Resonance boron-nitrogen bond compounds, methods of making, and photodetectors

Abstract

The present application relates to the field of organic short-wave infrared photoelectronic material and organic short-wave infrared dye, in particular to a resonance boron-nitrogen bond compound, a preparation method thereof and a photoelectric detector. The present application solves the problem of few construction units and single strategy in the molecular structure 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 has the following advantages: (1) the structural unit has high electron affinity, a planar molecular skeleton and narrow optical band gap; (2) the small molecules and polymers based on the structural unit have the characteristics of strong short-wave infrared absorption and low LUMO level, and are applied to organic short-wave infrared detectors to achieve excellent detection performance; (3) the acceptor structural unit based on the resonance boron-nitrogen bond and the small molecules and polymers based on the unit have simple preparation methods, high reaction yield, rich expandable structure and greatly adjustable photoelectric properties.

Description

Technical Field

[0001] This invention relates to the field of organic short-wave infrared optoelectronic materials and organic short-wave infrared dyes, specifically to resonant boron-nitrogen bond compounds, their preparation methods, and photodetectors. Background Technology

[0002] Short-wave infrared light, invisible to the naked eye in the wavelength range of 1000nm to 3000nm, is characterized by its low harm to the human eye, good penetration, and excellent recognition capabilities. Short-wave infrared light detection holds immense potential in industrial, defense, and scientific research applications, such as optoelectronic communication, aerospace, environmental monitoring, and biomedicine. Currently, short-wave infrared light detection primarily relies on epitaxially grown single-crystal inorganic semiconductors, such as germanium (Ge) and indium gallium arsenide (InGaAs), which typically possess 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 and achieve high specific detectivity (D*). Organic semiconductors exhibit characteristics such as tunable bandgap, low cost, low power consumption, and the ability to be processed in solution and fabricated into flexible devices. Organic photodetectors, on the other hand, can achieve flexible wearable devices and room-temperature operation, showing broad application prospects in low-cost civilian fields.

[0003] However, the development of short-wave infrared-responsive organic conjugated materials with absorption spectra exceeding 1000 nm is relatively lagging, limiting the range of material choices and the improvement of device performance. Currently, the commonly used design strategy is to employ quinone structures combined with intramolecular DA effects to reduce the band gap. Furthermore, the exciton dissociation, charge generation, and collection efficiencies of existing photodiodes have not yet reached optimal levels, resulting in responsivity (R) and specific detectivity (D*) values ​​that still lag behind traditional visible light detectors, making them difficult to widely apply 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 a resonant boron-nitrogen bond compound, its preparation method and a photodetector. The resonant boron-nitrogen bond compound provided by the present invention has an absorption spectrum exceeding 1000 nm and has excellent infrared detection performance when applied to a photodetector.

[0005] This invention provides resonant boron-nitrogen bond compounds having the 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 as self-solubilizing groups;

[0009] The R3 is selected from fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, phenyl, cyano, p-trifluoromethylphenyl, p-2,4,6-tris(trifluoromethyl)phenyl, pentafluorophenyl, C2-C 20 One of the alkyl-substituted phenyl groups; or R3 together with B to form a boron fluorenyl or oxaboron fluorenyl group;

[0010] A1 is selected from substituted or unsubstituted C4 to C1. 300 Aryl or substituted or unsubstituted C4-C 300 Heteroaryl groups; preferably, A1 is selected from substituted or unsubstituted C4-C5 groups. 274 Aryl or substituted or unsubstituted C4-C 274 More preferably, the A1 is selected from substituted or unsubstituted C4-C5 groups. 20 Aryl or substituted or unsubstituted C4-C 20 Mixed aromatics;

[0011] The A2 is selected from substituted or unsubstituted C8 to C8, which have electron-donating capabilities. 200 Aryl groups or substituted or unsubstituted C6-C groups with electron-donating ability 200 Heteroaryl groups; preferably, the A2 group is selected from substituted or unsubstituted C8-C6 groups with electron-donating ability. 158 Aryl groups or substituted or unsubstituted C6-C groups with electron-donating ability 158 More preferably, the A2 is selected from substituted or unsubstituted C8-C6 groups with electron-donating ability. 62 Aryl groups or substituted or unsubstituted C6-C groups with electron-donating ability 62 Mixed aromatics;

[0012] The A3 is selected from substituted or unsubstituted C3-C5 hydrocarbon groups with electron-withdrawing ability, and substituted or unsubstituted C6-C5 hydrocarbon groups with electron-withdrawing ability. 150 Aryl groups or substituted or unsubstituted C6-C groups with electron-withdrawing ability 150 Heteroaryl; preferably, A3 is selected from substituted or unsubstituted C3-C5 hydrocarbon groups with electron-withdrawing ability, and substituted or unsubstituted C6-C5 hydrocarbon groups with electron-withdrawing ability. 112 Aryl groups or substituted or unsubstituted C6-C groups with electron-withdrawing ability 112 Heteroaryl; more preferably, the A3 is selected from substituted or unsubstituted C3-C5 hydrocarbon groups with electron-withdrawing ability, substituted or unsubstituted C6-C5 hydrocarbon groups with electron-withdrawing ability. 15 Aryl groups or substituted or unsubstituted C6-C groups with electron-withdrawing ability 15 Mixed aromatics;

[0013] The A4 is selected from substituted or unsubstituted C6 to C4.250 Aryl or substituted or unsubstituted C6-C 250 Heteroaryl groups; preferably, the A4 is selected from substituted or unsubstituted C6-C6. 210 Aryl or substituted or unsubstituted C6-C 210 More preferably, the A4 is selected from substituted or unsubstituted C6-C6. 64 Aryl or substituted or unsubstituted C6-C 64 Mixed aromatic compounds.

[0014] Introducing resonant boron-nitrogen bonds into organic conjugated materials is an effective method to achieve ultra-narrow band gaps and strong short-wave infrared absorption. Resonant boron-nitrogen bonds refer to boron-nitrogen covalent bonds and boron-nitrogen coordinate bonds of equal length, which can interconvert. The introduction of resonant boron-nitrogen bonds can enhance the effective conjugation degree within and between molecules, and reduce the band gap by significantly lowering the LUMO energy level and slightly increasing the HOMO energy level. The resonant boron-nitrogen bonded compounds provided in this application, through the introduction of resonant boron-nitrogen bonds and planar molecular framework design, achieve high charge affinity, extremely low least unoccupied molecular orbital (LUMO) energy levels, ultra-narrow optical band gaps, and ultra-strong short-wave infrared absorption, exhibiting excellent infrared detection performance in organic short-wave infrared photodetectors. Simultaneously, they possess advantages such as short reaction steps, high reaction yield, abundant scalable structures, and highly tunable photoelectric properties.

[0015] The resonant boron-nitrogen bond compounds provided by this invention include a small acceptor molecule based on a resonant boron-nitrogen unit (Formula 1) and a conjugated polymer based on a resonant boron-nitrogen unit (Formula 2). Both Formula 1 and Formula 2 have A1, R1, R2, and R3 groups, where A1 is one of the groups constituting the skeleton of the resonant boron-nitrogen bond compound of Formula 1 or Formula 2. R1 and R2 are independently selected as self-solubilizing groups, and R1 and R2 can be selected as solubilizing side chains of different lengths. R3 is a boron-substituted group selected from fluorine, chlorine, bromine, iodine, phenyl, cyano, p-trifluoromethylphenyl, p-2,4,6-tris(trifluoromethyl)phenyl, pentafluorophenyl, C2-C4, etc. 20 One of the alkyl-substituted phenyl groups; or R3 together with the B group to form a boron fluorenyl or oxaboron fluorenyl group. All possible substituted sites in the resonance boron-nitrogen bond compounds provided by this invention can be substituted.

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

[0017]

[0018]

[0019] In formulas A1-1 to A1-35, the R e and R f Independently selected from hydrogen, fluorine, chlorine, bromine, -CN, -NO2, substituted or unsubstituted C1 to C2. 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 from 1 to 28. Specifically, the formula shown... It represents the substitution site where its group is bonded to other groups.

[0020] Preferably, R1 and R2 are independently selected from one of formulas 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. Specifically, the formula shown... It represents the substitution site where its group is bonded to other groups.

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

[0024]

[0025] In formulas A2-1 to A2-22, the R g Selected from substituted or unsubstituted C1 to C2 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; X is an integer from 1 to 28; R4 is selected as a self-solubilizing group. Specifically, the formula shown... It represents the substitution site where its group is bonded to other groups.

[0026] The A3 is selected from one of the groups with the structures shown in Formulas A3-1 to A3-15;

[0027]

[0028] In formulas A3-1 to A3-15, the Rh R i and R j Independently selected from hydrogen, fluorine, chlorine, bromine, -CN, -NO2, substituted or unsubstituted C1 to C2. 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. Specifically, the formula shown... It represents the substitution site where its group is bonded to other groups.

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

[0030]

[0031]

[0032] In formulas A4-1 to A4-30, the R k and R l Independently selected from hydrogen, fluorine, chlorine, bromine, -CN, -NO2, substituted or unsubstituted C1 to C2. 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. Specifically, the formula shown... It represents the substitution site where its group is bonded to other groups.

[0033] The resonant boron-nitrogen bond compounds provided by this invention are preferably compounds with structures shown in Formula 1 to Formula 1-39.

[0034]

[0035]

[0036]

[0037]

[0038]

[0039] The resonant boron-nitrogen bond compounds provided by the present invention are preferably compounds with structures shown in Formula 2-1 to Formula 2-12.

[0040]

[0041]

[0042] This invention also provides a method for preparing the resonance boron-nitrogen bond compound described in any of the above technical solutions, comprising the following steps:

[0043] The compound with the structure shown in Formula a was reacted with the compound with the structure shown in Formula b, and then the product of the reaction was reacted with the compound with the structure shown in Formula c to obtain the resonant boron-nitrogen bond compound with the structure shown in Formula 1.

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

[0045] or,

[0046] Reaction of the compound with the structure shown in Formula a and the compound with the structure shown in Formula d yields the resonant boron-nitrogen bond compound with the structure shown in Formula 1.

[0047] OHC-A2-A3 formula d;

[0048] or,

[0049] The compound with the structure shown in Formula a and the compound with the structure shown in Formula e are reacted, and then the product obtained from the reaction is subjected to self-polymerization to obtain the resonant boron-nitrogen bond compound with the structure shown in Formula 2.

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

[0051] In equation e, X is shown a Selected from halogens; preferably, the X a It is Br.

[0052] In equations a to e, R1, R2, R3, A1, A2, A3, and A4 are the same as described above and will not be repeated here.

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

[0054]

[0055] The specific process of the above reaction includes: under an inert atmosphere, dissolving the compound with the structure shown in formula a and the compound with the structure shown in formula b in a distilled organic solvent, and performing a Knoevenagel condensation reaction in the presence of piperidine and acetic acid to obtain the precursor Pr-1 molecule; this precursor will be used in the synthesis of acceptor small molecules with electron-withdrawing terminal groups linked by double bonds, specifically by performing a Knoevenagel condensation reaction between the precursor Pr-1 molecule and the compound with the structure shown in formula c in an organic solvent in the presence of pyridine, followed by separation and purification by column chromatography to obtain the resonance boron-nitrogen bond compound with the structure shown in formula 1.

[0056] Preferably, the water content of the organic solvent used in the distillation 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 reaction temperature of the compound with the structure shown in formula a and the compound with the structure shown in formula b is 80°C to 140°C, and the reaction time is 1 h to 8 h; the reaction temperature of the product obtained and the compound with 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 with the structure shown in Formula a to the compound with the structure shown in Formula b is 1:(4-10); the molar ratio of the compound with the structure shown in Formula a to piperidine is 1:(2-6); and the molar ratio of piperidine to acetic acid is 1:(1-5). Preferably, the molar ratio of the product obtained from the reaction to the compound with the structure shown in Formula c is 1:(3-8); and the molar ratio of the product obtained from the reaction to pyridine is 1:(10-50). Preferably, the molar concentration of each raw material in its respective reaction solution is 0.0002M to 0.001M.

[0058] In a second aspect of the invention, the compound with the structure shown in Formula a and the compound with the structure shown in Formula d can also be reacted to obtain the resonant boron-nitrogen bond compound with the structure shown in Formula 1. Specifically, the compound with the structure shown in Formula a and the compound with the structure shown in Formula d are reacted in an organic solvent under the action of piperidine and acetic acid to obtain the resonant boron-nitrogen bond compound with the structure shown in Formula 1. In some embodiments of the invention, the resonant boron-nitrogen bond compound with the structure shown in Formula 1 is synthesized according to the following reaction formula:

[0059]

[0060] The specific process of the above reaction 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 d in a distilled organic solvent, carrying out a Knoevenagel condensation reaction in the presence of piperidine and acetic acid, and then separating and purifying by column chromatography to obtain the resonance boron-nitrogen bond compound with the structure shown in formula 1.

[0061] Preferably, the water content of the organic solvent used in the distillation 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 reaction temperature of the compound with the structure shown in formula a and the compound with the structure shown in formula d is 80°C to 140°C, and the time is 1 h to 8 h.

[0062] Preferably, the molar ratio of the compound with the structure shown in formula a to the compound with the structure shown in formula d is 1:(3-10); the molar ratio of the compound with the structure shown in formula a to piperidine is 1:(3-8); and the molar ratio of piperidine to acetic acid is 1:(1-5). Preferably, the molar concentration of each raw material in its respective reaction solution is 0.0002M to 0.001M.

[0063] In a third aspect of the invention, the compound with the structure shown in Formula a and the compound with the structure shown in Formula e can be reacted, and the resulting product can be subjected to self-polymerization to obtain a resonant boron-nitrogen bond compound with the structure shown in Formula 2. Specifically, the compound with the structure shown in Formula a and the compound with the structure shown in Formula e are reacted in an organic solvent under the action of piperidine and acetic acid, and the resulting product is then subjected to Stille polymerization with an alkyl bistin salt and a Stille polymerization catalyst, or the resulting product is subjected to Yamamoto polymerization with a Yamamoto polymerization catalyst to obtain a resonant boron-nitrogen bond compound with the structure shown in Formula 2. In some embodiments of the invention, the resonant boron-nitrogen bond compound with the structure shown in Formula 2 is synthesized according to the following reaction formula:

[0064]

[0065] The specific process of the above reaction includes: under 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 distilled organic solvent, and carrying out a Knoevenagel condensation reaction under the action of piperidine and acetic acid to obtain monomer m-1 molecule; under an inert atmosphere, dissolving the monomer m-1 molecule, alkyl bistin salt, and catalyst in a distilled organic solvent, and carrying out a Stille polymerization reaction under light-protected and refluxed conditions, and purifying after the reaction to obtain a homopolymer based on resonant boron-nitrogen units, that is, a resonant boron-nitrogen compound with the structure shown in formula 2; or, under an inert atmosphere, dissolving the monomer m-1 molecule and catalyst in a distilled organic solvent, and carrying out a Yamamoto polymerization reaction under light-protected and refluxed conditions, and purifying after the reaction to obtain a homopolymer based on resonant boron-nitrogen units, that is, a resonant boron-nitrogen compound with the structure shown in formula 2.

[0066] Preferably, the water content of the organic solvent used in the distillation 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 Stille polymerization catalyst is selected from one or more of tris(dibenzylacetone)palladium, tris(o-methylphenyl)phosphine, or tetra(triphenylphosphine)palladium; the Yamamoto polymerization catalyst is selected from one or more of Ni(COD)2, bipyridine, or cyclooctadiene. Preferably, the alkyl ditin salt is hexa-n-butylditin, with the following structure:

[0067] Preferably, the reaction temperature of 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 reaction time is 1h to 8h; the self-polymerization temperature of the product obtained from the reaction is 55°C to 140°C, and the reaction time is 1h to 48h; if the self-polymerization is Stille polymerization, the self-polymerization temperature is 80°C to 140°C, and the reaction time is 1h to 48h; if the self-polymerization is Yamamoto polymerization, the self-polymerization temperature is 55°C to 140°C, and the reaction time is 1h to 48h.

[0068] Preferably, the molar ratio of the compound with the structure shown in Formula a to the compound with the structure shown in Formula e is 1:(2-6); the molar ratio of the compound with the structure shown in Formula a to piperidine is 1:(2-6); and the molar ratio of piperidine to acetic acid is 1:(1-5). If the present invention undergoes Stille polymerization, the molar ratio of the compound with the structure shown in Formula a, the alkyl bistin salt, and the Stille polymerization catalyst is 1:(1-1.05):(0.05-0.25). In one embodiment of the present invention, the Stille polymerization reaction is carried out in a molar ratio of the compound with the structure shown in Formula a, the alkyl bistin salt, tris(dibenzylacetone)dipalladium, and tris(o-methylphenyl)phosphine of 1:(1-1.05):(0.01-0.05):(0.04-0.2). In another embodiment of the present invention, the present invention undergoes a Stille polymerization reaction, wherein the molar ratio of the compound with the structure shown in Formula a, the alkyl bistin salt, and tetrakis(triphenylphosphine)palladium is 1:(1-1.05):(0.01-0.05). If the present invention undergoes a Yamamoto polymerization reaction, the molar ratio of the compound with the structure shown in Formula a to the Yamamoto polymerization catalyst is 1:(9-15). In another embodiment of the present invention, the present invention undergoes a Yamamoto polymerization reaction, wherein the molar ratio of the compound with the structure shown in 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 its respective reaction solution is 0.0002M to 0.001M.

[0069] The compound with the structure shown in formula a of this invention is also called a dimethyl BIP monomer, which can be obtained by boranization reaction of a boranization precursor. The structure of the boranization precursor is as follows: Specifically, the boranylation precursor, oxidant, and boranylating reagent are subjected to a boranylation reaction to obtain a compound with the structure shown in formula a. In some embodiments of the present invention, the compound with the structure shown in formula a is synthesized according to the following reaction formula:

[0070]

[0071] The specific process of the above reaction includes: under an inert atmosphere, dissolving the boranization precursor in a distilled organic solvent, then adding an oxidant and a boranization reagent in sequence, and conducting a boranization reaction under heating conditions. Subsequently, the mixture is separated and purified by column chromatography to obtain the compound with the structure shown in 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 organic solvent used for distillation is 20 ppm to 500 ppm. The boranylating agent of the present invention can be conventionally selected according to the structure of the R3 group. Preferably, the boranylating agent is selected from a mixture of boron trifluoride diethyl ether and an organic base, boron trichloride, boron tribromide, boron triiodide, triphenylboron, a 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]boron, and 10-chloro-10H-dibenzo[b,e][1,4]oxaborane. Preferably, the oxidant is 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ). Preferably, the boranization reaction is carried out at a temperature of 20°C to 30°C, more preferably at 25°C, and for a reaction time of 12h to 24h.

[0073] This invention also provides the application of the resonant boron-nitrogen bond compound described in any of the above technical solutions in the preparation of photodetectors. Specifically, this invention provides a photodetector, which is an organic photovoltaic short-wave infrared detector or an organic phototransistor short-wave infrared detector;

[0074] The organic photovoltaic shortwave infrared detector of the present invention comprises: 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 a resonant boron-nitrogen bond compound as described in any of the above technical solutions. The resonant boron-nitrogen bond compound serves as an electron acceptor material in the organic phototransistor shortwave infrared detector, preferably selected from the resonant boron-nitrogen bond compound with the structure shown in Formula 1. The organic photovoltaic shortwave infrared detector of the present invention also includes a substrate. If the organic photovoltaic shortwave infrared detector is an inverted device structure, its cathode is disposed on the substrate; if the organic photovoltaic shortwave infrared detector is an upright 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 resonant boron-nitrogen bond compound in a mass ratio of (1-10):(1-10), 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 10nm to 40nm; the anode interface layer is MoO3 with a thickness of 10nm to 40nm; and the cathode is Al with a thickness of 60nm to 140nm.

[0075] If the organic photovoltaic shortwave infrared detector of the present invention has an inverted device structure, it can be prepared by the following steps: first, cleaning the substrate and cathode; then, placing the cathode on the substrate; next, coating the cathode interface layer on the cathode; then, spin-coating the active layer material dissolved by the processing solvent onto the cathode interface layer; after post-treatment, forming the active layer; finally, sequentially covering the active layer with the anode interface layer and the anode to obtain the organic photovoltaic shortwave 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 donor and acceptor materials dissolved is 5 mg / mL to 40 mg / mL. Preferably, the post-treatment includes one or more of thermal annealing or solvent vapor annealing; the thermal annealing temperature is 60℃ to 220℃, and the thermal annealing time is 1 min to 120 min; the solvent for solvent vapor annealing is one or more of dichloroform, chloroform, diethyl ether, or toluene, and the solvent vapor annealing time is 0.1 min to 10 min. The active layer material dissolved by the processing solvent described in this invention may also contain additives, including but not limited to one or more of 1-chloronaphthalene, 1,8-diiodooctane, 1-phenylnaphthalene, 1,3,5-tribromobenzene or diiodomethane; the introduction of additives can regulate the film morphology and improve device performance.

[0076] If the organic photovoltaic shortwave infrared detector of the present invention has an upright device structure, it can be prepared by the following steps: first, cleaning the substrate and anode; then, placing the anode on the substrate; coating the anode interface layer on the anode; then, spin-coating the active layer material dissolved by the processing solvent onto the anode interface layer; after post-treatment, forming the active layer; finally, sequentially covering the active layer with the cathode interface layer and the cathode to obtain the organic photovoltaic shortwave infrared detector with an upright device structure. Preferably, the processing solvent is chloroform, chlorobenzene, o-dichlorobenzene, toluene, or tetrahydrofuran, and the total concentration of the donor and acceptor materials dissolved is 5 mg / mL to 40 mg / mL. Preferably, the post-treatment includes one or more of thermal annealing or solvent vapor annealing; the thermal annealing temperature is 60℃ to 220℃, and the thermal annealing time is 1 min to 120 min; the solvent for solvent vapor annealing is one or more of dichloroform, chloroform, diethyl ether, or toluene, and the solvent vapor annealing time is 0.1 min to 10 min. The active layer material dissolved by the processing solvent described in this invention may also contain additives, including but not limited to one or more of 1-chloronaphthalene, 1,8-diiodooctane, 1-phenylnaphthalene, 1,3,5-tribromobenzene or diiodomethane; the introduction of additives can regulate the film morphology and improve device performance.

[0077] The organic phototransistor type short-wave infrared detector of the present invention is preferably a bottom-gate top-contact structure, comprising, from top to bottom: heavily doped silicon, silicon dioxide disposed on the heavily doped silicon, a charge transport layer disposed on the silicon dioxide, an electrode disposed on the charge transport layer, and a polymer light-absorbing layer disposed on the electrode. The polymer light-absorbing layer is composed of a resonant boron-nitrogen bond compound as described in any of the above technical solutions. The resonant boron-nitrogen bond compound serves as an electron acceptor and infrared photon absorber in the organic phototransistor type short-wave infrared detector, and is preferably selected from the resonant boron-nitrogen bond compound with 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; and 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 phototransistor-type short-wave infrared detector of this invention is prepared by the following steps: silicon dioxide is deposited on heavily doped silicon to obtain a substrate; after cleaning the obtained substrate, a charge transport layer is transferred onto the substrate, such that the charge transport layer is deposited on the silicon dioxide; subsequently, an electrode is covered on the charge transport layer; finally, the resonant boron-nitrogen bond compound is dissolved in a processing solvent and coated onto the charge transport layer as an electron acceptor and infrared photon absorbing material; and a polymer light-absorbing layer is formed through post-treatment to obtain the final device. Preferably, the processing solvent is selected from dichloromethane, trichloromethane, chlorobenzene, o-dichlorobenzene, toluene, or tetrahydrofuran. Preferably, the post-treatment includes one or more of thermal annealing or solvent vapor annealing; the thermal annealing temperature is 60℃~220℃, and the thermal annealing time is 1min~120min; the solvent for solvent vapor annealing is one or more of dichloromethane, trichloromethane, diethyl ether, or toluene, and the solvent vapor annealing time is 0.1min~10min.

[0079] This invention provides resonant boron-nitrogen bond compounds, their preparation methods, and photodetectors. This invention develops and designs organic structural units based on resonant boron-nitrogen bonds, as well as small-molecule and polymeric resonant boron-nitrogen bond compounds based on these units, solving the problems of limited building blocks and singular strategies in existing organic short-wave infrared optoelectronic materials and organic short-wave infrared dye molecular structures. Compared with existing technologies, the resonant boron-nitrogen bond compounds provided by this invention have the following advantages: (1) The structural unit possesses high electron affinity, a planar molecular framework, and a narrow optical band gap. (2) Small molecules and polymers based on this structural unit exhibit strong short-wave infrared absorption and low LUMO energy levels, achieving excellent detection performance when applied to organic short-wave infrared detectors. (3) The acceptor structural unit based on resonant boron-nitrogen bonds and the small molecules and polymers based on these units in this invention have simple preparation methods, high reaction yields, abundant expandable structures, and significantly tunable photoelectric properties. Experiments show that the absorption spectrum of the resonant boron-nitrogen bond compounds provided by this invention exceeds 1000 nm, exhibiting excellent infrared detection performance when applied to photodetectors. Attached Figure Description

[0080] Figure 1 The UV-Vis shortwave infrared absorption spectra of small molecules L1, L4, and L5 based on resonant boron-nitrogen unit (BIP) are shown.

[0081] Figure 2 The film-state UV-Vis short-wave infrared absorption spectra of small molecules L6, L8, and L12 based on resonant boron-nitrogen unit (BIP);

[0082] Figure 3 The UV-Vis short-wave infrared absorption spectra of small molecules L13, L14 and L16 based on resonant boron-nitrogen unit (BIP) are shown.

[0083] Figure 4 The UV-Vis shortwave infrared absorption spectra of polymers L25, L26, L29 and L31 based on resonant boron-nitrogen unit (BIP) are shown.

[0084] Figure 5 This is a schematic diagram of the device structure of the photovoltaic detector described in this invention;

[0085] Figure 6 The EQE curves of the inverted organic photovoltaic detector based on the resonant boron-nitrogen small molecules L1, L4, L5, L6 and L8 are shown.

[0086] Figure 7 The EQE curves of the inverted organic photovoltaic detector based on the resonant boron-nitrogen small molecules L12, L13, L14 and L16 are shown.

[0087] Figure 8The responsivity curves of organic photovoltaic detectors based on resonant boron-nitrogen small molecules L1, L4, L5, L6, and L8 are shown.

[0088] Figure 9 The responsivity curves of organic photovoltaic detectors based on resonant boron-nitrogen small molecules L12, L13, L14 and L16 are shown.

[0089] Figure 10 The dark current curves are for organic photovoltaic detectors based on resonant boron-nitrogen small molecules L1, L4, L5, L6, and L8.

[0090] Figure 11 The dark current curves of organic photovoltaic detectors based on resonant boron-nitrogen small molecules L12, L13, L14 and L16 are shown.

[0091] Figure 12 This is a schematic diagram of the device structure of the phototransistor detector described in this invention;

[0092] Figure 13 The responsivity curves of organic phototransistor detectors based on resonant boron-nitrogen polymers L25, L26, L29, and L31 are shown.

[0093] Figure 14 The noise current density curves of organic phototransistor detectors based on resonant boron-nitrogen polymers L25, L26, L29, and L31 are shown.

[0094] Figure 15 The UV-Vis short-wave infrared absorption spectra of small molecules R35, R36, and R37 based on the resonant boron-nitrogen unit BODIPY.

[0095] Figure 16 The images show the film-state UV-Vis shortwave infrared absorption spectra of polymers R38, R39, and R40 based on the resonant boron-nitrogen unit BODIPY. Detailed Implementation

[0096] This invention discloses resonant boron-nitrogen bond compounds, their preparation methods, and photodetectors. Those skilled in the art can refer to the content of this document and appropriately modify the process parameters to achieve the desired results. It should be particularly noted that all similar substitutions and modifications are obvious to those skilled in the art and are considered to be included in this invention. The methods and applications of this invention have been described through preferred embodiments, and those skilled in the art will clearly be able to modify or appropriately change and combine the methods and applications described herein without departing from the content, spirit, and scope of this invention to realize and apply the technology of this invention.

[0097] The present invention will be further described below with reference to the embodiments:

[0098] Example 1

[0099] A small molecule receptor L1 based on resonant boron-nitrogen bonds, with the structural formula shown in Formula L1:

[0100]

[0101] Its synthetic route is as follows:

[0102]

[0103] Synthesis of compound 1-1:

[0104] Under an argon atmosphere, 20.0 mL of ultradry dichloromethane was added to a 100 mL round-bottom flask containing 0.40 g (1.38 mmol) of boron precursor. 0.35 g of DDQ (1.1 eq) was dissolved in 6 mL of toluene and added dropwise to the reaction system. The syringe containing residual DDQ was rinsed with ultradry dichloromethane, and the reaction was allowed to proceed for 3 h. Then, 6.19 mL (30 eq.) of DBU and 7.35 mL (40 eq.) of BF3·Et2O were slowly added dropwise at -78 °C, reacting for 5 min each time, followed by a 5 h reaction at room temperature. After cooling to room temperature, the reaction system was concentrated, and the crude product was purified by column chromatography to give 0.27 g of a deep red liquid, with a yield of 33%.

[0105] Synthesis of compounds 1-2:

[0106] Compound 1-1 24 mg (1.0 eq) and CPDT dialdehyde 165 mg (6.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 20 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 89 μL of piperidine and 69 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 1 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 36 mg of a pure, brownish-green product (46% yield) was obtained by column chromatography.

[0107] Synthesis of compound L1:

[0108] Compound 1-2 63 mg (1.0 eq), 2F-IC 57 mg (5.0 eq), and ultradry chloroform 20 mL were added to a polymerization tube. 0.15 mL of pyridine was added under an argon atmosphere, and the reaction was carried out overnight at 70 °C. The next day, the solution color changed from green to brownish-blue. After cooling, the solution was evaporated to dryness and then added to methanol for back precipitation to remove 2F-IC. The resulting solid was then separated by column chromatography to obtain 52 mg, with a yield of 62%.

[0109] Elemental analysis structure (C 96 H 90B2F8N8O2S4): 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 receptor L2 based on resonant boron-nitrogen bonds, with the structural formula shown in Formula L2:

[0113]

[0114] Its synthetic route is as follows:

[0115]

[0116] Synthesis of compound 2-1:

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

[0118] Synthesis of compounds 1-2:

[0119] Compound 2-1 58 mg (1.0 eq) and CPDT dialdehyde 275 mg (6.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 20 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 176 μL of piperidine and 138 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 1 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 73 mg of a pure, brownish-green product (50% yield) was obtained by column chromatography.

[0120] Synthesis of compound L2:

[0121] 73 mg (1.0 eq) of compound 2-2, 58 mg (5.0 eq) of 2F-IC, and 20 mL of ultradry chloroform were added to a polymerization tube. 0.16 mL of pyridine was added under an argon atmosphere, and the reaction was carried out at 70 °C for 18 h. The next day, the solution color changed from green to brownish-blue. After cooling, the solution was evaporated to dryness and then added to methanol for back precipitation to remove 2F-IC. The resulting solid was then separated by column chromatography to give 62 mg of a dark red solid, with a yield of 65%.

[0122] Elemental analysis structure (C 106 H 110B2F8N8O6S4): 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 receptor L3 based on resonant boron-nitrogen bonds has the structural formula 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 in 3-1 are the same as in 1-1, only the raw materials are changed.

[0131] Synthesis of compound 3-2:

[0132] Compound 3-1 68 mg (1.0 eq) and alkoxythiophene dialdehyde 194 mg (6.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 20 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 176 μL of piperidine and 138 μL of glacial acetic acid were added. The mixture was then reacted at 75 °C for 1 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 58 mg of a pure, brownish-green product (45% yield) was obtained by column chromatography.

[0133] Synthesis of compound L3:

[0134] Compound 3-2 58 mg (1.0 eq), 2F-IC 52 mg (5.0 eq), and ultradry chloroform 20 mL were added to a polymerization tube. 0.13 mL of pyridine was added under an argon atmosphere, and the reaction was carried out at 60 °C for 14 h. The next day, the solution color changed from green to brownish-blue. After cooling, the solution was evaporated to dryness and then added to methanol for back precipitation to remove 2F-IC. The resulting solid was then separated by column chromatography to give 50 mg of a black solid, with a yield of 65%.

[0135] Elemental analysis structure (C 98 H 90B2F8N8O6S2): 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 receptor based on a unit with resonant boron-nitrogen bonds, L4, has the structural formula 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 in 4-1 are the same as in 1-1, only the raw materials are changed.

[0144] Synthesis of compound 4-2:

[0145] Compound 4-1 56 mg (1.0 eq) and CPDT dialdehyde 229 mg (5.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 15 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 176 μL of piperidine and 138 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 1 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 61 mg of a pure, brownish-green product (42% yield) was obtained by column chromatography.

[0146] Synthesis of compound L4:

[0147] Compound 4-2 61 mg (1.0 eq), 2Cl-IC 55 mg (5.0 eq), and ultradry chloroform 20 mL were added to a polymerization tube. 0.15 mL of pyridine was added under an argon atmosphere, and the reaction was carried out at 65 °C for 12 h. The next day, the solution color changed from green to blue. After cooling, the solution was evaporated to dryness and then added to methanol for back precipitation to remove 2Cl-IC. The resulting solid was then separated by column chromatography to give 56 mg of a dark red solid, with a yield of 68%.

[0148] Elemental analysis structure (C 110 H 98 B2C l4F4N8O2S4): 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 receptor L5 based on resonant boron-nitrogen bonds, with the structural formula 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 in 5-1 are the same as in 1-1, only the raw materials are changed.

[0157] Synthesis of compound 5-2:

[0158] Compound 5-1 44 mg (1.0 eq) and CPDT dialdehyde 284 mg (5.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 15 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 176 μL of piperidine and 138 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 1 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 64 mg of a pure, brownish-green product (42% yield) was obtained by column chromatography.

[0159] Synthesis of compound L5:

[0160] Compound 5-2 64 mg (1.0 eq), 2Cl-IC 65 mg (6.0 eq), and ultradry chloroform 20 mL were added to a polymerization tube. 0.15 mL of pyridine was added under an argon atmosphere, and the reaction was carried out at 65 °C for 12 h. The next day, the solution color changed from green to blue. After cooling, the solution was evaporated to dryness and then added to methanol for back precipitation to remove 2Cl-IC. The resulting solid was then separated by column chromatography to give 56 mg of a 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 receptor based on a unit with resonant boron-nitrogen bonds, L6, has the structural formula 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 in 6-1 are the same as in 1-1, only the raw materials and reactants are changed.

[0170] Synthesis of compound 6-2:

[0171] Compound 6-1 134 mg (1.0 eq) and CPDT dialdehyde 229 mg (5.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 15 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 176 μL of piperidine and 138 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 1 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 94 mg of a pure, brownish-green product (42% yield) was obtained by column chromatography.

[0172] Synthesis of compound L6:

[0173] 94 mg (1.0 eq) of compound 6-2, 66 mg (6.0 eq) of 2Cl-IC, and 20 mL of ultradry chloroform were added to a polymerization tube. 0.15 mL of pyridine was added under an argon atmosphere, and the reaction was carried out at 65 °C for 12 h. The next day, the solution color changed from green to blue. After cooling, the solution was evaporated to dryness and then added to methanol for back precipitation to remove 2Cl-IC. The resulting solid was then separated by column chromatography to give 77 mg of a 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 receptor based on a unit with resonant boron-nitrogen bonds, L7, has the structural formula 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 in 7-1 are the same as in 1-1, only the raw materials and reactants are changed.

[0183] Synthesis of compound 7-2:

[0184] Compound 7-1 48 mg (1.0 eq) and thiophene dialdehyde 335 mg (6.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 15 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 180 μL of piperidine and 140 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 1 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 68 mg of a pure, brownish-green product (43% yield) was obtained by column chromatography.

[0185] Synthesis of compound L7:

[0186] Compound 7-2 68 mg (1.0 eq), 2F-IC 58 mg (6.0 eq), and ultradry chloroform 18 mL were added to a polymerization tube. 0.15 mL of pyridine was added under an argon atmosphere, and the reaction was carried out at 65 °C for 16 h. The next day, the solution color changed from green to blue. After cooling, the solution was evaporated to dryness and then added to methanol for back precipitation to remove 2F-IC. The resulting solid was then separated by column chromatography to give 59 mg of a black solid, with a yield of 71%.

[0187] Elemental analysis structure (C 118 H 126B2F8N8O2S4): 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 receptor based on a unit with resonant boron-nitrogen bonds, L8, has the structural formula 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 for 8-1 are the same as those for 1-1, only the raw materials are changed.

[0196] Synthesis of compound 8-2:

[0197] Compound 8-1 76 mg (1.0 eq) and CPDT dialdehyde 386 mg (6.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 15 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 190 μL of piperidine and 150 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 2 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 73 mg of a pure, brownish-green product (36% yield) was obtained by column chromatography.

[0198] Synthesis of compound L8:

[0199] 73 mg (1.0 eq) of compound 8-2, 50 mg (6.0 eq) of 2F-IC, and 18 mL of ultradry chloroform were added to a polymerization tube. 0.15 mL of pyridine was added under an argon atmosphere, and the reaction was carried out at 65 °C for 16 h. The next day, the solution color changed from green to blue. After cooling, the solution was evaporated to dryness and then added to methanol for back precipitation. The resulting solid was then separated by column chromatography to give 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 receptor based on a unit with resonant boron-nitrogen bonds, L9, has the structural formula shown in Formula L9:

[0204]

[0205] Its synthetic route is as follows:

[0206]

[0207] Synthesis of compound 9-1:

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

[0209] Synthesis of compound 9-2:

[0210] Compound 9-1 75 mg (1.0 eq) and CPDT dialdehyde 185 mg (6.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 15 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 190 μL of piperidine and 150 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 2 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 40 mg of a pure, brownish-green product (30% yield) was obtained by column chromatography.

[0211] Synthesis of compound L9:

[0212] Compound 9-2 40 mg (1.0 eq), 2F-IC 42 mg (6.0 eq), and ultradry chloroform 18 mL were added to a polymerization tube. 0.15 mL of pyridine was added under an argon atmosphere, and the reaction was carried out at 65 °C for 16 h. The next day, the solution color changed from green to blue. After cooling, the solution was evaporated to dryness and then added to methanol for back precipitation. The resulting solid was then separated by column chromatography to give 35 mg of a dark purple solid, with a yield of 67%.

[0213] Elemental analysis structure (C 102 H 118B2F8N8O4S2): 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 receptor based on a unit with resonant boron-nitrogen bonds, L10, has the structural formula 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 for 10-1 are the same as those for 1-1, only the raw materials are changed.

[0222] Synthesis of compound 10-2:

[0223] 10⁻¹ 55 mg (1.0 eq) of compound and 274 mg (6.0 eq) of CPDT dialdehyde were added to a polymerization tube. 200 mg of molecular sieve was added to 15 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 190 μL of piperidine and 150 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 2 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 57 mg of a pure, brownish-green product (40% yield) was obtained by column chromatography.

[0224] Synthesis of compound L10:

[0225] 57 mg (1.0 eq) of compound 10⁻², 55 mg (6.0 eq) of 2F-IC, and 18 mL of ultradry chloroform were added to a polymerization tube. 0.15 mL of pyridine was added under an argon atmosphere, and the reaction was carried out at 65 °C for 13 h. The next day, the solution color changed from green to blue. After cooling, the solution was evaporated to dryness and then added to methanol for back precipitation. The resulting solid was then separated by column chromatography to give 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 receptor based on a resonant boron-nitrogen bond, L11, has the structural formula 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 for 11-1 are the same as those for 1-1, only the raw materials are changed.

[0235] Synthesis of compound 11-2:

[0236] Compound 11-1 46 mg (1.0 eq) and carbazole dialdehyde 234 mg (6.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 15 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 178 μL of piperidine and 132 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 3 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 42 mg of a light green, pure product was obtained by column chromatography, with a yield of 35%.

[0237] Synthesis of compound L11:

[0238] Compound 11-2 42 mg (1.0 eq), 2F-IC 48 mg (6.0 eq), and ultradry chloroform 18 mL were added to a polymerization tube. 0.15 mL of pyridine was added under an argon atmosphere, and the reaction was carried out at 65 °C for 13 h. The next day, the solution color changed from green to blue. After cooling, the solution was evaporated to dryness and then added to methanol for back precipitation. The resulting solid was then separated by column chromatography to give 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 receptor based on a resonant boron-nitrogen bond, L12, has the structural formula shown in Formula L12:

[0243]

[0244] Its synthetic route is as follows:

[0245]

[0246] Synthesis of compound 12-1:

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

[0248] Synthesis of compound 12-2:

[0249] Compound 12-1 128 mg (1.0 eq) and CPDT dialdehyde 275 mg (6.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 15 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 178 μL of piperidine and 132 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 3 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 87 mg of a light green, pure product was obtained by column chromatography, with a yield of 40%.

[0250] Synthesis of compound L12:

[0251] Compound 12-2 42 mg (1.0 eq), 2Cl-IC 63 mg (6.0 eq), and ultradry chloroform 18 mL were added to a polymerization tube. 0.15 mL of pyridine was added under an argon atmosphere, and the reaction was carried out at 65 °C for 13 h. The next day, the solution color changed from green to blue. After cooling, the solution was evaporated to dryness and then added to methanol for back precipitation. The resulting solid was then separated by column chromatography to give 74 mg of a 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 receptor based on a resonant boron-nitrogen bond, L13, has the structural formula shown in Formula L13:

[0256]

[0257] Its synthetic route is as follows:

[0258]

[0259] Synthesis of compound 13-1:

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

[0261] Synthesis of compound 13-2:

[0262] Compound 13-1 62 mg (1.0 eq) and CPDT dialdehyde 275 mg (6.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 15 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 178 μL of piperidine and 132 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 3 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 56 mg of a light green, pure product was obtained by column chromatography, with a yield of 37%.

[0263] Synthesis of compound L13:

[0264] Compound 13-2 56 mg (1.0 eq), 2F-IC 51 mg (6.0 eq), and ultradry chloroform 18 mL were added to a polymerization tube. 0.15 mL of pyridine was added under an argon atmosphere, and the reaction was carried out at 65 °C for 13 h. The next day, the solution color changed from green to blue. After cooling, the solution was evaporated to dryness and then added to methanol for back precipitation. The resulting solid was then separated by column chromatography to give 44 mg of a black solid, with a yield of 62%.

[0265] Elemental analysis structure (C 110 H 113B2F8N9O4S4): 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 receptor based on a resonant boron-nitrogen bond, L14, has the structural formula shown in Formula L14:

[0269]

[0270] Its synthetic route is as follows:

[0271]

[0272] Synthesis of compound 14-1:

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

[0274] Synthesis of compound 14-2:

[0275] Compound 14-1 89 mg (1.0 eq) and CPDT dialdehyde 275 mg (6.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 16 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 150 μL of piperidine and 115 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 3 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 56 mg of a light green, pure product was obtained by column chromatography, with a yield of 32%.

[0276] Synthesis of compound L14:

[0277] Compound 14-2 56 mg (1.0 eq), 2Cl-IC 50 mg (6.0 eq), and ultradry chloroform 12 mL were added to a polymerization tube. 0.12 mL of pyridine was added under an argon atmosphere, and the reaction was carried out at 65 °C for 13 h. The next day, the solution color changed from green to blue. After cooling, the solution was evaporated to dryness and then added to methanol for back precipitation. The resulting solid was then separated by column chromatography to give 45 mg of a dark red solid, with a yield of 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 receptor based on a resonant boron-nitrogen bond, L15, has the structural formula 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 for 15-1 are the same as those for 1-1, only the raw materials are changed.

[0287] Synthesis of compound 15-2:

[0288] 15-165 mg (1.0 eq) of compound and 275 mg (6.0 eq) of CPDT dialdehyde were added to a polymerization tube. 200 mg of molecular sieve was added to 14 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 160 μL of piperidine and 118 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 3 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 54 mg of a green, pure product was obtained by column chromatography, with a yield of 35%.

[0289] Synthesis of compound L15:

[0290] 54 mg (1.0 eq) of compound 15-2, 55 mg (6.0 eq) of 2Cl-IC, and 12 mL of ultradry chloroform were added to a polymerization tube. 0.12 mL of pyridine was added under an argon atmosphere, and the reaction was carried out at 65 °C for 13 h. The next day, the solution color changed from green to blue. After cooling, the solution was evaporated to dryness and then added to methanol for back precipitation. The resulting solid was then separated by column chromatography to give 49 mg of a dark red solid, with a yield of 69%.

[0291] Elemental analysis structure (C 120 H 106B₂Cl₄N₈O₄S₄): 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 receptor based on a resonant boron-nitrogen bond, L16, has the structural formula 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 for 16-1 are the same as those for 1-1, only the raw materials are changed.

[0300] Synthesis of compound 16-2:

[0301] 16-1 56 mg (1.0 eq) of compound and 395 mg (6.0 eq) of CPDT dialdehyde were added to a polymerization tube. 200 mg of molecular sieve was added to 14 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 160 μL of piperidine and 118 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 3 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 74 mg of a light green, pure product was obtained by column chromatography, with a yield of 40%.

[0302] Synthesis of compound L16:

[0303] 74 mg (1.0 eq) of compound 16-2, 52 mg (5.0 eq) of 2Cl-IC, and 12 mL of ultradry chloroform were added to a polymerization tube. 0.12 mL of pyridine was added under an argon atmosphere, and the reaction was carried out at 65 °C for 13 h. The next day, the solution color changed from green to blue. After cooling, the solution was evaporated to dryness and then added to methanol for back precipitation. The resulting solid was then separated by column chromatography to give 62 mg of a dark red solid, with a yield of 66%.

[0304] Elemental analysis structure (C 140 H 138B₂Cl₄F₄N₈O₂S₄): 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. Tested 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 receptor based on a resonant boron-nitrogen bond, L17, has the structural formula 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 for 17-1 are the same as those for 1-1, only the raw materials are changed.

[0313] Synthesis of compound 17-2:

[0314] Compound 17-1 56 mg (1.0 eq) and thiophene dialdehyde 319 mg (6.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 16 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 160 μL of piperidine and 118 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 3 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 57 mg of a pure yellow product (36% yield) was obtained by column chromatography.

[0315] Synthesis of compound L17:

[0316] Compound 17-2 57 mg (1.0 eq), 2Cl-IC 57 mg (6.0 eq), and ultradry chloroform 12 mL were added to a polymerization tube. 0.13 mL of pyridine was added under an argon atmosphere, and the reaction was carried out at 65 °C for 13 h. The next day, the solution color changed from yellow to blue. After cooling, the solution was evaporated to dryness and then added to methanol for back precipitation. The resulting solid was then separated by column chromatography to give 52 mg of a dark red solid, with a yield of 70%.

[0317] Elemental analysis structure (C 120 H 126B₂Cl₄F₄N₈O₂S₄): 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 receptor based on a resonant boron-nitrogen bond, L18, has the structural formula shown in Formula L18:

[0321]

[0322] Its synthetic route is as follows:

[0323]

[0324] Synthesis of compound 18-1:

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

[0326] Synthesis of compound 18-2:

[0327] Compound 18-1 56 mg (1.0 eq) and thiophene dialdehyde 596 mg (6.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 16 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 160 μL of piperidine and 118 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 3 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 82 mg of a pure yellow product (33% yield) was obtained by column chromatography.

[0328] Synthesis of compound L18:

[0329] Compound 18-2 82 mg (1.0 eq), 2Cl-IC 52 mg (6.0 eq), and ultradry chloroform 12 mL were added to a polymerization tube. 0.13 mL of pyridine was added under an argon atmosphere, and the reaction was carried out at 65 °C for 13 h. The next day, the solution color changed from yellow to blue. After cooling, the solution was evaporated to dryness and then added to methanol for back precipitation. The resulting solid was then separated by column chromatography to give 58 mg of a dark red solid, with a yield of 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 receptor based on a resonant boron-nitrogen bond, L19, has the structural formula 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 for 19-1 are the same as those for 1-1, only the raw materials are changed.

[0339] Synthesis of compound 19-2:

[0340] Compound 19-1 56 mg (1.0 eq) and benzodiindene dithiophene dialdehyde 597 mg (6.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 16 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 160 μL of piperidine and 118 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 3 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 98 mg of a green, pure product was obtained by column chromatography, with a yield of 39%.

[0341] Synthesis of compound L19:

[0342] 98 mg (1.0 eq) of compound 19-2, 61 mg (6.0 eq) of 2Cl-IC, and 12 mL of ultradry chloroform were added to a polymerization tube. 0.13 mL of pyridine was added under an argon atmosphere, and the reaction was carried out at 65 °C for 13 h. The next day, the solution color changed from green to blue. After cooling, the solution was evaporated to dryness and then added to methanol for back precipitation. The resulting solid was then separated by column chromatography to give 78 mg of a dark 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 receptor L20 based on resonant boron-nitrogen bonds has the structural formula 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 for 20-1 are the same as those for 1-1, only the raw materials are changed.

[0352] Synthesis of compound 20-2:

[0353] 20-1 56 mg (1.0 eq) of compound and 335 mg (6.0 eq) of fluorenidine were added to a polymerization tube. 200 mg of molecular sieve was added to 16 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 160 μL of piperidine and 118 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 3 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 66 mg of a pure yellow product (40% yield) was obtained by column chromatography.

[0354] Synthesis of compound L20:

[0355] 82 mg (1.0 eq) of compound 20-2, 63 mg (6.0 eq) of 2Cl-IC, and 15 mL of ultradry chloroform were added to a polymerization tube. 0.16 mL of pyridine was added under an argon atmosphere, and the reaction was carried out at 65 °C for 13 h. The next day, the solution color changed from yellow to blue. After cooling, the solution was evaporated to dryness and then added to methanol for back precipitation. The resulting solid was then separated by column chromatography to give 53 mg of a dark red solid, with a yield of 62%.

[0356] Elemental analysis structure (C 134 H 138B₂Cl₄F₄N₈O₂): Theoretical values: C, 75.49; H, 6.52; B, 1.01; Cl, ​​6.65; F, 3.56; N, 5.26; O, 1.50. Test 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 receptor based on a unit with resonant boron-nitrogen bonds, L21, has the structural formula 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 for 21-1 are the same as those for 1-1, only the raw materials are changed.

[0365] Synthesis of compound 21-2:

[0366] Compound 21-1 56 mg (1.0 eq) and CPDT dialdehyde 275 mg (6.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 16 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 160 μL of piperidine and 118 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 3 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 50 mg of a green, pure product was obtained by column chromatography, with a yield of 40%.

[0367] Synthesis of compound L21:

[0368] Compound 21-2 50 mg (1.0 eq), 21-3 75 mg (6.0 eq), and 15 mL of ultradry chloroform were added to a polymerization tube. 0.16 mL of pyridine was added under an argon atmosphere, and the reaction was carried out at 65 °C for 13 h. The next day, the solution color changed from yellow to blue. After cooling, the solution was evaporated to dryness and then added to methanol for back precipitation. The resulting solid was then separated by column chromatography to give 55 mg of a dark red solid, with a yield of 68%.

[0369] Elemental analysis structure (C 118 H 102B₂Cl₄F₄N₈O₂S₄): 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 receptor based on a unit with resonant boron-nitrogen bonds, L22, has the structural formula 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 for 22-1 are the same as those for 1-1, only the raw materials are changed.

[0378] Synthesis of compound 22-2:

[0379] Compound 22-1 56 mg (1.0 eq) and CPDT dialdehyde 275 mg (6.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 16 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 160 μL of piperidine and 118 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 3 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 50 mg of a green, pure product was obtained by column chromatography, with a yield of 40%.

[0380] Synthesis of compound L22:

[0381] Compound 21-2 50 mg (1.0 eq), 22-3 75 mg (6.0 eq), and 15 mL of ultradry chloroform were added to a polymerization tube. 0.16 mL of pyridine was added under an argon atmosphere, and the reaction was carried out at 65 °C for 13 h. The next day, the solution color changed from yellow to blue. After cooling, the solution was evaporated to dryness and then added to methanol for back precipitation. The resulting solid was then separated by column chromatography to give 58 mg of a dark red solid, with a yield of 70%.

[0382] Elemental analysis structure (C 118 H 102B₂Cl₄F₄N₈O₂S₄): 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 receptor based on a resonant boron-nitrogen bond, L23, has the structural formula shown in formula L23:

[0386]

[0387] Its synthetic route is as follows:

[0388]

[0389] Synthesis of compound 23-1:

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

[0391] Synthesis of compound L23:

[0392] Compound 23-1 56 mg (1.0 eq) and compound 23-2 219 mg (3.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 16 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 160 μL of piperidine and 118 μL of glacial acetic acid were added. The mixture was then reacted at 120 °C for 5 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 119 mg of a pure black product was obtained by column chromatography, with a yield of 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 receptor based on resonant boron-nitrogen bonds, L24, has the following structural formula:

[0397]

[0398] Its synthetic route is as follows:

[0399]

[0400] Synthesis of compound 24-1:

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

[0402] Synthesis of compound L24:

[0403] Compound 24-1 56 mg (1.0 eq) and compound 24-2 234 mg (3.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 16 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 160 μL of piperidine and 118 μL of glacial acetic acid were added. The mixture was then reacted at 120 °C for 5 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 131 mg of a pure black product was obtained by column chromatography, with a yield of 63%.

[0404] Elemental analysis structure (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. Test 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 resonant boron-nitrogen bond units, with the structural formula shown in formula L25:

[0408]

[0409] Its synthetic route is as follows:

[0410]

[0411] Synthesis of compound 25-1:

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

[0413] Synthesis of compound 25-3:

[0414] Compound 25-1 56 mg (1.0 eq) and compound 25-2 153 mg (3.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 16 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 160 μL of piperidine and 118 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 1 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 108 mg of a green, pure product was obtained by column chromatography, with a yield of 70%.

[0415] Synthesis of compound L25:

[0416] Compound 25-3 77 mg (1.0 eq), hexa-n-butylditin 29 mg (1.0 eq), tris(dibenzylacetone)dipalladium (0.9 mg, 0.02 eq), and tris(o-methylphenyl)phosphine (2.4 mg, 0.16 eq) were added to a polymerization tube. 2.5 mL of ultra-dry toluene was added under an argon atmosphere, and the reaction was carried out at 120 °C for 12 h in the dark. After the reaction was complete, the reaction system was precipitated in methanol, and the polymer was extracted sequentially with acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain 66 mg of the final product, with a yield of 95%.

[0417] Elemental analysis results: Theoretical values: C, 72.92; H, 6.70; B, 1.56; F, 5.49; N, 4.05; S, 9.27. Tested values: C, 72.88; H, 6.68; N, 4.01.

[0418] The obtained product was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene as standard, 150℃), yielding: M n =20152, PDI=2.21.

[0419] Example 26

[0420] A polymer L26 based on resonant boron-nitrogen bond units, with the structural formula shown in Formula L26:

[0421]

[0422] Its synthetic route is as follows:

[0423]

[0424] Synthesis of compound 26-1:

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

[0426] Synthesis of compound 26-3:

[0427] Compound 26-1, 146 mg (1.0 eq), and compound 26-2, 149 mg (3.0 eq), were added to a polymerization tube. 200 mg of molecular sieve was added to 16 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 200 μL of piperidine and 140 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 1 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 164 mg of a green, pure product was obtained by column chromatography, with a yield of 68%.

[0428] Synthesis of compound L26:

[0429] Compound 26-3 121 mg (1.0 eq), hexa-n-butylditin 29 mg (1.0 eq), tris(dibenzylacetone)dipalladium (0.9 mg, 0.02 eq), and tris(o-methylphenyl)phosphine (2.4 mg, 0.16 eq) were added to a polymerization tube. 2.5 mL of ultra-dry toluene was added under an argon atmosphere, and the reaction was carried out at 120 °C for 12 h in the dark. After the reaction was complete, the reaction system was precipitated in methanol, and the polymer was extracted sequentially with acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain 105 mg of the final product, with a yield of 93%.

[0430] Elemental analysis results: Theoretical values: C, 86.96; H, 9.61; B, 0.95; N, 2.47. Tested values: C, 86.99; H, 9.57; N, 2.45.

[0431] The obtained product was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene as standard, 150℃), yielding: M n =18326, PDI=2.35.

[0432] Example 27

[0433] A polymer L27 based on resonant boron-nitrogen bond units, with the structural formula shown in Formula L27:

[0434]

[0435] Its synthetic route is as follows:

[0436]

[0437] Synthesis of compound 27-1:

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

[0439] Synthesis of compound 27-3:

[0440] Compound 27-1 56 mg (1.0 eq) and compound 27-2 182 mg (3.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 13 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 200 μL of piperidine and 140 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 1 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 115 mg of a green, pure product was obtained by column chromatography, with a yield of 66%.

[0441] Synthesis of compound L27:

[0442] Compound 27-3 (87 mg, 1.0 eq), hexa-n-butylditin (29 mg, 1.0 eq), tris(dibenzylacetone)dipalladium (0.9 mg, 0.02 eq), and tris(o-methylphenyl)phosphine (2.4 mg, 0.16 eq) were added to a polymerization tube. 2.2 mL of ultra-dry toluene was added under an argon atmosphere, and the reaction was carried out at 120 °C for 12 h in the dark. After the reaction was complete, the reaction system was precipitated in methanol, and the polymer was extracted sequentially with acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain 71 mg of the final product, with a yield of 90%.

[0443] Elemental analysis results: Theoretical values: C, 74.31; H, 7.89; B, 1.36; F, 4.80; N, 3.54; S, 8.10. Tested values: C, 74.30; H, 7.85; N, 3.56.

[0444] The obtained product was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene as standard, 150℃), yielding: M n =26535, PDI=2.30.

[0445] Example 28

[0446] A polymer L28 based on resonant boron-nitrogen bond units, with the structural formula shown in Formula L28:

[0447]

[0448] Its synthetic route is as follows:

[0449]

[0450] Synthesis of compound 28-1:

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

[0452] Synthesis of compound 28-3:

[0453] Compound 28-1 38 mg (1.0 eq) and 28-2 112 mg (3.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 13 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 200 μL of piperidine and 140 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 1 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 69 mg of a green, pure product was obtained by column chromatography, with a yield of 63%.

[0454] Synthesis of compound L28:

[0455] 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 were added to a polymerization tube and stirred at 80 °C for 30 min to activate the reaction. Compound 28-3 (55 mg, 1.0 eq) was dissolved in anhydrous toluene (10 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 was completed, the reaction system was precipitated in methanol, and the polymer was extracted. The precipitate was extracted sequentially with acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain 45 mg of the final product, with a yield of 95%.

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

[0457] The obtained product was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene as standard, 150℃), yielding: M n =28176, PDI=2.40.

[0458] Example 29

[0459] A polymer L29 based on resonant boron-nitrogen bond units has the structural formula shown in formula L29:

[0460]

[0461] Its synthetic route is as follows:

[0462]

[0463] Synthesis of compound 29-1:

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

[0465] Synthesis of compound 29-3:

[0466] Compound 29-1 56 mg (1.0 eq) and compound 29-2 308 mg (3.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 13 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 200 μL of piperidine and 140 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 1 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 144 mg of a green, pure product was obtained by column chromatography, with a yield of 58%.

[0467] Synthesis of compound L29:

[0468] Compound 29-3, 124 mg (1.0 eq), hexa-n-butylditin, 29 mg (1.0 eq), tris(dibenzylacetone)dipalladium (0.9 mg, 0.02 eq), and tris(o-methylphenyl)phosphine (2.4 mg, 0.16 eq) were added to a polymerization tube. 2.5 mL of ultra-dry toluene was added under an argon atmosphere, and the reaction was carried out at 120 °C for 12 h in the dark. After the reaction was complete, the reaction system was precipitated in methanol, and the polymer was extracted sequentially with acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain 106 mg of the final product, with a yield of 88%.

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

[0470] The obtained product was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene as standard, 150℃), yielding: M n =18625, PDI=2.55.

[0471] Example 30

[0472] A polymer L30 based on resonant boron-nitrogen bond units, with the structural formula shown in formula L30:

[0473]

[0474] Its synthetic route is as follows:

[0475]

[0476] Synthesis of Compound 30-1

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

[0478] Synthesis of compound 30-3:

[0479] Compounds 30-1 (38 mg, 1.0 eq) and 30-2 (313 mg, 3.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 13 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 200 μL of piperidine and 140 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 1 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 151 mg of a green, pure product was obtained by column chromatography, with a yield of 62%.

[0480] Synthesis of compound L30:

[0481] Compound 30-3, 122 mg (1.0 eq), hexa-n-butylditin, 29 mg (1.0 eq), tris(dibenzylacetone)dipalladium (0.9 mg, 0.02 eq), and tris(o-methylphenyl)phosphine (2.4 mg, 0.16 eq) were added to a polymerization tube. 2.5 mL of ultra-dry toluene was added under an argon atmosphere, and the reaction was carried out at 120 °C for 12 h in the dark. After the reaction was complete, the reaction system was precipitated in methanol, and the polymer was extracted sequentially with acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain 103 mg of the final product, with a yield of 90%.

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

[0483] The obtained product was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene as standard, 150℃), yielding: M n =32158, PDI=2.66.

[0484] Example 31

[0485] A polymer L31 based on resonant boron-nitrogen bond units has 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 for 31-1 are the same as those for 1-1, only the raw materials have changed.

[0491] Synthesis of compound 31-3:

[0492] Compound 31-1 56 mg (1.0 eq) and compound 31-2 107 mg (3.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 13 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 175 μL of piperidine and 115 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 2 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 82 mg of a green, pure product was obtained by column chromatography, with a yield of 66%.

[0493] Synthesis of compound L31:

[0494] Compound 31-3 74 mg (1.0 eq), hexa-n-butylditin 35 mg (1.0 eq), tris(dibenzylacetone)dipalladium (1.1 mg, 0.02 eq), and tris(o-methylphenyl)phosphine (2.9 mg, 0.16 eq) were added to a polymerization tube. 3.0 mL of ultra-dry toluene was added under an argon atmosphere, and the reaction was carried out at 120 °C for 12 h in the dark. After the reaction was complete, the reaction system was precipitated in methanol, and the polymer was extracted sequentially with acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain 103 mg of the final product, with a yield of 90%.

[0495] Elemental analysis results: Theoretical values: C, 73.19; H, 6.70; B, 2.00; F, 7.02; N, 5.17; S, 5.92. Tested values: C, 73.18; H, 6.72; N, 5.19.

[0496] The obtained product was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene as standard, 150℃), yielding: M n =29138, PDI=2.45.

[0497] Example 32

[0498] A polymer L32 based on resonant boron-nitrogen bond units, with the structural formula shown in Formula L32:

[0499]

[0500] Its synthetic route is as follows:

[0501]

[0502] Synthesis of compound 32-1:

[0503] The synthesis steps and experimental conditions for 31-1 are the same as those for 1-1, only the raw materials have changed.

[0504] Synthesis of compound 32-3:

[0505] Compound 32-1 129 mg (1.0 eq) and 32-2 107 mg (3.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 13 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 175 μL of piperidine and 115 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 1 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 116 mg of a green, pure product was obtained by column chromatography, with a yield of 59%.

[0506] Synthesis of compound L32:

[0507] 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 to a polymerization tube and stirred at 80 °C for 30 min to activate the reaction. 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 was completed, the reaction system was precipitated in methanol, and the polymer was extracted. The precipitate was extracted sequentially with acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain 51 mg of the final product, with a yield of 94%.

[0508] Elemental analysis results: Theoretical values: C, 82.35; H, 9.81; B, 1.20; N, 3.10; S, 3.55. Tested values: C, 82.32; H, 9.81; N, 3.11.

[0509] The obtained product was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene as standard, 150℃), yielding: M n =14328, PDI=2.50.

[0510] Example 33

[0511] A polymer L33 based on resonant boron-nitrogen bond units, with 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 for 33-1 are the same as those for 1-1, only the raw materials have changed.

[0517] Synthesis of compound 33-3:

[0518] Compound 33-1 56 mg (1.0 eq) and compound 33-2 212 mg (3.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 13 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 175 μL of piperidine and 115 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 1 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 109 mg of a green, pure product was obtained by column chromatography, with a yield of 56%.

[0519] Synthesis of compound L33:

[0520] Compound 33-3 78 mg (1.0 eq), hexa-n-butylditin 23 mg (1.0 eq), tris(dibenzylacetone)dipalladium (0.7 mg, 0.02 eq), and tris(o-methylphenyl)phosphine (1.9 mg, 0.16 eq) were added to a polymerization tube. 3.0 mL of ultra-dry toluene was added under an argon atmosphere, and the reaction was carried out at 120 °C for 12 h in the dark. After the reaction was complete, the reaction system was precipitated in methanol, and the polymer precipitated. The precipitate was extracted sequentially with acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain 66 mg of the final product, with a yield of 93%.

[0521] Elemental analysis results: Theoretical values: C, 76.74; H, 7.46; B, 1.21; F, 4.26; N, 3.14; S, 7.19. Tested values: C, 76.73; H, 7.44; N, 3.07.

[0522] The obtained product was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene as standard, 150℃), yielding: M n =41225, PDI=2.36.

[0523] Example 34

[0524] A polymer L34 based on resonant boron-nitrogen bond units, with the structural formula shown in Formula L34:

[0525]

[0526] Its synthetic route is as follows:

[0527]

[0528] Synthesis of compound 34-1:

[0529] The synthesis steps and experimental conditions for 34-1 are the same as those for 1-1, only the raw materials have changed.

[0530] Synthesis of compound 34-3:

[0531] Compound 34-1 56 mg (1.0 eq) and compound 34-2 240 mg (3.0 eq) were added to a polymerization tube. 200 mg of molecular sieve was added to 15 mL of ultra-dry toluene under an argon atmosphere. After complete dissolution, 175 μL of piperidine and 115 μL of glacial acetic acid were added. The mixture was then reacted at 85 °C for 1 h. After cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 131 mg of a green, pure product was obtained by column chromatography, with a yield of 62%.

[0532] Synthesis of compound L34:

[0533] Compound 34-3, 106 mg (1.0 eq), hexa-n-butylditin, 29 mg (1.0 eq), tris(dibenzylacetone)dipalladium (0.9 mg, 0.02 eq), and tris(o-methylphenyl)phosphine (2.4 mg, 0.16 eq) were added to a polymerization tube. 3.0 mL of ultra-dry toluene was added under an argon atmosphere, and the reaction was carried out at 120 °C for 12 h in the dark. After the reaction was complete, the reaction system was precipitated in methanol, and the polymer was extracted sequentially with acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain 90 mg of the final product, with a yield of 92%.

[0534] Elemental analysis results: Theoretical values: C, 67.12; H, 6.35; B, 1.10; F, 3.86; N, 8.54; S, 13.03. Tested values: C, 67.14; H, 6.33; N, 8.46.

[0535] The obtained product was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene as standard, 150℃), yielding: M n =21305, PDI=2.67.

[0536] Resonance UV-Vis and short-wave infrared absorption spectroscopy of small and large boron-nitrogen molecules in film:

[0537] The ultraviolet-visible shortwave infrared absorption spectra of films L1, L4, L5, L6, L8, L12, L13, L14, L16, L25, L26, L29, and L31 were measured, and the results are as follows: Figures 1-4 As shown, Figure 1 The UV-Vis shortwave infrared absorption spectra of small molecules L1, L4, and L5 based on resonant boron-nitrogen unit (BIP) are shown. Figure 2 The film-state UV-Vis short-wave infrared absorption spectra of small molecules L6, L8, and L12 based on resonant boron-nitrogen unit (BIP); Figure 3 The UV-Vis short-wave infrared absorption spectra of small molecules L13, L14 and L16 based on resonant boron-nitrogen unit (BIP) are shown. Figure 4The following are the film-state UV-Vis short-wave infrared absorption spectra of polymers L25, L26, L29, and L31 based on resonant boron-nitrogen unit (BIP). The absorption wavelengths are listed in Table 1.

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

[0539] Photovoltaic detectors were fabricated using resonant 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 for detection performance testing. The chemical structure of PBDB-T is as follows: The chemical structural formula of PCE10 is as follows: The PCE10 used has a molecular weight range of 50,000 to 150,000. The photovoltaic detector, also known as a short-wave infrared organic photodetector, has the following device structure: Figure 5 As shown, Figure 5 This is a schematic diagram of the device structure of the photovoltaic detector described in this invention. Figure 5 As can be seen, the structure of the photovoltaic detector, from bottom to top, 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. For specific fabrication processes, please refer to Test Examples 1-9.

[0540] Test Example 1

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

[0542] The specific fabrication process of the aforementioned short-wave infrared organic photodetector is as follows:

[0543] A 20 nm layer of zinc oxide (ZnO) was spin-coated onto ITO glass and then annealed at 200 °C for 60 minutes to serve as the anode interface layer. The polymer donor PBDB-T and the small molecule acceptor L1 were dissolved in chloroform, and 1% (v / v) of chloronaphthalene was added. A 120 nm blended photoactive layer was then spin-coated and annealed at 120 °C for 10 minutes. A 10 nm layer of MoO3 was then spin-coated as the anode interface layer, followed by the deposition of a 100 nm Al layer, thus completing the device fabrication.

[0544] Test Example 2

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

[0546] The specific fabrication process of the aforementioned short-wave infrared organic photodetector is as follows:

[0547] A 20 nm layer of zinc oxide (ZnO) was spin-coated onto ITO glass and then annealed at 200 °C for 60 minutes to serve as the anode interface layer. The polymer donor PBDB-T and the small molecule acceptor L4 were dissolved in chloroform, and 1% (v / v) of chloronaphthalene was added. A 120 nm blended photoactive layer was then spin-coated and annealed at 120 °C for 10 minutes. A 10 nm layer of MoO3 was then spin-coated as the anode interface layer, followed by the deposition of a 100 nm Al layer, thus completing the device fabrication.

[0548] Test Example 3

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

[0550] The specific fabrication process of the aforementioned short-wave infrared organic photodetector is as follows:

[0551] A 20 nm layer of zinc oxide (ZnO) was spin-coated onto ITO glass and then annealed at 200 °C for 60 minutes to serve as the anode interface layer. The polymer donor PBDB-T and the small molecule acceptor L5 were dissolved in chloroform, and 1.5% (v / v) of chloronaphthalene was added. A 130 nm blended photoactive layer was then spin-coated and annealed at 120 °C for 10 minutes. A 10 nm layer of MoO3 was then spin-coated as the anode interface layer, followed by the deposition of a 100 nm Al layer, thus completing the device fabrication.

[0552] Test Example 4

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

[0554] The specific fabrication process of the aforementioned short-wave infrared organic photodetector is as follows:

[0555] A 20 nm layer of zinc oxide (ZnO) was spin-coated onto ITO glass and then annealed at 200 °C for 60 minutes to serve as the anode interface layer. The polymer donor PCE10 and the small molecule acceptor L6 were dissolved in chloroform, and 1.5% (v / v) of chloronaphthalene was added. A 130 nm blended photoactive layer was then spin-coated and annealed at 150 °C for 10 minutes. A 10 nm layer of MoO3 was then spin-coated as the anode interface layer, followed by the deposition of a 100 nm Al layer, thus completing the device fabrication.

[0556] Test Example 5

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

[0558] The specific fabrication process of the aforementioned short-wave infrared organic photodetector is as follows:

[0559] A 20 nm layer of zinc oxide (ZnO) was spin-coated onto ITO glass and then annealed at 200 °C for 60 minutes to serve as the anode interface layer. The polymer donor PCE10 and the small molecule acceptor L8 were dissolved in chloroform, and 1.2% (v / v) of chloronaphthalene was added. A 160 nm blended photoactive layer was then spin-coated and annealed at 150 °C for 10 minutes. A 10 nm layer of MoO3 was then spin-coated as the anode interface layer, followed by the deposition of a 100 nm Al layer, thus completing the device fabrication.

[0560] Test Example 6

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

[0562] The specific fabrication process of the aforementioned short-wave infrared organic photodetector is as follows:

[0563] A 20 nm layer of zinc oxide (ZnO) was spin-coated onto ITO glass and then annealed at 200 °C for 60 minutes to serve as the anode interface layer. The polymer donor PBDB-T and the small molecule acceptor L12 were dissolved in chloroform, and 1.2% (v / v) of chloronaphthalene was added. A 160 nm blended photoactive layer was then spin-coated and annealed at 150 °C for 10 minutes. A 10 nm layer of MoO3 was then spin-coated as the anode interface layer, followed by the deposition of a 100 nm Al layer, thus completing the device fabrication.

[0564] Test Example 7

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

[0566] The specific fabrication process of the aforementioned short-wave infrared organic photodetector is as follows:

[0567] A 20 nm layer of zinc oxide (ZnO) was spin-coated onto ITO glass and then annealed at 200 °C for 60 minutes to serve as the anode interface layer. The polymer donor PBDB-T and the small molecule acceptor L13 were dissolved in chloroform, and 1.2% (v / v) of chloronaphthalene was added. A 160 nm blended photoactive layer was then spin-coated and annealed at 150 °C for 10 minutes. A 10 nm layer of MoO3 was then spin-coated as the anode interface layer, followed by the deposition of a 100 nm Al layer, thus completing the device fabrication.

[0568] Test Example 8

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

[0570] The specific fabrication process of the aforementioned short-wave infrared organic photodetector is as follows:

[0571] A 20 nm layer of zinc oxide (ZnO) was spin-coated onto ITO glass and then annealed at 200 °C for 60 minutes to serve as the anode interface layer. The polymer donor PBDB-T and the small molecule acceptor L13 were dissolved in chloroform, and 1.2% (v / v) of chloronaphthalene was added. A 160 nm blended photoactive layer was then spin-coated and annealed at 150 °C for 10 minutes. A 10 nm layer of MoO3 was then spin-coated as the anode interface layer, followed by the deposition of a 100 nm Al layer, thus completing the device fabrication.

[0572] Test Example 9

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

[0574] The specific fabrication process of the aforementioned short-wave infrared organic photodetector is as follows:

[0575] A 20 nm layer of zinc oxide (ZnO) was spin-coated onto ITO glass and then annealed at 200 °C for 60 minutes to serve as the anode interface layer. The polymer donor PBDB-T and the small molecule acceptor L13 were dissolved in chloroform, and 1.4% (v / v) of chloronaphthalene was added. A 160 nm blended photoactive layer was then spin-coated and annealed at 150 °C for 10 minutes. A 10 nm layer of MoO3 was then spin-coated as the anode interface layer, followed by the deposition of a 100 nm Al layer, thus completing the device fabrication.

[0576] The EQE and dark current of the organic photodetectors in Test Examples 1 to 9 were measured at 0V bias, and the corresponding responsivity R and detectivity D* were calculated. Responsivity R is the ratio of photocurrent to incident light intensity of the photodetector, measured in A / W, and is calculated using the following formula:

[0577]

[0578] Detectivity D* is defined as the reciprocal of noise equivalent power (NEP) and is an indicator of a detector's ability to detect the smallest incident light signal. The unit is Jones, and the calculation formula is shown below:

[0579]

[0580] Where R is the responsivity, q is the charge, and J d This represents the dark current density.

[0581] The results are as follows Figures 6 to 11 It can be seen that, Figure 6 The image shows the EQE curves of an inverted organic photovoltaic detector based on resonant boron-nitrogen small molecules L1, L4, L5, L6, and L8. Figure 7The image shows the EQE curves of an inverted organic photovoltaic detector based on resonant boron-nitrogen small molecules L12, L13, L14, and L16. Figure 8 The graph shows the responsivity of organic photovoltaic detectors based on resonant boron-nitrogen small molecules L1, L4, L5, L6, and L8. Figure 9 The graph shows the responsivity of organic photovoltaic detectors based on resonant boron-nitrogen small molecules L12, L13, L14, and L16. Figure 10 The image shows the dark current curves of organic photovoltaic detectors based on resonant boron-nitrogen small molecules L1, L4, L5, L6, and L8. Figure 11 The dark current curves are shown for organic photovoltaic detectors based on resonant boron-nitrogen small molecules L12, L13, L14, and L16.

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

[0583] Table 1

[0584]

[0585] Based on the above test results, it can be seen that using the resonant boron-nitrogen small molecule acceptor L1 prepared in Example 1 as the acceptor material and PBDB-T as the donor material, the inverted organic photodetector device has a detection range exceeding 1350 nm. At 0 V bias, the EQE value at 1200 nm is 18.5%, and the dark current is 7.26 × 10⁻⁶. -10 A / cm -2 The corresponding responsivity and detectivity are 0.18 A / W and 1.17 × 10⁻⁶, respectively. 13 Jones.

[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 photodetector device was fabricated. Specific performance parameters are shown in Table 1. The device has a detection range exceeding 1400 nm, and at 0 V bias, the EQE value at 1250 nm is 25.6%, and the dark current is 9.28 × 10⁻⁶. -10 A / cm -2 The corresponding responsivity and detectivity are 0.26 A / W and 1.50 × 10⁻⁶, respectively. 13 Jones.

[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 photodetector device was fabricated. Specific performance parameters are shown in Table 1. The device has a detection range exceeding 1400 nm, and at 0 V bias, the EQE value at 1270 nm is 17.2%, and the dark current is 1.25 × 10⁻⁶. -9A / cm -2 The corresponding responsivity and detectivity are 0.19 A / W and 9.50 × 10⁻⁶, respectively. 12 Jones.

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

[0589] Using the resonant boron-nitrogen small molecule acceptor L8 prepared in Example 8 as the acceptor material and PCE10 as the donor material, an inverted organic photodetector device was fabricated. Specific performance parameters are shown in Table 1. The device has a detection range exceeding 1400 nm, and at 0 V bias, the EQE value at 1250 nm is 22.6%, and the dark current is 8.92 × 10⁻⁶. -10 A / cm -2 The corresponding responsivity and detectivity are 0.23 A / W and 1.36 × 10⁻⁶, respectively. 13 Jones.

[0590] Using the resonant boron-nitrogen small molecule acceptor L12 prepared in Example 12 as the acceptor material and PCE10 as the donor material, an inverted organic photodetector device was fabricated. Specific performance parameters are shown in Table 1. The device has a detection range exceeding 1400 nm, and at 0 V bias, the EQE value at 1200 nm is 23.2%, and the dark current is 1.12 × 10⁻⁶. -9 A / cm -2 The corresponding responsivity and detectivity are 0.22 A / W and 1.16 × 10⁻⁶, respectively. 13 Jones.

[0591] Using the resonant boron-nitrogen small molecule acceptor L13 prepared in Example 13 as the acceptor material and PBDB-T as the donor material, an inverted organic photodetector device was fabricated. Specific performance parameters are shown in Table 1. The device has a detection range exceeding 1400 nm, and at 0 V bias, the EQE value at 1170 nm is 20.1%, and the dark current is 1.30 × 10⁻⁶. -9 A / cm -2 The corresponding responsivity and detectivity are 0.19 A / W and 9.32 × 10⁻⁶, respectively. 12 Jones.

[0592] Using the resonant boron-nitrogen small molecule acceptor L13 prepared in Example 13 as the acceptor material and PBDB-T as the donor material, an inverted organic photodetector device was fabricated. Specific performance parameters are shown in Table 1. The device has a detection range exceeding 1400 nm, an EQE value of 20.5% at 1220 nm under 0 V bias, and a dark current of 1.50 × 10⁻⁶. -9 A / cm -2 The corresponding responsivity and detectivity are 0.20 A / W and 9.13 × 10⁻⁶, respectively. 12 Jones.

[0593] Using the resonant boron-nitrogen small molecule acceptor L16 prepared in Example 16 as the acceptor material and PBDB-T as the donor material, an inverted organic photodetector device was fabricated. Specific performance parameters are shown in Table 1. The device has a detection range exceeding 1400 nm, and at 0 V bias, the EQE value at 1240 nm is 24.2%, and the dark current is 1.55 × 10⁻⁶. -9 A / cm -2 The corresponding responsivity and detectivity are 0.24 A / W and 1.07 × 10⁻⁶, respectively. 13 Jones.

[0594] Performance testing of phototransistor detectors using resonant boron-nitrogen polymers as infrared absorbing materials:

[0595] Using resonant boron-nitrogen polymers such as L25, L26, L29, and L31 as infrared absorbing materials, a phototransistor-type detector was fabricated, and its detection performance was tested. The device structure of the phototransistor-type detector is as follows: Figure 12 As shown, Figure 12 This is a schematic diagram of the device structure of the phototransistor detector described in this invention. Figure 12 It can be seen that the structure of the phototransistor detector, from bottom to top, includes P... + The substrate is composed of a Si / SiO2 substrate, a graphene charge transport layer, a Ti / Au alloy electrode, and a polymer infrared absorbing layer. For details of the fabrication process, please refer to Test Examples 10–13.

[0596] Test Case 10

[0597] Taking the resonant boron-nitrogen polymer L25 obtained in Example 25 as an example, its detection performance is explained.

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

[0599] In P +A layer of graphene was transferred and coated onto a Si / SiO2 substrate as a charge transport layer, followed by co-evaporation of a Ti / Au alloy electrode with a Ti thickness of 20 nm and an Au thickness of 60 nm. Polymer L25 was dissolved in chloroform and coated onto the charge transport layer as an electron acceptor and infrared photon absorber, with a thickness of approximately 80 nm. The coating was then annealed at 150 °C for 10 minutes to obtain the final device.

[0600] Test Example 11

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

[0602] The specific fabrication process of the short-wave infrared organic phototransistor detector is as follows:

[0603] In P + A layer of graphene was transferred and coated onto a Si / SiO2 substrate as a charge transport layer, followed by co-evaporation of a Ti / Au alloy electrode with a Ti thickness of 20 nm and an Au thickness of 60 nm. Polymer L26 was dissolved in chloroform and coated onto the charge transport layer as an electron acceptor and infrared photon absorber, with a thickness of approximately 70 nm. The coating was then annealed at 160 °C for 10 minutes to obtain the final device.

[0604] Test Example 12

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

[0606] The specific fabrication process of the short-wave infrared organic phototransistor detector is as follows:

[0607] In P + A layer of graphene was transferred and coated onto a Si / SiO2 substrate as a charge transport layer, followed by co-evaporation of a Ti / Au alloy electrode with a Ti thickness of 20 nm and an Au thickness of 60 nm. Polymer L29 was dissolved in chloroform and coated onto the charge transport layer as an electron acceptor and infrared photon absorber, with a thickness of approximately 80 nm. The coating was then annealed at 160 °C for 10 minutes to obtain the final device.

[0608] Test Example 13

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

[0610] The specific fabrication process of the short-wave infrared organic phototransistor detector is as follows:

[0611] In P +A layer of graphene was transferred and coated onto a Si / SiO2 substrate as a charge transport layer, followed by co-evaporation of a Ti / Au alloy electrode with a Ti thickness of 20 nm and an Au thickness of 60 nm. Polymer L29 was dissolved in chloroform and coated onto the charge transport layer as an electron acceptor and infrared photon absorber, with a thickness of approximately 80 nm. The coating was then annealed at 160 °C for 10 minutes to obtain the final device.

[0612] Noise current density was measured for the phototransistor detectors in Test Examples 10 to 13, and the corresponding responsivity R and detectivity D* were calculated. The calculation of responsivity R and detectivity D* is the same as described above and will not be repeated. The results are as follows... Figures 13-14 It can be seen that, Figure 13 This is a responsivity graph of an organic phototransistor detector based on resonant boron-nitrogen polymers L25, L26, L29, and L31. Figure 14 This is a graph showing the noise current density of organic phototransistor detectors based on resonant boron-nitrogen polymers L25, L26, L29, and L31.

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

[0614] Table 2

[0615]

[0616] Based on the above test results, it can be seen that using the resonant boron-nitrogen polymer L25 prepared in Example 25 as the light-absorbing material to fabricate an organic phototransistor detector device, the device structure is as follows: Figure 6 Specific performance parameters are shown in Table 2. The device has a detection range exceeding 2000 nm, and a responsivity of 1.4 × 10⁻⁶ at 1550 nm with a gate voltage of 60 V. 4 A / W, noise level is 5.50 × 10 -10 A / Hz 1 / 2 The detection rate is 2.30×10 10 Jones.

[0617] Using the resonant boron-nitrogen polymer L26 prepared in Example 26 as the light-absorbing material, an organic phototransistor detector was fabricated. Specific performance parameters are shown in Table 2. The device has a detection range exceeding 2000 nm, and at a gate voltage of 60 V, the responsivity at 1550 nm is 2.5 × 10⁻⁶. 4 A / W, noise level is 3.50 × 10 -10 A / Hz 1 / 2 The detection rate is 6.45 × 10⁻⁶. 10 Jones.

[0618] Using the resonant boron-nitrogen polymer L29 prepared in Example 29 as the light-absorbing material, an organic phototransistor detector was fabricated. Specific performance parameters are shown in Table 2. The device has a detection range exceeding 2000 nm, and at a gate voltage of 60 V, the responsivity at 1550 nm is 3.0 × 10⁻⁶. 4 A / W, noise level 1.00 × 10 -10 A / Hz 1 / 2 The detection rate is 2.70×10 11 Jones.

[0619] Using the resonant boron-nitrogen polymer L31 prepared in Example 31 as the light-absorbing material, an organic phototransistor detector was fabricated. Specific performance parameters are shown in Table 2. The device has a detection range exceeding 2000 nm, and at a gate voltage of 60 V, the responsivity at 1550 nm is 3.5 × 10⁻⁶. 4 A / W, noise level is 2.10 × 10 -10 A / Hz 1 / 2 The detection rate is 1.51×10 11 Jones.

[0620] Comparative Example 1

[0621] A small molecule receptor R35 based on the BODIPY unit has the following structural formula:

[0622]

[0623] Its synthetic route is as follows:

[0624]

[0625] Synthesis of Compound 35-1: Under an argon atmosphere, 20.0 mL of ultradry dichloromethane was added to a 100 mL round-bottom flask containing a 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 syringe containing residual DDQ was rinsed with ultradry dichloromethane, and the reaction was allowed to proceed for 3 h. Then, 5.31 mL (30 eq.) of Et3N and 6.30 mL (40 eq.) of BF3·Et2O were slowly added dropwise at room temperature, and the reaction was allowed to proceed for 5 h. Subsequently, 0.20 g (1.1 eq.) of NBS was added, and the reaction was allowed to proceed for 8 h at room temperature. The mixture was then concentrated, and the crude product was purified by column chromatography to give 0.23 g of a red solid, with a yield of 36%.

[0626] Synthesis of compound 35-2: 52 mg (1.0 eq) of compound 35-1, 144 mg (2.5 eq) of CPDT monoaldehyde tin salt, and 3.6 mg (0.04 eq) of tetrakis(triphenylphosphine)palladium were added to a polymerization tube. 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 cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 81 mg of a pure yellow product (75% yield) was obtained by column chromatography.

[0627] Synthesis of compound R35: 67 mg (1.0 eq) of compound 35-2, 58 mg (5.0 eq) of 2F-IC, and 20 mL of ultradry chloroform were added to a polymerization tube. 0.15 mL of pyridine was added under an argon atmosphere, and the reaction was carried out overnight at 65 °C. The next day, the solution color changed from yellow to brownish-green. After cooling, the solution was evaporated to dryness and then added to methanol for back precipitation to remove 2F-IC. The resulting solid was then separated by column chromatography to obtain 58 mg, with a yield of 66%.

[0628] Elemental analysis 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. Test 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 has the following structural formula:

[0632]

[0633] Its synthetic 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: 52 mg (1.0 eq) of compound 36-1, 166 mg (2.5 eq) of CPDT monoaldehyde tin salt, and 3.6 mg (0.04 eq) of tetrakis(triphenylphosphine)palladium were added to a polymerization tube. 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 cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 90 mg of a pure yellow product was obtained by column chromatography, with a yield of 72%.

[0637] Synthesis of compound R36: 78 mg (1.0 eq) of compound 36-2, 65 mg (5.0 eq) of 2Cl-IC, and 20 mL of ultradry chloroform were added to a polymerization tube. 0.15 mL of pyridine was added under an argon atmosphere, and the reaction was carried out overnight at 65 °C. The next day, the solution color changed from yellow to brownish-green. After cooling, the solution was evaporated to dryness and then added to methanol for back precipitation to remove 2Cl-IC. The resulting solid was then separated by column chromatography to obtain 70 mg, with a yield of 68%.

[0638] Elemental analysis 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. Test 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 receptor R37 based on the BODIPY unit has the following structural formula:

[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: 52 mg (1.0 eq) of compound 37-1, 131 mg (2.5 eq) of carbazole monoaldehyde tin salt, and 3.6 mg (0.04 eq) of tetrakis(triphenylphosphine)palladium were added to a polymerization tube. 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 cooling, the mixture was extracted twice with dichloromethane / water, dried, and then evaporated to dryness. 58 mg of a pure yellow product was obtained by column chromatography, with a yield of 60%.

[0647] Synthesis of compound R37: 60 mg (1.0 eq) of compound 37-2, 58 mg (5.0 eq) of 2F-IC, and 20 mL of ultradry chloroform were added to a polymerization tube. 0.15 mL of pyridine was added under an argon atmosphere, and the reaction was carried out overnight at 65 °C. The next day, the solution color changed from yellow to brownish-green. After cooling, the solution was evaporated to dryness and then added to methanol for back precipitation to remove 2F-IC. The resulting solid was then separated by column chromatography to obtain 56 mg, with a yield of 68%.

[0648] Elemental analysis 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. Test 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 resonant boron-nitrogen bond units has the following structural formula:

[0652]

[0653] Its synthetic route is as follows:

[0654]

[0655] Synthesis of polymer R38: 128 mg (1.0 eq) of dibromo-BODIPY units, 196 mg (1.0 eq) of CPDT bistin salt, 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 the reaction was carried out at 110 °C for 12 h in the dark. After the reaction was complete, the reaction system was precipitated in methanol, and the polymer was extracted sequentially with acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain 160 mg of the final product, with a yield of 90%.

[0656] Elemental analysis results: Theoretical values: C, 69.21; H, 7.63; B, 1.22; F, 4.29; N, 3.17; O, 3.62; S, 10.87. Tested values: C, 69.19; H, 7.59; N, 3.16.

[0657] The obtained product was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene as standard, 150℃), yielding: M n =13212, PDI=2.31.

[0658] Comparative Example 5

[0659] A polymer R39 based on resonant boron-nitrogen bond units has the following structural formula:

[0660]

[0661] Its synthetic route is as follows:

[0662]

[0663] Synthesis of polymer R39: 128 mg (1.0 eq) of dibromo-BODIPY units, 194 mg (1.0 eq) of benzofluorene bistin salt, 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 the reaction was carried out at 110 °C for 12 h in the dark. After the reaction was complete, the reaction system was precipitated in methanol, and the polymer was extracted sequentially with acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain 165 mg of the final product, with a yield of 93%.

[0664] Elemental analysis results: Theoretical values: C, 75.67; H, 8.20; B, 1.24; F, 4.35; N, 3.21; O, 3.67; S, 3.67. Tested values: C, 75.68; H, 8.21; N, 3.19.

[0665] The obtained product was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene as standard, 150℃), yielding: M n =9569, PDI=2.56.

[0666] Comparative Example 6

[0667] A polymer R40 based on resonant boron-nitrogen bond units has the following structural formula:

[0668]

[0669] Its synthetic route is as follows:

[0670]

[0671] Synthesis of polymer R40: 128 mg (1.0 eq) of dibromo-BODIPY units, 217 mg (1.0 eq) of bithiophene bistin salt, 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 the reaction was carried out at 110 °C for 12 h in the dark. After the reaction was complete, the reaction system was precipitated in methanol, and the polymer precipitated. The precipitate was extracted sequentially with acetone, n-hexane, and chloroform using a Soxhlet extractor to obtain 179 mg of the final product, with a yield of 91%.

[0672] Elemental analysis results: Theoretical values: C, 70.70; H, 8.49; B, 1.10; F, 3.86; N, 2.84; O, 3.25; S, 9.76. Tested values: C, 70.72; H, 8.46; N, 2.88.

[0673] The obtained product was analyzed by gel permeation chromatography (GPC, trichlorobenzene, polystyrene as standard, 150℃), yielding: M n =15387, PDI=2.44.

[0674] The final products of Comparative Examples 1-6 were subjected to film-state ultraviolet-visible short-wave infrared absorption spectroscopy, and the results are as follows: Figure 15 and Figure 16 As shown, Figure 15 The images show the film-state UV-Vis short-wave infrared absorption spectra of small molecules R35, R36, and R37 based on the resonant boron-nitrogen unit BODIPY. Figure 16 The images show the film-state UV-Vis shortwave infrared absorption spectra of polymers R38, R39, and R40 based on the resonant boron-nitrogen unit BODIPY.

[0675] The above description is only a preferred embodiment of the present invention, but the scope of protection of the present invention is not limited thereto. Any equivalent substitutions or modifications made by those skilled in the art within the scope of the technology disclosed in the present invention, based on the technical solution and inventive concept of the present invention, should be covered within the scope of protection of the present invention.

Claims

1. A resonance boron-nitrogen bond compound, characterized in that, The resonant boron-nitrogen bonded compound is a compound with the structure shown in Formulas 1-1 to 1-39; ； Alternatively, the resonant boron-nitrogen bond compound is a compound with the structure shown in Formula 2-1 to Formula 2-12; ； Wherein, n is an integer from 2 to 200.

2. The method for preparing the resonance boron-nitrogen bond compound according to claim 1, characterized in that, Includes the following steps: The compound with the structure shown in Formula a and the compound with the structure shown in Formula b are reacted, and then the product of the reaction is reacted with the compound with the structure shown in Formula c to obtain the resonant boron-nitrogen bond compound with the structure shown in Formula 1. Formula a; Formula b; Formula c; R1 and R2 are independently selected from one of the groups shown in the following formula: 、 、 、 、 ； The R3 is selected from one of the groups shown in the following formula: , , Alternatively, R3 and the B group together form one of the groups shown in the following formula: 、 ； One of the groups represented by the following formula in A1: 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 ； or, Reaction of the compound with the structure shown in Formula a and the compound with the structure shown in Formula d yields the resonant boron-nitrogen bond compound with the structure shown in Formula 1. Formula d; The A2 is selected from one of the groups shown in the following formula: 、 、 、 、 、 、 、 、 、 、 、 、 ； The A3 is selected from one of the groups shown in the following formula: 、 、 、 、 、 ； or, The compound with the structure shown in Formula a and the compound with the structure shown in Formula e are reacted, and then the product obtained from the reaction is subjected to self-polymerization to obtain the resonant boron-nitrogen bond compound with the structure shown in Formula 2. Formula e; In equation e, X is shown a Selected from halogens; The A4 is selected from one of the groups shown in the following formula: 、 、 、 、 、 、 、 、 、 。 3. A photodetector, characterized in that, It is either an organic photovoltaic shortwave infrared detector or an organic phototransistor shortwave infrared detector; The organic photovoltaic shortwave infrared detector 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, wherein the active layer is composed of a donor material and the resonant boron-nitrogen bond compound of claim 1; The organic phototransistor type short-wave infrared detector includes: heavily doped silicon, silicon dioxide disposed on the heavily doped silicon, a charge transport layer disposed on the silicon dioxide, an electrode disposed on the charge transport layer, and a polymer light-absorbing layer disposed on the electrode, wherein the polymer light-absorbing layer is composed of the resonant boron-nitrogen bond compound as described in claim 1.

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

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