.02 eq) of tris(dibenzylideneacetone)dipalladium(0) and 2.4 mg (0.16 eq) of tris(o-tolyl)phosphine into a polymerization tube. Under an argon atmosphere, add 3.0 mL of super-dry toluene, and then react under dark at 120 °C for 12 h. After the reaction, precipitate the reaction system in methanol, and the polymer precipitates. Extract the precipitate successively by Soxhlet extraction with acetone, n-hexane and chloroform to obtain 90 mg of the final product with a yield of 92%.

[0534] Theoretical values of elemental analysis structure: C, 67.12; H, 6.35; B, 1.10; F, 3.86; N, 8.54; S, 13.03. Measured values: C, 67.14; H, 6.33; N, 8.46.

[0535] Analyze the obtained product by gel permeation chromatography (GPC, trichlorobenzene, polystyrene as standard, 150 °C), and obtain: M n = 21305, PDI = 2.67.

[0536] Measurement of film-state ultraviolet-visible short-wave infrared absorption spectra of resonance boron-nitrogen small molecules and polymers:

[0537] Measure the film-state ultraviolet-visible short-wave infrared absorption spectra of the above L1, L4, L5, L6, L8, L12, L13, L14, L16, L25, L26, L29 and L31. The results are as Figures 1 to 4 shown, Figure 1 are the film-state ultraviolet-visible short-wave infrared absorption spectra of small molecules L1, L4 and L5 based on the resonance boron-nitrogen unit BIP; Figure 2 are the film-state ultraviolet-visible short-wave infrared absorption spectra of small molecules L6, L8 and L12 based on the resonance boron-nitrogen unit BIP; Figure 3 are the film-state ultraviolet-visible short-wave infrared absorption spectra of small molecules L13, L14 and L16 based on the resonance boron-nitrogen unit BIP; Figure 4Membrane - state ultraviolet - visible short - wave infrared absorption spectra of polymers L25, L26, L29, and L31 based on the resonance boron - nitrogen unit BIP. The absorption wavelengths are listed in Table 1.

[0538] Performance testing of photovoltaic detectors with resonance boron - nitrogen small molecules as acceptors:

[0539] Using resonance boron - nitrogen small molecules such as L1, L4, L5, L6, L8, L12, L13, L14, and L16 as acceptors, and PBDB - T or PCE10 as donors, photovoltaic detectors were fabricated for detection performance testing. Among them, the chemical structural formula of PBDB - T is The chemical structural formula of PCE10 is The molecular weight range of the PCE10 used is 50000 - 150000. The photovoltaic detector is also called a short - wave infrared organic optoelectronic detector, and its device structure is as Figure 5 shown, Figure 5 This is the schematic diagram of the device structure of the photovoltaic detector described in the present invention. As Figure 5 can be seen, the structure of the photovoltaic detector from bottom to top sequentially includes an ITO / Glass transparent conductive cathode, a ZnO cathode interface layer, a polymer donor / small - molecule acceptor active layer, a MoO3 anode interface layer, and an Al anode. The specific preparation process is shown in Test Examples 1 - 9.

[0540] Test Example 1

[0541] Taking the resonance boron - nitrogen small - molecule acceptor L1 obtained in Example 1 as an example, its detection performance is described.

[0542] The specific preparation process of the short - wave infrared organic optoelectronic detector with the aforementioned structure is as follows:

[0543] Spin - coat a 20 - nm layer of zinc oxide (ZnO) on ITO glass, and then anneal it at 200 °C for 60 minutes as the anode interface layer. Dissolve the polymer donor PBDB - T and the small - molecule acceptor L1 in chloroform, add 1% by volume of chloronaphthalene, and then spin - coat a co - blended photoactive layer of about 120 nm, anneal it at 120 °C for 10 minutes, then spin - coat a 10 - nm layer of MoO3 as the anode interface layer, and then evaporate a 100 - nm Al layer to complete the preparation of the device.

[0544] Test Example 2

[0545] Taking the resonance boron - nitrogen small - molecule acceptor L4 obtained in Example 4 as an example, its detection performance is described.

[0546] The specific preparation process of the short - wave infrared organic optoelectronic detector with the aforementioned structure is as follows:

[0547] Spin-coat a 20-nm layer of zinc oxide (ZnO) on the ITO glass, and then anneal it at 200 °C for 60 minutes as the anode interface layer. Dissolve the polymer donor PBDB-T and the small molecule acceptor L4 in chloroform, add 1% by volume of chloronaphthalene, and then spin-coat a blend photoactive layer of about 120 nm, anneal it at 120 °C for 10 minutes, then spin-coat a 10-nm layer of MoO3 as the anode interface layer, and then evaporate a 100-nm Al layer to complete the preparation of the device.

[0548] Test Example 3

[0549] Taking the resonance boron-nitrogen small molecule acceptor L5 obtained in Example 5 as an example, its detection performance is described.

[0550] The specific preparation process of the short-wave infrared organic optoelectronic detector with the aforementioned structure is as follows:

[0551] Spin-coat a 20-nm layer of zinc oxide (ZnO) on the ITO glass, and then anneal it at 200 °C for 60 minutes as the anode interface layer. Dissolve the polymer donor PBDB-T and the small molecule acceptor L5 in chloroform, add 1.5% by volume of chloronaphthalene, and then spin-coat a blend photoactive layer of about 130 nm, anneal it at 120 °C for 10 minutes, then spin-coat a 10-nm layer of MoO3 as the anode interface layer, and then evaporate a 100-nm Al layer to complete the preparation of the device.

[0552] Test Example 4

[0553] Taking the resonance boron-nitrogen small molecule acceptor L6 obtained in Example 6 as an example, its detection performance is described.

[0554] The specific preparation process of the short-wave infrared organic optoelectronic detector with the aforementioned structure is as follows:

[0555] Spin-coat a 20-nm layer of zinc oxide (ZnO) on the ITO glass, and then anneal it at 200 °C for 60 minutes as the anode interface layer. Dissolve the polymer donor PCE10 and the small molecule acceptor L6 in chloroform, add 1.5% by volume of chloronaphthalene, and then spin-coat a blend photoactive layer of about 130 nm, anneal it at 150 °C for 10 minutes, then spin-coat a 10-nm layer of MoO3 as the anode interface layer, and then evaporate a 100-nm Al layer to complete the preparation of the device.

[0556] Test Example 5

[0557] Taking the resonance boron-nitrogen small molecule acceptor L8 obtained in Example 8 as an example, its detection performance is described.

[0558] The specific preparation process of the short-wave infrared organic optoelectronic detector with the aforementioned structure is as follows:

[0559] Spin-coat a 20-nm layer of zinc oxide (ZnO) on ITO glass, and then anneal it at 200 °C for 60 minutes as the anode interface layer. Dissolve the polymer donor PCE10 and the small-molecule acceptor L8 in chloroform, add 1.2% by volume of chloronaphthalene, and then spin-coat a blend photoactive layer of about 160 nm, anneal at 150 °C for 10 minutes, then spin-coat a 10-nm layer of MoO3 as the anode interface layer, and then evaporate a 100-nm Al layer to complete the preparation of the device.

[0560] Test Example 6

[0561] Taking the resonance boron-nitrogen small-molecule acceptor L12 obtained in Example 12 as an example, its detection performance is described.

[0562] The specific preparation process of the short-wave infrared organic optoelectronic detector with the aforementioned structure is as follows:

[0563] Spin-coat a 20-nm layer of zinc oxide (ZnO) on ITO glass, and then anneal it at 200 °C for 60 minutes as the anode interface layer. Dissolve the polymer donor PBDB-T and the small-molecule acceptor L12 in chloroform, add 1.2% by volume of chloronaphthalene, and then spin-coat a blend photoactive layer of about 160 nm, anneal at 150 °C for 10 minutes, then spin-coat a 10-nm layer of MoO3 as the anode interface layer, and then evaporate a 100-nm Al layer to complete the preparation of the device.

[0564] Test Example 7

[0565] Taking the resonance boron-nitrogen small-molecule acceptor L13 obtained in Example 13 as an example, its detection performance is described.

[0566] The specific preparation process of the short-wave infrared organic optoelectronic detector with the aforementioned structure is as follows:

[0567] Spin-coat a 20-nm layer of zinc oxide (ZnO) on ITO glass, and then anneal it at 200 °C for 60 minutes as the anode interface layer. Dissolve the polymer donor PBDB-T and the small-molecule acceptor L13 in chloroform, add 1.2% by volume of chloronaphthalene, and then spin-coat a blend photoactive layer of about 160 nm, anneal at 150 °C for 10 minutes, then spin-coat a 10-nm layer of MoO3 as the anode interface layer, and then evaporate a 100-nm Al layer to complete the preparation of the device.

[0568] Test Example 8

[0569] Taking the resonance boron-nitrogen small-molecule acceptor L14 obtained in Example 14 as an example, its detection performance is described.

[0570] The specific preparation process of the short-wave infrared organic optoelectronic detector with the aforementioned structure is as follows:

[0571] Spin-coat a 20-nm layer of zinc oxide (ZnO) on ITO glass, and then anneal it at 200 °C for 60 minutes as the anode interface layer. Dissolve the polymer donor PBDB-T and the small-molecule acceptor L13 in chloroform, add 1.2% by volume of chloronaphthalene, and then spin-coat a blend photoactive layer of about 160 nm, anneal it at 150 °C for 10 minutes, then spin-coat a 10-nm layer of MoO3 as the anode interface layer, and then evaporate a 100-nm Al layer to complete the preparation of the device.

[0572] Test Example 9

[0573] Taking the resonance boron-nitrogen small-molecule acceptor L16 obtained in Example 16 as an example, its detection performance is described.

[0574] The specific preparation process of the short-wave infrared organic optoelectronic detector with the foregoing structure is as follows:

[0575] Spin-coat a 20-nm layer of zinc oxide (ZnO) on ITO glass, and then anneal it at 200 °C for 60 minutes as the anode interface layer. Dissolve the polymer donor PBDB-T and the small-molecule acceptor L13 in chloroform, add 1.4% by volume of chloronaphthalene, and then spin-coat a blend photoactive layer of about 160 nm, anneal it at 150 °C for 10 minutes, then spin-coat a 10-nm layer of MoO3 as the anode interface layer, and then evaporate a 100-nm Al layer to complete the preparation of the device.

[0576] The EQE and dark current of the organic optoelectronic detectors in Test Examples 1 to 9 were measured under a 0 V bias voltage, and the corresponding responsivity R and detectivity D* were calculated. Among them, the responsivity R refers to the ratio of the photocurrent of the optoelectronic detector to the incident light intensity, and the unit is A / W. The calculation formula is as follows:

[0577]

[0578] The detectivity D* is defined as the reciprocal of the noise equivalent power (NEP), and is an index to measure the ability of the detector to detect the minimum incident light signal. The unit is Jones, and the calculation formula is as follows:

[0579]

[0580] Among them, R is the responsivity, q is the charge, and J d is the dark current density.

[0581] The results are as Figures 6 to 11 can be seen, Figure 6 is the EQE curve graph of the inverted organic photovoltaic detectors based on the resonance boron-nitrogen small molecules L1, L4, L5, L6, and L8, Figure 7EQE curves of inverted organic photovoltaic detectors based on resonant boron-nitrogen small molecules L12, L13, L14, and L16 Figure 8 Responsivity curves of organic photovoltaic detectors based on resonant boron-nitrogen small molecules L1, L4, L5, L6, and L8 Figure 9 Responsivity curves of organic photovoltaic detectors based on resonant boron-nitrogen small molecules L12, L13, L14, and L16 Figure 10 Dark current curves of organic photovoltaic detectors based on resonant boron-nitrogen small molecules L1, L4, L5, L6, and L8 Figure 11 Dark current curves of organic photovoltaic detectors based on resonant boron-nitrogen small molecules L12, L13, L14, and L16

[0582] In Test Examples 1 to 9, the device parameters of organic optoelectronic detectors with resonant boron-nitrogen small molecules / donors as the active layer under a 0 V bias are shown in Table 1:

[0583] Table 1

[0584]

[0585] Combined with the above test results, using the resonant boron-nitrogen small molecule acceptor L1 prepared in Example 1 as the acceptor material and PBDB-T as the donor material, an inverted organic optoelectronic detection device was fabricated. The detection range of this device exceeds 1350 nm. Under a 0 V bias, the EQE value at 1200 nm is 18.5%, and the dark current is 7.26×10 -10 A / cm -2 , and the corresponding responsivity and detectivity are 0.18 A / W and 1.17×10 13 Jones, respectively.

[0586] Using the resonant boron-nitrogen small molecule acceptor L4 prepared in Example 4 as the acceptor material and PBDB-T as the donor material, an inverted organic optoelectronic detection device was fabricated. The specific performance parameters are shown in Table 1. The detection range of this device exceeds 1400 nm. Under a 0 V bias, the EQE value at 1250 nm is 25.6%, and the dark current is 9.28×10 -10 A / cm -2 , and the corresponding responsivity and detectivity are 0.26 A / W and 1.50×10 13 Jones, respectively.

[0587] Using the resonant boron-nitrogen small molecule acceptor L5 prepared in Example 5 as the acceptor material and PBDB-T as the donor material, an inverted organic optoelectronic detection device was fabricated. The specific performance parameters are shown in Table 1. The detection range of this device exceeds 1400 nm. Under a 0 V bias, the EQE value at 1270 nm is 17.2%, and the dark current is 1.25×10 -9A / cm -2 , the corresponding responsivity and detectivity are 0.19 A / W and 9.50×10 12 Jones, respectively.

[0588] Using the resonance boron-nitrogen small molecule acceptor L6 prepared in Example 6 as the acceptor material and PCE10 as the donor material, an inverted organic optoelectronic detector device was fabricated. The specific performance parameters are shown in Table 1. The detection range of this device exceeds 1400 nm. At a bias voltage of 0 V, the EQE value at 1220 nm is 15.4%, and the dark current is 9.32×10 -10 A / cm -2 , the corresponding responsivity and detectivity are 0.15 A / W and 8.69×10 12 Jones, respectively.

[0589] Using the resonance boron-nitrogen small molecule acceptor L8 prepared in Example 8 as the acceptor material and PCE10 as the donor material, an inverted organic optoelectronic detector device was fabricated. The specific performance parameters are shown in Table 1. The detection range of this device exceeds 1400 nm. At a bias voltage of 0 V, the EQE value at 1250 nm is 22.6%, and the dark current is 8.92×10 -10 A / cm -2 , the corresponding responsivity and detectivity are 0.23 A / W and 1.36×10 13 Jones, respectively.

[0590] Using the resonance boron-nitrogen small molecule acceptor L12 prepared in Example 12 as the acceptor material and PCE10 as the donor material, an inverted organic optoelectronic detector device was fabricated. The specific performance parameters are shown in Table 1. The detection range of this device exceeds 1400 nm. At a bias voltage of 0 V, the EQE value at 1200 nm is 23.2%, and the dark current is 1.12×10 -9 A / cm -2 , the corresponding responsivity and detectivity are 0.22 A / W and 1.16×10 13 Jones, respectively.

[0591] Using the resonance boron-nitrogen small molecule acceptor L13 prepared in Example 13 as the acceptor material and PBDB-T as the donor material, an inverted organic optoelectronic detector device was fabricated. The specific performance parameters are shown in Table 1. The detection range of this device exceeds 1400 nm. At a bias voltage of 0 V, the EQE value at 1170 nm is 20.1%, and the dark current is 1.30×10 -9 A / cm -2 , the corresponding responsivity and detectivity are 0.19 A / W and 9.32×10 12 Jones, respectively.

[0592] Using the resonance boron-nitrogen small molecule acceptor L13 prepared in Example 13 as the acceptor material and PBDB-T as the donor material, an inverted organic optoelectronic detector was fabricated. The specific performance parameters are shown in Table 1. The detection range of this device exceeds 1400 nm. At a bias voltage of 0 V, the EQE value at 1220 nm is 20.5%, and the dark current is 1.50×10 -9 A / cm -2 , and the corresponding responsivity and detectivity are 0.20 A / W and 9.13×10 12 Jones, respectively.

[0593] Using the resonance boron-nitrogen small molecule acceptor L16 prepared in Example 16 as the acceptor material and PBDB-T as the donor material, an inverted organic optoelectronic detector was fabricated. The specific performance parameters are shown in Table 1. The detection range of this device exceeds 1400 nm. At a bias voltage of 0 V, the EQE value at 1240 nm is 24.2%, and the dark current is 1.55×10 -9 A / cm -2 , and the corresponding responsivity and detectivity are 0.24 A / W and 1.07×10 13 Jones, respectively.

[0594] Performance test of a phototransistor-type detector using a resonance boron-nitrogen polymer as an infrared light-absorbing material:

[0595] Using resonance boron-nitrogen polymers such as L25, L26, L29, and L31 as infrared light-absorbing materials, a phototransistor-type detector was fabricated for detection performance testing. The device structure of the phototransistor-type detector is as Figure 12 shown, Figure 12 which is a schematic diagram of the device structure of the phototransistor-type detector of the present invention. As can be Figure 12 seen, the structure of the phototransistor-type detector sequentially includes a P + Si / SiO2 substrate, a graphene charge transport layer, a Ti / Au alloy electrode, and a polymer infrared light-absorbing layer from bottom to top. The specific preparation process is shown in Test Examples 10 to 13.

[0596] Test Example 10

[0597] Taking the resonance boron-nitrogen polymer L25 obtained in Example 25 as an example, its detection performance was described.

[0598] The specific preparation process of the short-wave infrared organic phototransistor detector is as follows:

[0599] On the P +Transfer and cover a layer of graphene on the Si / SiO2 substrate as the charge transport layer, and then co-evaporate the Ti / Au alloy electrodes with a Ti thickness of 20 nm and an Au thickness of 60 nm. Dissolve the polymer L25 in chloroform, and coat it as an electron acceptor and an infrared photon absorption material on the charge transport layer with a thickness of about 80 nm, and anneal at 150 °C for 10 minutes to obtain the final device.

[0600] Test Example 11

[0601] Taking the resonance boron-nitrogen polymer L26 obtained in Example 26 as an example, illustrate its detection performance.

[0602] The specific preparation process of the short-wave infrared organic optoelectronic transistor detector is as follows:

[0603] On P + Transfer and cover a layer of graphene on the Si / SiO2 substrate as the charge transport layer, and then co-evaporate the Ti / Au alloy electrodes with a Ti thickness of 20 nm and an Au thickness of 60 nm. Dissolve the polymer L26 in chloroform, and coat it as an electron acceptor and an infrared photon absorption material on the charge transport layer with a thickness of about 70 nm, and anneal at 160 °C for 10 minutes to obtain the final device.

[0604] Test Example 12

[0605] Taking the resonance boron-nitrogen polymer L29 obtained in Example 29 as an example, illustrate its detection performance.

[0606] The specific preparation process of the short-wave infrared organic optoelectronic transistor detector is as follows:

[0607] On P + Transfer and cover a layer of graphene on the Si / SiO2 substrate as the charge transport layer, and then co-evaporate the Ti / Au alloy electrodes with a Ti thickness of 20 nm and an Au thickness of 60 nm. Dissolve the polymer L29 in chloroform, and coat it as an electron acceptor and an infrared photon absorption material on the charge transport layer with a thickness of about 80 nm, and anneal at 160 °C for 10 minutes to obtain the final device.

[0608] Test Example 13

[0609] Taking the resonance boron-nitrogen polymer L31 obtained in Example 31 as an example, illustrate its detection performance.

[0610] The specific preparation process of the short-wave infrared organic optoelectronic transistor detector is as follows:

[0611] On P +A layer of graphene is transferred and covered on the Si / SiO2 substrate as the charge transport layer, and then the Ti / Au alloy electrodes are co-evaporated. The thickness of Ti is 20 nm and the thickness of Au is 60 nm. The polymer L29 is dissolved in chloroform and coated on the charge transport layer as the electron acceptor and the infrared photon absorption material, with a thickness of about 80 nm, and annealed at 160 °C for 10 minutes to obtain the final device.

[0612] The noise current density of the phototransistor-type detectors in Test Examples 10 to 13 was measured, and the corresponding responsivity R and detectivity D* were calculated. Among them, the calculation methods of the responsivity R and the detectivity D* are the same as above and will not be elaborated. The results are as Figures 13 to 14 It can be seen that Figure 13 is the responsivity curve diagram of the organic phototransistor-type detectors based on the resonant boron nitride polymers L25, L26, L29, and L31, Figure 14 is the noise current density curve diagram of the organic phototransistor-type detectors based on the resonant boron nitride polymers L25, L26, L29, and L31.

[0613] In Test Examples 10 to 13, the device parameters of the organic photodetectors with resonant boron nitride as the active layer under a gate voltage of 60 V are shown in Table 2:

[0614] Table 2

[0615]

[0616] Combined with the above test results, it can be seen that using the resonant boron nitride polymer L25 prepared in Example 25 as the light-absorbing material to prepare an organic phototransistor detection device, the device structure is as Figure 6 , and the specific performance parameters are shown in Table 2. The detection range of this device exceeds 2000 nm. Under a gate voltage of 60 V, the responsivity at 1550 nm is 1.4×10 4 A / W, the noise is 5.50×10 -10 A / Hz 1 / 2 , and the detectivity is 2.30×10 10 Jones.

[0617] Using the resonant boron nitride polymer L26 prepared in Example 26 as the light-absorbing material to prepare an organic phototransistor detection device, the specific performance parameters are shown in Table 2. The detection range of this device exceeds 2000 nm. Under a gate voltage of 60 V, the responsivity at 1550 nm is 2.5×10 4 A / W, the noise is 3.50×10 -10 A / Hz 1 / 2 , and the detectivity is 6.45×10 10 Jones.

[0618] Using the resonance boron nitride polymer L29 prepared in Example 29 as the light-absorbing material, an organic optoelectronic transistor detection device was fabricated. The specific performance parameters are shown in Table 2. The detection range of this device exceeds 2000 nm. At a gate voltage of 60 V, the responsivity at 1550 nm is 3.0×10 4 A / W, and the noise is 1.00×10 -10 A / Hz 1 / 2 , and the detectivity is 2.70×10 11 Jones.

[0619] Using the resonance boron nitride polymer L31 prepared in Example 31 as the light-absorbing material, an organic optoelectronic transistor detection device was fabricated. The specific performance parameters are shown in Table 2. The detection range of this device exceeds 2000 nm. At a gate voltage of 60 V, the responsivity at 1550 nm is 3.5×10 4 A / W, and the noise is 2.10×10 -10 A / Hz 1 / 2 , and the detectivity is 1.51×10 11 Jones.

[0620] Comparative Example 1

[0621] A small molecule acceptor R35 based on the BODIPY unit, and its structural formula is shown as follows:

[0622]

[0623] Its synthetic route is as follows:

[0624]

[0625] Synthesis of Compound 35-1: Under an argon atmosphere, ultradry dichloromethane (20.0 mL) was added to a 100 mL round-bottom flask containing the boron precursor (0.44 g, 1.00 mmol). 0.30 g of DDQ (1.1 eq) was dissolved in 6 mL of toluene and added dropwise to the reaction system. The residual DDQ in the syringe was rinsed with ultradry dichloromethane, and the reaction was carried out for 3 h. At room temperature, 5.31 mL (30 eq.) of Et3N and 6.30 mL (40 eq.) of BF3·Et2O were slowly added dropwise successively, and the reaction was carried out for 5 h. Subsequently, 0.20 g (1.1 eq.) of NBS was added and the reaction was carried out at room temperature for 8 h. Then it was concentrated, and the crude product was purified by column chromatography to obtain 0.23 g of a red solid with a yield of 36%.

[0626] Synthesis of Compound 35-2: Add 52 mg (1.0 eq) of Compound 35-1, 144 mg (2.5 eq) of CPDT mono-aldehyde stannate salt, and 3.6 mg (0.04 eq) of tetrakis(triphenylphosphine)palladium into a polymerization tube. Add 20 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, react at 110 °C for 8 h. After the system cools down, extract with dichloromethane / water twice, dry, and rotary evaporate to dryness. The yellow pure product (81 mg) is obtained by column chromatography separation, with a yield of 75%.

[0627] Synthesis of Compound R35: Add 67 mg (1.0 eq) of Compound 35-2 and 58 mg (5.0 eq) of 2F-IC into a polymerization tube, and add 20 mL of ultra-dry chloroform. Add 0.15 mL of pyridine under an argon atmosphere, and then react at 65 °C overnight. The next day, the color of the solution changes from yellow to brownish green. After the system cools down, rotary evaporate and then add it to methanol for reverse sedimentation to remove 2F-IC. The resulting solid is separated by column chromatography to obtain 58 mg, with a yield of 66%.

[0628] Elemental analysis of the structure (C 102 H 109 BF6N6O4S5): Theoretical values: C, 69.29; H, 6.21; B, 0.61; F, 6.45; N, 4.75; O, 3.62; S, 9.07. Measured values: C, 69.27; H, 6.20; N, 4.69.

[0629] MALDI-TOF analysis, theoretical value: 1766.71; experimental value: 1766.7.

[0630] Comparative Example 2

[0631] A small molecule receptor R36 based on the BODIPY unit, with the structural formula shown below:

[0632]

[0633] Its synthesis route is as follows:

[0634]

[0635] Synthesis of Compound 36-1: The synthesis method is the same as that of 35-1 in Comparative Example 1.

[0636] Synthesis of Compound 36-2: In a polymerization tube, 52 mg (1.0 eq) of Compound 36-1, 166 mg (2.5 eq) of CPDT monoaldehyde stannous salt, and 3.6 mg (0.04 eq) of tetrakis(triphenylphosphine)palladium were added. 20 mL of ultradry toluene was added under an argon atmosphere. After complete dissolution, the mixture was reacted at 110 °C for 8 h. After the system cooled down, it was extracted twice with dichloromethane / water, dried, and concentrated by rotary evaporation. 90 mg of a yellow pure product was obtained by column chromatography separation, with a yield of 72%.

[0637] Synthesis of Compound R36: In a polymerization tube, 78 mg (1.0 eq) of Compound 36-2 and 65 mg (5.0 eq) of 2Cl-IC were added, along with 20 mL of ultradry chloroform. 0.15 mL of pyridine was added under an argon atmosphere, and then the mixture was reacted at 65 °C overnight. The next day, the color of the solution changed from yellow to brownish green. After the system cooled down, it was concentrated by rotary evaporation and then added to methanol for reverse sedimentation to remove 2Cl-IC. Subsequently, 70 mg of a solid was obtained by column chromatography separation, with a yield of 68%.

[0638] Elemental analysis of the structure (C 118 H 107 BCl4F2N8O4S5): Theoretical values: C, 69.07; H, 5.26; B, 0.53; Cl, 6.91; F, 1.85; N, 5.46; O, 3.12; S, 7.81. Measured values: C, 69.07; H, 5.25; N, 5.45.

[0639] MALDI-TOF analysis, theoretical value: 2048.58; experimental value: 2048.6.

[0640] Comparative Example 3

[0641] A small molecule acceptor R37 based on the BODIPY unit, with the structural formula shown below:

[0642]

[0643] Its synthetic route is as follows:

[0644]

[0645] Synthesis of Compound 37-1: The synthesis method is the same as that of 35-1 in Comparative Example 1.

[0646] Synthesis of Compound 37-2: In a polymerization tube, 52 mg (1.0 eq) of Compound 37-1, 131 mg (2.5 eq) of carbazole monoaldehyde stannate, and 3.6 mg (0.04 eq) of tetrakis(triphenylphosphine)palladium were added. 20 mL of ultra-dry toluene was added under an argon atmosphere. After complete dissolution, the mixture was reacted at 110 °C for 8 h. After the system cooled down, it was extracted twice with dichloromethane / water, dried, and concentrated by rotary evaporation. The yellow pure product (58 mg) was obtained by column chromatography separation, with a yield of 60%.

[0647] Synthesis of Compound R37: In a polymerization tube, 60 mg (1.0 eq) of Compound 37-2 and 58 mg (5.0 eq) of 2F-IC were added, along with 20 mL of ultra-dry chloroform. 0.15 mL of pyridine was added under an argon atmosphere, and then the mixture was reacted at 65 °C overnight. The next day, the color of the solution changed from yellow to brownish green. After the system cooled down, it was concentrated by rotary evaporation and then added to methanol for reverse sedimentation to remove 2F-IC. The resulting solid was separated by column chromatography to obtain 56 mg, with a yield of 68%.

[0648] Elemental analysis of the structure (C 100 H 99 BF6N8O4S): Theoretical values: C, 73.52; H, 6.11; B, 0.66; F, 6.98; N, 6.86; O, 3.92; S, 1.96. Measured values: C, 73.51; H, 6.10; N, 6.83.

[0649] MALDI-TOF analysis, theoretical value: 1632.75; experimental value: 1632.8.

[0650] Comparative Example 4

[0651] A polymer R38 based on a resonance boron-nitrogen bond unit has the following structural formula:

[0652]

[0653] Its synthetic route is as follows:

[0654]

[0655] Synthesis of Polymer R38: In a polymerization tube, 128 mg (1.0 eq) of dibromo BODIPY unit, 196 mg (1.0 eq) of CPDT double stannate, and 4.6 mg (0.02 eq) of tetrakis(triphenylphosphine)palladium were added. 5.0 mL of ultra-dry toluene was added under an argon atmosphere, and then the mixture was reacted under light protection at 110 °C for 12 h. After the reaction ended, the reaction system was sedimented in methanol, and the polymer precipitated. The precipitate was successively extracted with acetone, n-hexane, and chloroform by Soxhlet extraction to obtain 160 mg of the final product, with a yield of 90%.

[0656] Theoretical values of elemental analysis structure: C, 69.21; H, 7.63; B, 1.22; F, 4.29; N, 3.17; O, 3.62; S, 10.87. Test values: C, 69.19; H, 7.59; N, 3.16.

[0657] The obtained product was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene as the standard, 150 °C), and the following results were obtained: M n = 13212, PDI = 2.31.

[0658] Comparative Example 5

[0659] A polymer R39 based on a resonance boron-nitrogen bond unit has the following structural formula:

[0660]

[0661] Its synthesis route is as follows:

[0662]

[0663] Synthesis of polymer R39: 128 mg (1.0 eq) of dibromo BODIPY unit, 194 mg (1.0 eq) of benzo[a]fluorene bisstannane, and 4.6 mg (0.02 eq) of tetrakis(triphenylphosphine)palladium were added to a polymerization tube. 5.0 mL of ultra-dry toluene was added under an argon atmosphere, and then the reaction was carried out at 110 °C for 12 h in the dark. After the reaction was completed, the reaction system was precipitated in methanol, and the polymer was precipitated. The precipitate was successively extracted by Soxhlet extraction with acetone, n-hexane, and chloroform to obtain 165 mg of the final product with a yield of 93%.

[0664] Theoretical values of elemental analysis structure: C, 75.67; H, 8.20; B, 1.24; F, 4.35; N, 3.21; O, 3.67; S, 3.67. Test values: C, 75.68; H, 8.21; N, 3.19.

[0665] The obtained product was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene as the standard, 150 °C), and the following results were obtained: M n = 9569, PDI = 2.56.

[0666] Comparative Example 6

[0667] A polymer R40 based on a resonance boron-nitrogen bond unit has the following structural formula:

[0668]

[0669] Its synthesis route is as follows:

[0670]

[0671] Synthesis of Polymer R40: 128 mg (1.0 eq) of dibromo BODIPY unit, 217 mg (1.0 eq) of bithiophene bisstannane salt, and 4.6 mg (0.02 eq) of tetrakis(triphenylphosphine)palladium were added into a polymerization tube. 5.0 mL of ultra-dry toluene was added under an argon atmosphere, and then the reaction was carried out at 110 °C for 12 h in the dark. After the reaction, the reaction system was precipitated in methanol, and the polymer was precipitated. The precipitate was successively extracted by Soxhlet extraction with acetone, n-hexane, and chloroform to obtain 179 mg of the final product with a yield of 91%.

[0672] Theoretical values of elemental analysis structure: C, 70.70; H, 8.49; B, 1.10; F, 3.86; N, 2.84; O, 3.25; S, 9.76. Measured values: C, 70.72; H, 8.46; N, 2.88.

[0673] The obtained product was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene as the standard, 150 °C), and the results were as follows: M n = 15387, PDI = 2.44.

[0674] The final products of the above Comparative Examples 1-6 were tested for film-state ultraviolet-visible short-wave infrared absorption spectra, and the results were as shown in Figure 15 and Figure 16 shown. Figure 15 are the film-state ultraviolet-visible short-wave infrared absorption spectra of small molecules R35, R36, and R37 based on the resonance boron-nitrogen unit BODIPY, Figure 16 are the film-state ultraviolet-visible short-wave infrared absorption spectra of polymers R38, R39, and R40 based on the resonance boron-nitrogen unit BODIPY.

[0675] As mentioned above, it is only the preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art within the technical scope disclosed by the present invention, according to the technical solution and inventive concept of the present invention, makes equivalent substitutions or changes, and all should be covered within the protection scope of the present invention.

Claims

1. A resonant boron-nitrogen bond compound, characterized in that: It has a structure of Formula 1 or a structure of Formula 2; Wherein, n is an integer from 2 to 200; Said R1 and R2 are independently selected from self-solubilizing groups; The R3 is selected from the group consisting of fluorine atom, chlorine atom, bromine atom, iodine atom, phenyl, cyano, p-trifluoromethylphenyl, p-2,4,6-tris(trifluoromethyl)phenyl, pentafluorophenyl, C2-C 20 One of the alkyl-substituted phenyl groups; or the R3 and the B where it is located together form a borofluorenyl group or an oxaborofluorenyl group; The A1 is selected from substituted or unsubstituted C4~C 300 Aryl or substituted or unsubstituted C4~C 300 heteroaryl; The A2 is selected from substituted or unsubstituted C8 to C 200 Aryl or substituted or unsubstituted C6~C 200 heteroaryl; A3 is selected from a substituted or unsubstituted C3-C5 hydrocarbon group having electron withdrawing ability, a substituted or unsubstituted C6-C 150 Aryl or substituted or unsubstituted C6~C 150 heteroaryl; The A4 is selected from substituted or unsubstituted C6~C 250 Aryl or substituted or unsubstituted C6~C 250 Heteroaryl.

2. The resonant boron-nitrogen bond compound according to claim 1, characterized in that: A1 is selected from one of the groups represented by the structures of formula A1-1 to formula A1-35; In formula A1-1 to formula A1-35, R e and R f independently selected from hydrogen, fluorine, chlorine, bromine, -CN, -NO2, substituted or unsubstituted C1-C 32 Alkyl, substituted or unsubstituted C1~C 32 Alkoxy, substituted or unsubstituted C6~C 28 Aryl, substituted or unsubstituted C3~C 28 One of the heteroaryl groups, wherein X is an integer of 1 to 28.

3. The resonant boron-nitrogen bond compound according to claim 1, characterized in that: A2 is selected from one of the groups represented by the structures of formula A2-1 to formula A2-22; In formula A2-1 to formula A2-22, the R g Selected from substituted or unsubstituted C1~C 32 Alkyl, substituted or unsubstituted C1~C 32 Alkoxy, substituted or unsubstituted C6~C 28 Aryl, substituted or unsubstituted C3~C 28 wherein X is an integer of 1 to 28; and R4 is selected from a self-solubilizing group; In formula A3-1 to formula A3-15, R h , R i and R j independently selected from hydrogen, fluorine, chlorine, bromine, -CN, -NO2, substituted or unsubstituted C1-C 32 Alkyl, substituted or unsubstituted C1~C 32 Alkoxy, substituted or unsubstituted C6~C 28 Aryl, substituted or unsubstituted C3~C 28 One of the heteroaryl groups.

4. The resonant boron-nitrogen bond compound according to claim 1, characterized in that: A4 is selected from one of the groups represented by the structures of formula A4-1 to formula A4-30; In formula A4-1 to formula A4-30, the R k and R l independently selected from hydrogen, fluorine, chlorine, bromine, -CN, -NO2, substituted or unsubstituted C1-C 32 Alkyl, substituted or unsubstituted C1~C 32 Alkoxy, substituted or unsubstituted C6~C 28 Aryl, substituted or unsubstituted C6~C 28 One of the heteroaryl groups.

5. The resonant boron-nitrogen bond compound according to claim 1, characterized in that: The R1 and R2 are independently selected from one of formulas R-1 to R-27: Wherein, the m, j, x and y are independently integers of 1 to 28, and the p is an integer of 1 to 20.

6. The resonant boron-nitrogen bond compound according to any one of claims 1 to 4, characterized in that: The resonant boron-nitrogen bond compound is a compound with structures shown in Formula 1-1 to Formula 1-39; 7. The resonant boron-nitrogen bond compound according to claim 1, characterized in that: The resonant boron-nitrogen bond compound is a compound with structures shown in Formula 2-1 to Formula 2-12; 8. The method for preparing the resonant boron-nitrogen bond compound according to any one of claims 1 to 7, characterized in that: The following steps are involved: The compound of the structure shown in formula a is reacted with the compound of the structure shown in formula b, and then the reaction product is reacted with the compound of the structure shown in formula c to obtain a resonant boron-nitrogen bond compound of the structure shown in formula 1; or, The compound of the structure shown in formula a and the compound of the structure shown in formula d are reacted to obtain a resonant boron-nitrogen bond compound of the structure shown in formula 1; OHC-A2-A3 formula d; or, The compound of the structure shown in formula a is reacted with the compound of the structure shown in formula e, and then the reaction product is subjected to self-polymerization to obtain a resonant boron-nitrogen bond compound of the structure shown in formula 2; OHC-A4-X a Formula e; In formula e, X a Selected from halogen.

9. A photodetector, characterized in that It is an organic photovoltaic short-wave infrared detector or an organic phototransistor short-wave infrared detector; The organic photovoltaic short-wave infrared detector comprises: a cathode, a cathode interface layer arranged on the cathode, an active layer arranged on the cathode interface layer, an anode interface layer arranged on the active layer, and an anode arranged on the anode interface layer, wherein the active layer is composed of a donor material and the resonant boron-nitrogen bond compound according to any one of claims 1 to 6; The organic phototransistor short-wave infrared detector comprises: heavily doped silicon, silicon dioxide arranged on the heavily doped silicon, a charge transfer layer arranged on the silicon dioxide, an electrode arranged on the charge transfer layer and a polymer light absorption layer arranged on the electrode, wherein the polymer light absorption layer is composed of the resonant boron-nitrogen bond compound described in any one of claims 1 to 6.

10. The photodetector according to claim 9, characterized in that: In the organic photovoltaic short-wave infrared detector, the donor material is one or more of P3HT, PTB7-Th, PBDB-T or PM6; In the organic phototransistor short-wave infrared detector, the concentration of the polymer light-absorbing layer is 3 mg / mL to 20 mg / mL.

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