Halogen atom-containing fused-bodipy dimer compounds, preparation and use thereof

Abstract

The application provides a halogen atom-containing fused BODIPY dimer compound and preparation and application. The structure of the compound is shown as formula (I). The halogen atom-containing fused BODIPY dimer compound provided by the application has a very narrow optical band gap, the absorption spectrum can be extended to 1100nm, and the molar absorption coefficient can be as high as 3.2*10 5 M ‑1 cm ‑1 Meanwhile, the photo-thermal stability of the compound is good, and the compound provides a new material system for an organic near-infrared light response material.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic functional materials, in particular to a fused BODIPY dimer compound containing halogen atoms and preparation and application thereof. BACKGROUND

[0002] Organic conjugated materials with near-infrared absorption characteristics have broad application prospects in the fields of dyes, fine chemicals, optoelectronic devices, and life sciences due to their low toxicity, low cost, and unique advantages such as flexibility and large-area devices. For example, they can be used as dyes in dyeing and coloring fields, can be used to prepare special inks for printing, and can be used as photoactive materials in organic solar cells, photodetectors, cell imaging, and photodynamic therapy. However, as of now, there are still few organic compounds with strong absorption characteristics in the wavelength range greater than 800 nm and excellent photothermal stability, which limits the widespread application of such materials.

[0003] Fluoroboron dipyrromethene (BODIPY) compounds are a common class of organic dyes. Due to their good photothermal stability and easily controllable optoelectronic properties, they are favored by the scientific community. However, the maximum absorption / emission wavelength of the BODIPY structural unit is around 500 nm, which is much smaller than 800 nm, and does not have near-infrared response characteristics. Based on this, scientists have carried out a series of work, effectively red-shifting the spectrum through conjugation extension of the BODIPY structure. However, molecules based on this structure still cannot simultaneously achieve a film-state maximum absorption value greater than 850 nm and high molar absorption coefficients (greater than 2.5 x 10 5 M -1 cm -1 ). SUMMARY

[0004] One object of the present application is to provide a fused BODIPY dimer compound containing halogen atoms on the terminal aromatic heterocycle.

[0005] The present application extends the conjugation of the BODIPY structure through fusion and dimerization strategies, thereby red-shifting the absorption spectrum, and further significantly improves the molar absorption coefficient of the compound by halogenation on the terminal aromatic heterocycle. The fused BODIPY dimer material containing halogen atoms on the terminal aromatic heterocycle provided by the present application has few related literature reports in terms of design, synthesis, and application, and is worthy of in-depth exploration and development.

[0006] Another object of the present application is to provide a method for preparing the fused BODIPY dimer compound containing halogen atoms.

[0007] Still another object of the present application is to provide the use of the halogen atom-containing fused BODIPY dimer compound.

[0008] To achieve the above object, in one aspect, the present application provides a halogen atom-containing fused BODIPY dimer compound, wherein the structure of the compound is shown in formula (I):

[0009]

[0010] wherein,

[0011] X is selected from -CH=, -C(CF3)=, -C(Aryl)=, -C(Alkyl)= or -N=;

[0012] each Y is independently selected from O, S or Se;

[0013] each of R1 and R2 is independently selected from F, Cl, Br, I, cyano, nitro, amino, hydroxyl, carboxyl, ester, Aryl, Alkynyl, Alkenyl, Alkyl, -O-Alkyl or -O-Aryl;

[0014] each R3 is independently selected from H, Alkyl, Aryl, Alkynyl or Alkenyl;

[0015] each of G1 and G2 is independently selected from F, Cl, Br or I;

[0016] Aryl is a substituted or unsubstituted aryl group, Alkyl is a substituted or unsubstituted alkyl group, Alkynyl is a substituted or unsubstituted alkynyl group, and Alkenyl is a substituted or unsubstituted alkenyl group.

[0017] According to some specific embodiments of the present application, Aryl is a substituted or unsubstituted aryl group containing 6 to 18 carbon atoms or a heteroaryl group containing 4 to 12 carbon atoms (e.g. thienyl, furanyl, etc.), preferably a substituted or unsubstituted aryl group containing 6 to 12 carbon atoms or a heteroaryl group containing 4 to 10 carbon atoms, more preferably a substituted or unsubstituted aryl group containing 6 to 10 carbon atoms or a heteroaryl group containing 4 to 8 carbon atoms, and most preferably a substituted or unsubstituted phenyl group; when Aryl is substituted, it is substituted with one or more substituents selected from C 1-10 alkyl, C 1-10 alkenyl, C 1-10 alkynyl, C 1-10 alkoxy, F, Cl, Br, I, CN, hydroxyl, nitro, carboxyl, ester, an aryl group containing 6 to 12 carbon atoms or a heteroaryl group containing 4 to 10 carbon atoms; the heteroaryl group contains 1, 2, 3 or 4 heteroatoms selected from N, O or S.

[0018] The number of carbon atoms in the aryl or heteroaryl groups according to the present application refers to the number of carbon atoms in the ring of the aryl or heteroaryl group, for example, the aryl group having 6 to 18 carbon atoms refers to the number of carbon atoms in the ring structure of the aromatic ring being 6 to 18, and for another example, the heteroaryl group having 4 to 12 carbon atoms refers to the number of carbon atoms in the ring structure of the heteroaromatic ring being 4 to 12.

[0019] According to some embodiments of the application, Alkyl is a substituted or unsubstituted C 1-30 alkyl, preferably a substituted or unsubstituted C 1-20 alkyl, more preferably a substituted or unsubstituted C 1-10 alkyl, most preferably a substituted or unsubstituted C 1-7 alkyl; when substituted, is substituted with one or more selected from the group consisting of C 1-10 alkyl, C 1-10 alkenyl, C 1-10 alkynyl, C 1-10 alkoxy, F, Cl, Br, I, CN, hydroxyl, nitro, carboxyl, ester, aryl having 6 to 12 carbon atoms or heteroaryl having 4 to 10 carbon atoms.

[0020] According to some embodiments of the application, Alkynyl is a substituted or unsubstituted C 1-20 alkynyl, preferably a substituted or unsubstituted C 1-10 alkynyl, more preferably a substituted or unsubstituted C 1-5 alkynyl; when substituted, is substituted with one or more selected from the group consisting of C 1-10 alkyl, C 1-10 alkenyl, C 1-10 alkynyl, C 1-10 alkoxy, F, Cl, Br, I, CN, hydroxyl, nitro, carboxyl, ester, aryl having 6 to 12 carbon atoms or heteroaryl having 4 to 10 carbon atoms.

[0021] According to some embodiments of the application, Alkenyl is a substituted or unsubstituted C 1-20 alkenyl, preferably a substituted or unsubstituted C 1-10 alkenyl, more preferably a substituted or unsubstituted C 1-5 alkenyl; when substituted, is substituted with one or more selected from the group consisting of C 1-10 alkyl, C 1-10 alkenyl, C 1-10 alkynyl, C 1-10 alkoxy, F, Cl, Br, I, CN, hydroxyl, nitro, carboxyl, ester, aryl having 6 to 12 carbon atoms or heteroaryl having 4 to 10 carbon atoms.

[0022] According to some embodiments of the present application, R1 and R2 are each independently selected from F, cyano, aryl, alkynyl, alkyl, alkoxy or -O-aryl.

[0023] According to some embodiments of the present application, G1 and G2 are each independently selected from F, Cl, Br or I.

[0024] According to some embodiments of the present application, G1 and G2 are the same.

[0025] According to some embodiments of the present application, Y is selected from O, S or Se; and R3 is selected from H, alkyl, aryl, alkynyl or alkenyl.

[0026] The compounds of the present application can achieve near-infrared response, and have strong absorption characteristics in the near-infrared region. The compounds provided by the present application have a film state maximum absorption wavelength of more than 880 nm, and the highest can reach 928 nm, and a molar absorption coefficient of more than 2.5 x 10 5 M -1 cm -1 , and the maximum can reach 3.2 x 10 5 M -1 cm -1 . By comparison, the molar absorption coefficient of the fused BODIPY dimer compound provided by the present application, which contains halogen atoms on the terminal heterocyclic ring, is much higher than that of the same type of compound.

[0027] According to some embodiments of the present application, X is selected from -CH=, -C(CF3)=, -N=,

[0028]

[0029] R4 is an optional substituent;

[0030] m1 is 0, 1, 2, 3, 4 or 5;

[0031] n1 is any integer from 0 to 12;

[0032] x1, y1 and z1 are each independently an integer from 0 to 30.

[0033] According to some embodiments of the present application, R4 is C 1-10 alkyl, C 1-10 alkoxy or a halogen atom, and the alkyl or alkoxy is substituted or unsubstituted, and when substituted, the alkyl or alkoxy is substituted with F, Cl, Br or I.

[0034] According to some embodiments of the present application, Y is selected from O or S.

[0035] According to some embodiments of the present application, R1and R2are each independently selected from F, cyano,

[0036]

[0037] R5is an optional substituent;

[0038] m2 is 0, 1, 2, 3, 4 or 5;

[0039] n4 is any integer from 0 to 12, preferably 0, 1, 2, 3, 4 or 5.

[0040] According to some embodiments of the present application, R5is C 1-10 alkyl, C 1-10 alkoxy or a halogen atom.

[0041] According to some embodiments of the present application, R3is selected from H,

[0042] n2 and n3 are each independently an integer from 0 to 12;

[0043] x2, y2, z2, x3, y3, z3 are each independently an integer from 0 to 30.

[0044] According to some embodiments of the present application, wherein,

[0045] X is selected from -CH=, -C(CF3)=, or -N=;

[0046] R4is C 1-10 alkyl, C 1-10 alkoxy or a halogen atom, said alkyl or alkoxy being substituted or unsubstituted, when substituted, said alkyl or alkoxy is substituted with F, Cl, Br or I; m1 is 0, 1, 2 or 3; n1 is any integer from 0 to 8; x1, y1, z1 are each independently any integer from 0 to 12;

[0047] Y is selected from O or S;

[0048] R1and R2are each independently selected from F, cyano, R5is C 1-10 alkyl, C 1-10 alkoxy or a halogen atom;

[0049] R3is selected from H,

[0050] n2 and n3 are each independently 0, 1, 2, 3, 4 or 5;

[0051] x2, y2, z2, x3, y3, z3 are each independently any integer from 0 to 12;

[0052] According to some embodiments of the present application, G1and G2are each independently selected from F, Cl, Br or I, simultaneously or separately.

[0053] According to some embodiments of the present application, wherein,

[0054] X is selected from -CH=, -C(CF3)=, or -N=;

[0055] R4is a methyl group, an ethyl group, a n-propyl group, an i-propyl group, a n-butyl group, a t-butyl group, a s-butyl group, an i-butyl group, a methoxy group, an ethoxy group, a n-propoxy group, an i-propoxy group, a n-butoxy group, an i-butoxy group, a s-butoxy group, a t-butoxy group, a trifluoromethyl group or a fluorine atom; m1 is 0, 1, 2 or 3;

[0056] n1 is 0, 1, 2, 3, 4 or 5;

[0057] x1, y1, z1 are each independently 0, 1, 2 or 3.

[0058] According to some embodiments of the present application, R4is a methyl group, an ethyl group, an i-propyl group, a t-butyl group, a methoxy group, an ethoxy group, an i-propoxy group, a trifluoromethyl group or a fluorine atom.

[0059] According to some embodiments of the present application, X is selected from -CH=, -C(CF3)=, -N=,

[0060] R4is a methyl group, an ethyl group, a n-propyl group, an i-propyl group, a n-butyl group, a t-butyl group, a s-butyl group or an i-butyl group;

[0061] x1, y1, z1 are each independently 1, 2 or 3.

[0062] According to some embodiments of the present application, wherein,

[0063] R1and R2are each independently selected from F, a cyano group, R5is fluorine, chlorine, bromine, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, -CH2CH2CH2CH2CH3, -CH(CH3)CH2CH2CH3, -CH2CH(CH3)CH2CH3, -CH2CH2CH(CH3)2, -CH(C2H5)CH2CH3, -C(CH3)2CH2CH3, -CH(CH3)CH(CH3)2, -CH2C(CH3)3, -CH2-CH2-CH2-CH2-CH2-CH3, -CH2-CH2-CH2-CH(CH3)-CH3, -CH2-CH2-CH(CH3)-CH2-CH3, -CH2-CH(CH3)-CH2-CH2-CH3, -CH(CH3)-CH2-CH2-CH2-CH3, -CH2-CH(CH3)-CH(CH3)-CH3, -CH(CH3)-CH(CH3)-CH2-CH3, -CH(CH3)-CH2-CH(CH3)-CH3, -CH2-CH2-C(CH3)2-CH3, -CH2-C(CH3)2-CH2-CH3, -C(CH3)3-CH2-CH2-CH3, -CH2-CH(CH2CH3)-CH2-CH3, -CH(CH2CH3)-CH2-CH2-CH3, -CH(CH2CH3)-CH(CH3)-CH3, -C(CH3)2-CH(CH3)-CH3, -CH(CH3)-C(CH3)2-CH3, or -C(CH3)(CH2CH3)-CH2-CH3.

[0064] According to some embodiments of the application, R5is a fluorine atom, n-butyl or n-hexyl.

[0065] According to some embodiments of the application, m2is 0, 1, 2 or 3.

[0066] According to some embodiments of the application, R1and R2are each independently selected from F, cyano or phenyl.

[0067] According to some embodiments of the application, R1and R2are each independently selected from F, cyano or phenyl.

[0068] R3is selected from H,

[0069] n2and n3are each independently 0, 1, 2, 3, 4 or 5;

[0070] x2, y2, z2, x3, y3, z3are each independently 0, 1, 2, 3, 4 or 5.

[0071] According to some embodiments of the present application, R3 is selected from H, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl,

[0072] n3 is 0, 1, 2, 3, 4 or 5;

[0073] x2, y2, z2, x3, y3, z3 are each independently 0, 1, 2 or 3.

[0074] According to some embodiments of the present application, G1 and G2 are simultaneously or independently each selected from Cl or Br.

[0075] By selecting the above-mentioned structures of X, Y, R1, R2, R3, G1 and G2, it is not only beneficial to improve the near-infrared absorption of the compound, but also beneficial to the efficient synthesis of the material.

[0076] According to some embodiments of the present application, the compound is selected from the following structures:

[0077]

[0078]

[0079] In another aspect, the present application also provides a method for preparing the halogen atom-containing fused BODIPY dimer compound according to the present application, wherein the method comprises preparing the compound of formula (I) by using the dimer of formula (II) as a raw material:

[0080]

[0081] According to some embodiments of the present application, the preparation of the compound of formula (I) by using the dimer of formula (II) as a raw material comprises:

[0082] When R1 and R2 are not halogen atoms at the same time, it comprises the steps of substituting one or two fluorine atoms on the boron atom by a nucleophilic substitution reaction, and the step of modifying the halogen atom on the terminal aromatic heterocycle of the dimer by a halogenation reaction;

[0083] Alternatively,

[0084] When R1 and R2 are halogen atoms at the same time, the preparation of the compound of formula (I) by using the dimer of formula (II) as a raw material comprises the step of modifying the halogen atom on the terminal aromatic heterocycle of the dimer by a halogenation reaction.

[0085] It is understood that the step of substituting one or both of the fluorine atoms on the boron atom by a nucleophilic substitution reaction and the step of modifying the halogen atom on the terminal aromatic heterocycle of the dimer by a halogenation reaction can be interchanged in order; and according to some embodiments of the present application, when R1and R2are not the same halogen atom, the nucleophilic substitution reaction is performed first by substituting one or both of the fluorine atoms on the boron atom, and then the halogenation reaction is performed to modify the halogen atom on the terminal aromatic heterocycle of the dimer.

[0086] According to some embodiments of the present application, when R1and / or R2is Aryl, the nucleophilic substitution reaction comprises: using an aryl Grignard reagent to perform a nucleophilic substitution reaction on a compound of formula (II) to obtain the target product.

[0087] According to some embodiments of the present application, when R1and / or R2is Aryl, the nucleophilic substitution reaction comprises: dissolving a compound of formula (II) in an organic solvent at low temperature, then slowly adding an aryl Grignard reagent, maintaining low temperature after adding, and obtaining the target product after processing.

[0088] According to some embodiments of the present application, when R1and / or R2is Aryl, the nucleophilic substitution reaction comprises: dissolving a compound of formula (II) in an organic solvent at 0°C under an inert atmosphere, then slowly adding an aryl Grignard reagent, maintaining low temperature (0-10°C) after adding, and obtaining the target product after processing.

[0089] According to some embodiments of the present application, the aryl Grignard reagent is selected from (bromophenylmagnesium).

[0090] According to some embodiments of the present application, the organic solvent is dry dichloromethane.

[0091] According to some embodiments of the present application, the reaction time of the low-temperature reaction is 4-10 hours.

[0092] According to some embodiments of the present application, when a mono-aryl-substituted product is prepared, the molar ratio of the compound of formula (II) to the aryl Grignard reagent is preferably 1:2; and when a di-aryl-substituted product is prepared, the molar ratio of the compound of formula (II) to the aryl Grignard reagent is preferably 1:(4-8).

[0093] According to some embodiments of the present application, when R1and / or R2is cyano, the nucleophilic substitution reaction comprises: using trimethylsilyl cyanide and tin tetrachloride to perform a reaction on a compound of formula (II) to obtain the target product.

[0094] According to some embodiments of the present application, when R1and / or R2is cyano, the nucleophilic substitution reaction comprises: dissolving the compound of formula (II), trimethylsilyl cyanide and tin tetrachloride in an organic solvent, and reacting at room temperature, and after treatment, obtaining the target product.

[0095] According to some embodiments of the present application, when R1and / or R2is cyano, the nucleophilic substitution reaction comprises: dissolving the compound of formula (II), trimethylsilyl cyanide and tin tetrachloride in an organic solvent, and reacting at room temperature in an inert atmosphere, and after treatment, obtaining the target product.

[0096] According to some embodiments of the present application, the organic solvent is dry dichloromethane.

[0097] According to some embodiments of the present application, the reaction time at room temperature is preferably 4-10 hours.

[0098] According to some embodiments of the present application, when preparing a mono-cyano substituted product, the molar ratio of the compound of formula (II), trimethylsilyl cyanide and tin tetrachloride is 1:2:1, and when preparing a di-cyano substituted product, the molar ratio of the compound of formula (II), trimethylsilyl cyanide and tin tetrachloride is 1:4:1.

[0099] According to some embodiments of the present application, when G1and G2are the same halogen atom, the halogenation reaction comprises: using the dimer after the nucleophilic substitution reaction as a raw material to react with a halogenated succinimide to obtain the target product.

[0100] According to some embodiments of the present application, the halogenation reaction comprises: dissolving the dimer after the nucleophilic substitution reaction and the halogenated succinimide in an organic solvent, and reacting at room temperature to obtain the target product.

[0101] According to some embodiments of the present application, the halogenation reaction comprises: dissolving the dimer after the nucleophilic substitution reaction and the halogenated succinimide in an organic solvent, and reacting at room temperature, and after treatment, obtaining the target product.

[0102] According to some embodiments of the present application, the halogenated succinimide is bromosuccinimide (NBS) or chlorosuccinimide (NCS).

[0103] According to some embodiments of the present application, the organic solvent is dichloromethane.

[0104] According to some embodiments of the present application, the molar ratio of the dimer after the nucleophilic substitution reaction and the halogenated succinimide is 1:(2-4).

[0105] According to some embodiments of the present application, the reaction time of the reaction is 4-20 hours, preferably 4-12 hours.

[0106] According to some embodiments of the present application, when G1, G2 are different halogen atoms, the halogenation reaction comprises two steps:

[0107] Step 1, the dimer after nucleophilic substitution reaction is mixed with an appropriate amount of the first halogenated succinimide, dissolved in dichloromethane, and reacted at room temperature, and the monohalogenated compound of formula (II) is obtained after post-treatment;

[0108] According to some embodiments of the present application, the first halogenated succinimide is bromosuccinimide (NBS) or chlorosuccinimide (NCS);

[0109] According to some embodiments of the present application, the molar ratio of the dimer after nucleophilic substitution reaction and the first halogenated succinimide is 1: (0.8-1.5), preferably 1: (0.9-1.1);

[0110] According to some embodiments of the present application, the reaction time of the reaction is 4-20 hours, preferably 4-12 hours.

[0111] Step 2, the monohalogenated compound of formula (II) is mixed with the second halogenated succinimide, dissolved in dichloromethane, and reacted at room temperature, and the target compound of formula (I) is obtained after post-treatment;

[0112] According to some embodiments of the present application, the second halogenated succinimide is bromosuccinimide (NBS) or chlorosuccinimide (NCS), and the halogen atoms of the second halogenated succinimide are different from those of the first halogenated succinimide;

[0113] According to some embodiments of the present application, the molar ratio of the monohalogenated compound of formula (II) and the second halogenated succinimide is 1: (1.0-3.0), preferably 1: (1.0-2.0);

[0114] According to some embodiments of the present application, the reaction time of the reaction is 4-20 hours, preferably 4-12 hours.

[0115] According to some embodiments of the present application, the method further comprises preparing the compound of formula (II) from the compound of formula (III):

[0116]

[0117] According to some embodiments of the present application, the monobromination reaction comprises dissolving the compound of formula (III) and bromosuccinimide (NBS) in an organic solvent at a molar ratio of 1 : (0.8-1.5) to react to obtain the monobromide of the compound of formula (III).

[0118] According to some embodiments of the present application, the monobromination reaction comprises dissolving the compound of formula (III) and bromosuccinimide (NBS) in an organic solvent at a molar ratio of 1 : (0.8-1.5) to react to obtain the monobromide of the compound of formula (III).

[0119] According to some embodiments of the present application, the molar ratio of the compound of formula (III) to bromosuccinimide (NBS) is 1 : (1-1.5); preferably 1 : 1.

[0120] According to some embodiments of the present application, the organic solvent is dichloromethane.

[0121] According to some embodiments of the present application, the monobromination reaction comprises reacting at 0°C for 1-5 hours.

[0122] According to some embodiments of the present application, the monobromination reaction comprises reacting at 0°C for 3 hours.

[0123] According to some embodiments of the present application, the monobromination reaction comprises dissolving the compound of formula (III) and bromosuccinimide (NBS) in an organic solvent at a molar ratio of 1 : (1-1.5) to react, and then post-treating to obtain the monobromide of the compound of formula (III).

[0124] According to some embodiments of the present application, the bimolecular Stille coupling reaction comprises using the monobromide of the compound of formula (III) as a raw material, and performing Stille coupling reaction in the presence of a tin reagent, a palladium catalyst and a ligand to obtain the compound of formula (II).

[0125] According to some embodiments of the present application, the bimolecular Stille coupling reaction comprises dissolving the monobromide of the compound of formula (III), a tin reagent, a palladium catalyst and a ligand in an organic solvent, and performing Stille coupling reaction under light-shielding and heating conditions to obtain the compound of formula (II).

[0126] According to some embodiments of the present application, the bimolecular Stille coupling reaction comprises dissolving the monobromide of the compound of formula (III), a tin reagent, a palladium catalyst and a ligand in an organic solvent under protection of an inert atmosphere, and performing Stille coupling reaction under light-shielding and heating conditions.

[0127] According to some embodiments of the present application, the tin reagent is hexa-n-butyl ditin.

[0128] According to some embodiments of the present application, the organic solvent is toluene.

[0129] According to some embodiments of the present application, the palladium catalyst is tris(dibenzylideneacetone)dipalladium.

[0130] According to some embodiments of the present application, the ligand is tris(o- methylphenyl)phosphine.

[0131] According to some embodiments of the present application, the molar ratio of the monobromide of the compound of formula (III), the tin reagent, the palladium catalyst, and the ligand is 1:0.5:(0.01-0.1):(0.04-0.2), preferably 1:0.5:0.05:(0.1-0.15), more preferably 1:0.5:0.05:0.12.

[0132] According to some embodiments of the present application, the reaction temperature of the Stille coupling reaction is 80-120°C, preferably 90-115°C.

[0133] According to some embodiments of the present application, the reaction time of the Stille coupling reaction is 1-96h, preferably 10-48h.

[0134] According to some embodiments of the present application, the method further comprises preparing the compound of formula (III) from the compound of formula (IV):

[0135]

[0136] According to some embodiments of the present application, the compound of formula (IV) is prepared into the compound of formula (III) by hydrolysis, formylation, condensation and borylation reactions in sequence, or by de-esterification, condensation and borylation reactions.

[0137] According to some embodiments of the present application, in the step of preparing the compound of formula (III) from the compound of formula (IV):

[0138] (1) when X is -CH=, the step comprises:

[0139] ① first performing a hydrolysis reaction: comprising hydrolyzing the compound of formula (IV) to obtain a hydrolysis product of the compound of formula (IV);

[0140] Preferably, the hydrolysis reaction comprises hydrolyzing the compound of formula (IV) in a solvent under catalysis of a base, and obtaining the hydrolysis product of the compound of formula (IV) after post-treatment;

[0141] Preferably, the base is an inorganic base, preferably sodium hydroxide or potassium hydroxide;

[0142] Preferably, the molar ratio of the compound of formula (IV) to the base is 1:(5-20), more preferably 1:(10-16);

[0143] Preferably, the solvent is a mixture of ethanol and distilled water;

[0144] Preferably, the volume ratio of ethanol to distilled water is (1-4):1, more preferably (2-3):1;

[0145] The reaction temperature is preferably 50-100°C, more preferably 60-80°C;

[0146] The reaction time is preferably 1-5h, more preferably 2-3h.

[0147] Then, the formylation reaction is carried out: the hydrolysis product of the compound of formula (IV) is dissolved in an organic acid solvent, heated for a period of time (40-60°C, 10-60min), and then triethyl orthoformate is added to continue the reaction (40-60°C, 0.5-5h), and after post-treatment, the formylate of the compound of formula (IV) is obtained.

[0148] Preferably, the organic acid solvent is trifluoroacetic acid;

[0149] Preferably, the molar ratio of the hydrolysis product of the compound of formula (IV) to triethyl orthoformate is 1:(2-10), more preferably 1:(3-5);

[0150] The reaction temperature is preferably 50°C; the reaction time of the first stage (after the hydrolysis product of the compound of formula (IV) is dissolved in an organic acid solvent, heating reaction) is preferably 15-30min, and the reaction time of the second stage (after triethyl orthoformate is added to continue the reaction) is preferably 1-3h.

[0151] Finally, the condensation and boronation reaction is carried out: the hydrolysis product of the compound of formula (IV) and the formylate of the compound of formula (IV) are subjected to condensation reaction, and then boronation reaction is carried out in the presence of boron trifluoride etherate to obtain the compound of formula (III).

[0152] Preferably, the condensation reaction includes dissolving the hydrolysis product of the compound of formula (IV), the formylate of the compound of formula (IV), and trifluoroacetic acid in an organic solvent, and reacting at 20-50°C for 1-5h;

[0153] Preferably, the condensation reaction includes dissolving the hydrolysis product of the compound of formula (IV), the formylate of the compound of formula (IV), and trifluoroacetic acid in an organic solvent under an argon atmosphere, and reacting at 20-50°C for 1-5h;

[0154] Preferably, the boronation reaction comprises adding triethylamine and boron trifluoride diethyl ether complex to the reaction system after the condensation reaction, and after the addition, the reaction is continued at low temperature for a period of time (-78°C, 30-60 min), then the reaction system is returned to room temperature and the reaction is continued (5-12 h), and after post-treatment, the compound of formula (III) is obtained.

[0155] Preferably, the boronation reaction comprises cooling the reaction system after the condensation reaction in a dry ice / acetone bath (-78°C), adding triethylamine and boron trifluoride diethyl ether complex to the reaction system, and after the addition, the reaction is continued at low temperature for a period of time (-78°C, 30-60 min), then the reaction system is returned to room temperature and the reaction is continued (5-12 h), and after post-treatment, the compound of formula (III) is obtained.

[0156] Preferably, the molar ratio of the hydrolysis product of the compound of formula (IV), the formylate of the compound of formula (IV), trifluoroacetic acid, triethylamine and boron trifluoride diethyl ether complex is 1.0:1.0:(0.1-10):(2.0-30.0):(5.0-45.0), more preferably 1.0:1.0:(0.8-1.5):(5.0-10.0):(10.0-20.0);

[0157] Preferably, the organic solvent is dry dichloromethane.

[0158] (2) When X is -C(CF3)=, -C(Aryl)= or -C(Alkyl)=, the step comprises:

[0159] ① First, the esterification reaction is carried out: the compound of formula (IV) is subjected to an esterification reaction in the presence of a base to obtain the esterification product of the compound of formula (IV);

[0160] Preferably, the esterification reaction comprises mixing the compound of formula (IV) with a base in an organic solvent, heating the mixture for a period of time, and after post-treatment, the esterification product of the compound of formula (IV) is obtained;

[0161] Preferably, the base is an inorganic base, preferably sodium hydroxide or potassium hydroxide;

[0162] The organic solvent is preferably ethylene glycol;

[0163] Preferably, the molar ratio of the compound of formula (IV) to the base is 1:(3-20), more preferably 1:(5-8);

[0164] The reaction temperature is preferably 110-200°C, more preferably 130-180°C;

[0165] The reaction time is preferably 2-10 h, more preferably 4-8 h.

[0166] (ii) then condensation and boronation: including reacting the de-esterified product of the compound of formula (IV) with an acyl chloride reagent (reaction time 2-8 h), then sequentially adding triethylamine and boron trifluoride diethyl ether complex to the reaction system, and continuing to react (reaction time 2-8 h) to obtain the compound of formula (III).

[0167] Preferably, the step includes dissolving the de-esterified product of the compound of formula (IV) and the acyl chloride reagent in an organic solvent and reacting for a period of time (2-8 h), then sequentially adding triethylamine and boron trifluoride diethyl ether complex to the reaction system, and continuing to react for a period of time (2-8 h), and obtaining the compound of formula (III) after post-treatment.

[0168] Preferably, the step includes, under an argon atmosphere, dissolving the de-esterified product of the compound of formula (IV) and the acyl chloride reagent in an organic solvent and reacting;

[0169] Preferably, the acyl chloride reagent is selected from aryl formyl chloride, alkyl formyl chloride or trifluoromethyl formyl chloride;

[0170] Preferably, after dissolving the de-esterified product of the compound of formula (IV) and the acyl chloride reagent in an organic solvent, the reaction is carried out at room temperature;

[0171] Preferably, after adding triethylamine and boron trifluoride diethyl ether complex, the reaction is carried out at room temperature;

[0172] Preferably, the molar ratio of the de-esterified product of the compound of formula (IV), the acyl chloride reagent, triethylamine and boron trifluoride diethyl ether complex is 1.0:(0.3-0.8):(2.0-10.0):(4.0-20.0), more preferably 1.0:(0.4-0.6):(2.0-5.0):(4.0-10.0);

[0173] Preferably, the organic solvent is dry dichloromethane;

[0174] Preferably, the reaction time for reacting the de-esterified product of the compound of formula (IV) and the acyl chloride reagent in an organic solvent is 2-8 hours, more preferably 4-6 hours; and the reaction time for reacting after adding triethylamine and boron trifluoride diethyl ether complex is 2-8 hours, more preferably 4-6 hours.

[0175] (3) when X is -N=, the step includes:

[0176] (i) first de-esterification: including de-esterifying the compound of formula (IV) in the presence of a base to obtain a de-esterified product of the compound of formula (IV);

[0177] Preferably, the de-esterification of the compound of formula (IV) is carried out by mixing the compound of formula (IV) with a base in an organic solvent, heating the reaction mixture for a period of time, and isolating the compound of formula (IV) after work-up;

[0178] Preferably, the base is an inorganic base, preferably sodium hydroxide or potassium hydroxide;

[0179] Preferably, the organic solvent is ethylene glycol;

[0180] Preferably, the molar ratio of the compound of formula (IV) to the base is 1 : (3-20), more preferably 1 : (5-8);

[0181] Preferably, the reaction temperature is 110-200 °C, more preferably 130-180 °C;

[0182] Preferably, the reaction time is 2-10 h, more preferably 4-8 h.

[0183] Preferably, the de-esterification of the compound of formula (IV) is carried out by mixing the compound of formula (IV) with a base in an organic solvent, heating the reaction mixture for a period of time, and isolating the compound of formula (IV) after work-up;

[0184] Preferably, the de-esterification of the compound of formula (IV) is carried out by mixing the compound of formula (IV) with a base in an organic solvent, heating the reaction mixture for a period of time, and isolating the compound of formula (IV) after work-up;

[0185] Preferably, the de-esterification of the compound of formula (IV) is carried out by mixing the compound of formula (IV) with a base in an organic solvent, heating the reaction mixture for a period of time, and isolating the compound of formula (IV) after work-up;

[0186] Preferably, the de-esterification of the compound of formula (IV) is carried out by mixing the compound of formula (IV) with a base in an organic solvent, heating the reaction mixture for a period of time, and isolating the compound of formula (IV) after work-up;

[0187] Preferably, the de-esterification of the compound of formula (IV) is carried out by mixing the compound of formula (IV) with a base in an organic solvent, heating the reaction mixture for a period of time, and isolating the compound of formula (IV) after work-up;

[0188] Preferably, the organic solvent is dry toluene;

[0189] Preferably, the molar ratio of the de-esterification product of the compound of formula (IV), sodium nitrite, pyrrole, triethylamine and boron trifluoride etherate complex is 1.0:1.0:1.0:(2.0-10.0):(4.0-20.0), more preferably 1.0:1.0:1.0:(2.0-5.0):(4.0-10.0);

[0190] Preferably, the volume ratio of acetic acid and acetic anhydride in the mixed solution of acetic acid and acetic anhydride is (1-3):1, more preferably 2:1;

[0191] Preferably, the temperature is raised to 50-120℃, more preferably 80℃.

[0192] Preferably, the temperature is raised to 50-120℃, more preferably 80℃.

[0193] The preparation process of the present application is as a whole shown below:

[0194]

[0195] In still another aspect, the present application also provides the application of the halogen atom-containing fused BODIPY dimer compound in the fields of organic solar cells, photodetectors, cell imaging and photodynamic therapy.

[0196] In summary, the present application provides a halogen atom-containing fused BODIPY dimer compound at the end of an aromatic heterocycle and its preparation and application. The compound of the present application has the following advantages:

[0197] 1. The present application adopts a strategy of annulation and dimerization, which can effectively extend the conjugation of the basic structure of BODIPY, red-shift the absorption spectrum of the material, and reduce the optical band gap;

[0198] 2. The present application can further improve the molar absorption coefficient of the material by modifying the halogen atom (e.g. bromine atom, chlorine atom) at the end of the aromatic heterocycle;

[0199] 3. The preparation method of the material of the present application is simple, easy to modify later, and easy to scale up synthesis.

[0200] 4. Experimental results show that the halogen atom-containing fused BODIPY dimer near-infrared responsive material provided by the present application has a very narrow optical band gap, and the maximum absorption wavelength of the film state is more than 880nm, and the highest can reach 928nm. The compound provided by the present application has strong absorption characteristics in the near-infrared region, and the molar absorption coefficient is more than 2.5×10 5 M -1 cm -1 , and the maximum can reach 3.2×10 5 M -1 cm.-1 The molar absorption coefficient is much higher than that of the same type of compound. Meanwhile, the photo-thermal stability of the compound is good. The present application provides a new material system for organic near-infrared light-responsive materials. BRIEF DESCRIPTION OF DRAWINGS

[0201] Figure 1 The H NMR spectrum of compound 2. 1 H NMR spectrum.

[0202] Figure 2 The H NMR spectrum of compound 3. 1 H NMR spectrum.

[0203] Figure 3 The H NMR spectrum of compound 4. 1 H NMR spectrum.

[0204] Figure 4 The H NMR spectrum of compound 5. 1 H NMR spectrum.

[0205] Figure 5 The H NMR spectrum of compound 6. 1 H NMR spectrum.

[0206] Figure 6 The H NMR spectrum of compound B1. 1 H NMR spectrum.

[0207] Figure 7 The UV-Vis absorption spectrum of compound B1 in chloroform solution.

[0208] Figure 8 The UV-Vis absorption spectrum of compound B1 in thin film state.

[0209] Figure 9 The thermogravimetric analysis (TGA) curve of compound B1.

[0210] Figure 10 The curve of the maximum absorption peak intensity of compound B1 thin film changing with sunlight irradiation time. DETAILED DESCRIPTION

[0211] The following detailed description of the implementation process and beneficial effects of the present application is intended to help the reader better understand the essence and characteristics of the present application, and is not intended to limit the scope of the present application.

[0212] Example 1: Synthesis of compound B1

[0213]

[0214] The synthesis of compound 1 is implemented according to the published patent (CN114249758A).

[0215] Synthesis of compound 2:

[0216] Compound 1 (8.81 g, 30.1 mmol), sodium hydroxide (17.89 g, 450.1 mmol), ethanol (150 mL) and distilled water (50 mL) were sequentially weighed in a 500 mL round-bottom flask under argon atmosphere, and the reaction system was heated to 80 °C for 2 hours. After the reaction was completed, the pH value of the reaction system was adjusted to 1 with 4M hydrochloric acid solution. The reaction solution was extracted with dichloromethane three times, and the organic phase was combined, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure to obtain compound 2 (7.5 g, 93%). Compound 2 was analyzed by nuclear magnetic resonance (1H NMR) and mass spectrometry (MS), and the results were as follows: Figure 1

[0217] Nuclear magnetic resonance analysis: 1 1H NMR (500 MHz, DMSO-d6) δ 12.43 (br, 1H), 11.50 (s, 1H), 7.46 (d, J = 5.3 Hz, 1H), 6.93 (d, J = 4.6 Hz, 1H), 2.92 (t, J = 7.6 Hz, 2H), 1.69 - 1.62 (m, 2H), 1.33 - 1.23 (m, 8H), 0.85 (t, J = 6.9 Hz, 3H).

[0218] Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: Theoretical value 265.1; experimental value 265.1.

[0219] Synthesis of compound 3:

[0220] Compound 2 (4.6 g, 17.4 mmol) and trifluoroacetic acid (50 mL) were weighed in a 100 mL round-bottom flask under argon atmosphere, and the reaction system was heated to 50 °C for 20 min. Then, triethyl orthoformate (10.9 g, 72.1 mmol) was added to the reaction system, and the reaction was continued at 50 °C for 1.5 h. After the reaction was completed, saturated NaHCO3 aqueous solution was added to the reaction solution to neutralize the reaction system. The reaction solution was extracted with dichloromethane three times, and the organic phase was combined, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained crude product was separated by silica gel column chromatography (eluent: a mixture of petroleum ether and ethyl acetate, volume ratio 5:1) to obtain compound 3 (2.6 g, yield 57%). Compound 3 was analyzed by nuclear magnetic resonance (1H NMR) and mass spectrometry (MS), and the results were as follows: Figure 2

[0221] Nuclear magnetic resonance analysis: 1 ​​H NMR (500 MHz, CDC13) δ 9.75 (s, 1H), 9.06 (br, 1H), 7.45 (d, J = 5.3 Hz, 1H), 6.94 (d, J = 4.6 Hz, 1H), 2.95 (t, J = 7.6 Hz, 2H), 1.81 - 1.75 (m, 2H), 1.41 - 1.25 (m, 8H), 0.88 (t, J = 6.9 Hz, 3H).

[0222] Matrix Assisted Laser Desorption Time of Flight Mass Spectrometry (MALDI-TOF) analysis: Theoretical value 249.1 ; Experimental value 249.1.

[0223] Synthesis of compound 4:

[0224] Compound 2 (2.7 g, 10.0 mmol), compound 3 (2.5 g, 10.0 mmol) and trifluoroacetic acid (0.6 mL) were weighed into a 100 mL round bottom flask under argon atmosphere, dry dichloromethane (25 mL) was added, the reaction system was heated to 40 °C for 2 h, then the reaction system was cooled in dry ice acetone bath, triethylamine (7.0 mL) and boron trifluoride etherate (28 mL) were added to the reaction system, the low temperature reaction was maintained for 50 min, the dry ice acetone bath was removed, the reaction system was placed at room temperature for 8 hours. The solvent was removed by reduced pressure distillation, the obtained crude product was separated by silica gel column chromatography (eluent was a mixture of petroleum ether: ethyl acetate, volume ratio was 5:1), compound 4 (3.0 g, yield 55%) was obtained. Compound 4 was analyzed by nuclear magnetic resonance (NMR) and mass spectrometry, and the results were as follows: Figure 3

[0225] NMR analysis: 1 H NMR (500 MHz, CDC13) δ 7.63 (d, J = 5.3 Hz, 2H), 7.36 (s, 1H), 7.11 (d, J = 5.3 Hz, 2H), 2.79 (t, J = 7.6 Hz, 4H), 1.79 - 1.71 (m, 4H), 1.42 - 1.24 (m, 16H), 0.89 (t, J = 6.9 Hz, 6H).

[0226] Matrix Assisted Laser Desorption Time of Flight Mass Spectrometry (MALDI-TOF) analysis: Theoretical value 500.2; Experimental value 500.2.

[0227] Synthesis of compound 5:

[0228] ​Compound 4 (1.0 g, 2.0 mmol) was weighed into a 50 mL round bottom flask, dichloromethane (25 mL) was added, the reaction system was shielded from light, and stirred in an ice water bath. NBS (534.0 mg, 3.0 mmol) was added to the reaction system in batches, and then the reaction was maintained at low temperature for 1 hour. The reaction liquid was poured into a large amount of distilled water, the reaction liquid was extracted with dichloromethane 3 times, the organic phase was combined, dried over anhydrous magnesium sulfate, and the organic phase was concentrated under reduced pressure. The obtained crude product was separated by silica gel column chromatography (eluent was a mixed solution of petroleum ether: dichloromethane, volume ratio was 3:1) to obtain compound 5 (464.0 mg, yield 40%). Compound 5 was analyzed by nuclear magnetic resonance (NMR) and mass spectrometry, and the results were as follows: Figure 4

[0229] NMR analysis: 1 H NMR (500 MHz, CDCl3) δ 7.66 (d, J = 5.3 Hz, 1H), 7.34 (s, 1H), 7.23 (s, 1H), 7.10 (d, J = 5.3 Hz, 1H), 2.82-2.73 (m, 4H), 1.81-1.67 (m, 4H), 1.42-1.23 (m, 16H), 0.89 (t, J = 5.0 Hz, 6H).

[0230] Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 578.1; experimental value 578.1.

[0231] Synthesis of compound 6:

[0232] Compound 5 (463 mg, 0.8 mmol), hexa-n-butyl ditin (217 mg, 0.4 mmol), tris(dibenzylideneacetone)dipalladium (41 mg, 0.04 mmol), and tris(o-methylphenyl)phosphine (30 mg, 0.1 mmol) were weighed into a 100 mL polymerization tube under an argon atmosphere, 20 mL of dry toluene was added, the reaction system was heated to reflux under light shielding conditions, and the reaction was carried out for 12 h. After the reaction was completed, the reaction liquid was concentrated under reduced pressure, and the obtained crude product was separated by silica gel column chromatography (eluent was a mixed solution of petroleum ether: dichloromethane, volume ratio was 2:1) to obtain compound 6 (220 mg, yield 55%). Compound 6 was analyzed by nuclear magnetic resonance (NMR) and mass spectrometry, and the results were as follows: Figure 5

[0233] NMR analysis: 1 ​​H NMR (500 MHz, CDCI3) δ 7.66 (d, J = 5.3 Hz, 2H), 7.35 (s, 2H), 7.25 (s, 2H), 7.12 (d, J = 5.2 Hz, 2H), 2.80-2.73 (m, 8H), 1.79-1.70 (m, 8H), 1.43-1.24 (m, 32H), 0.95-0.86 (m, 12H).

[0234] MALDI-TOF analysis: Theoretical value 998.4; experimental value 998.4.

[0235] Synthesis of compound B1:

[0236] Compound 6 (141 mg, 0.14 mmol) was weighed into a 50 mL round-bottom flask, dichloromethane (10 mL) was added, the reaction system was kept away from light, and was stirred in an ice water bath. NBS (53 mg, 0.29 mmol) was added to the reaction system, and then the reaction system was allowed to naturally restore room temperature and react for 12 hours. The reaction liquid was poured into a large amount of distilled water, the reaction liquid was extracted with dichloromethane for 3 times, the organic phase was combined, anhydrous magnesium sulfate was added for drying, and the organic phase was concentrated under reduced pressure. The obtained crude product was separated by silica gel column chromatography (eluent was a mixed solution of petroleum ether and dichloromethane, volume ratio was 1:1) to obtain compound B1 (148 mg, yield 91 %). Compound B1 was analyzed by nuclear magnetic analysis ( Figure 6 ) and mass spectrometry, and the results were as follows:

[0237] Nuclear magnetic analysis: 1 H NMR (500 MHz, CDCI3) δ 7.36 (s, 2H), 7.28 (s, 2H), 7.24 (s, 2H), 2.83-2.73 (m, 8H), 1.83-1.65 (m, 8H), 1.46-1.23 (m, 32H), 0.97-0.85 (m, 12H).

[0238] MALDI-TOF analysis: Theoretical value 1154.3; experimental value 1154.3.

[0239] Performance test:

[0240] The photophysical performance of the near-infrared response material based on fused BODIPY prepared in Example 1 of the application was characterized by using a UV-visible spectrophotometer. The absorption spectrum obtained in a dilute chloroform solution is shown in Figure 7 , and the absorption spectrum under a film state is shown in Figure 8 . In a dilute chloroform solution, the maximum absorption peak of the material is located at 810 nm, and the molar absorption coefficient of the maximum absorption peak is as high as 2.9 x 10 5 M-1 cm -1 ; under film state, the maximum absorption peak of the material is red-shifted to 909 nm, and the optical band gap of the material is calculated to be 1.25 eV according to the band of the film state absorption spectrum. The above results show that the compound B1 synthesized in the application has strong absorption characteristics in the near-infrared region.

[0241] Photothermal stability test:

[0242] The near-infrared responsive material based on fused BODIPY prepared in Example 1 of the application was analyzed by thermogravimetric analysis (TGA). As shown in the TGA curve Figure 9 , the thermal decomposition temperature of the material reaches 330℃ (the temperature corresponding to a 5% mass loss of the material). The TGA results show that the material has excellent thermal stability. The material thin film is placed under a simulated solar light source (100 mW cm -2 , AM 1.5G), and the absorption spectrum at different irradiation times is tested by using a UV-visible spectrophotometer to compare the change of the maximum absorption peak intensity. As shown in Figure 10 , the intensity of the maximum absorption peak of the material thin film basically remains after continuous irradiation for 48 h, and the attenuation amplitude is less than 2%, indicating that the material has excellent light stability.

[0243] Example 2-4: Synthesis of compounds B2, B3 and B10

[0244] The preparation method of compounds B2, B3 and B10 is the same as that of compound B1 prepared in Example 1, except that the initial raw material compound 1 of the reaction is replaced by compounds 7, 8 and 9, respectively. The synthesis of compounds 7, 8 and 9 is implemented by referring to the published patent (CN114249758A). The synthesis results and material characterization data are listed in the following table.

[0245]

[0246] Through Examples 2-4, compounds B2, B3 and B10 are synthesized, respectively. The absorption spectrum test results show that the three compounds all exhibit very strong near-infrared absorption characteristics, among which the molar absorption coefficient of compound B3 is as high as 3.2×10 5 M -1 cm -1 , and the maximum absorption peak of the film state is 915 nm. The three compounds all exhibit excellent photothermal stability, and the thermal decomposition temperature is higher than 300℃, and the absorbance attenuation amplitude is within 3% after 48 h of solar irradiation.

[0247] Example 5: Synthesis of compound B4

[0248]

[0249] Compound B1 (57.8 mg, 0.05 mmol) was weighed into a 50 mL two-necked flask under argon atmosphere, and dry dichloromethane 4 mL was added, and stirred in an ice-water bath. A solution of phenyl magnesium bromide in THF (1.0 M, 0.3 mL, 0.30 mmol) was slowly added dropwise into the reaction system, and the reaction was maintained at low temperature for 5 h after the dropwise addition was completed. After the reaction was completed, the reaction solution was poured into saturated aqueous ammonium chloride solution and stirred, and the aqueous phase was extracted with dichloromethane 3 times, and the organic phase was successively washed with distilled water, saturated brine, dried over anhydrous sodium sulfate, and concentrated. The obtained crude product was separated by silica gel column chromatography to obtain compound B4 (52.1 mg, yield 75%).

[0250] Compound B4 was subjected to nuclear magnetic analysis: 1 H NMR (500 MHz, CDC13) δ 7.27 (s, 2H), 7.24-7.15 (m, 20H), 6.18 (s, 2H), 6.05 (s, 2H), 2.85-2.75 (m, 8H), 1.81-1.63 (m, 8H), 1.47-1.22 (m, 32H), 0.98-0.83 (m, 12H).

[0251] Compound B4 was subjected to elemental analysis, and the results were as follows: calculated value C, 67.44; H, 6.24; N, 4.03; S, 9.23. Experimental value C, 67.34; H, 6.22; N, 4.03; S, 9.19.

[0252] Compound B4 was subjected to MALDI-TOF analysis: theoretical value 1386.4; experimental value 1386.4.

[0253] Performance test:

[0254] The compound B4 prepared in Example 5 of the present application was subjected to photophysical performance characterization by using a UV-visible spectrophotometer. In a dilute chloroform solution, the maximum absorption peak of the material was located at 811 nm, and the molar absorption coefficient reached 2.7 x 10 5 M -1 cm -1 ; under film state, the maximum absorption peak was red-shifted to 895 nm. According to the band of the absorption spectrum under film state, the optical band gap of the dimer was calculated to be 1.37 eV. The above results show that the compound B4 synthesized in the present application has strong absorption characteristics in the near-infrared region. The compound B4 has excellent photothermal stability, and the thermal decomposition temperature is 318°C, and the absorbance attenuation amplitude is about 2% after solar irradiation for 48 h.

[0255] Example 6: Synthesis of compound B5

[0256]

[0257] Compound B1 (69.4 mg, 0.06 mmol) was weighed into a 50 mL two-necked flask under argon atmosphere, and dry dichloromethane (4 mL) was added, and the mixture was stirred in an ice-water bath. A solution of phenyl magnesium bromide in THF (1.0 M, 0.12 mL, 0.12 mmol) was added dropwise to the reaction system, and the mixture was stirred at low temperature for 5 h after the dropwise addition was completed. After the reaction was completed, the reaction solution was poured into saturated aqueous ammonium chloride solution, and the aqueous phase was extracted with dichloromethane three times. The organic phases were combined and washed with distilled water, saturated brine, dried over anhydrous sodium sulfate, and concentrated. The obtained crude product was separated by silica gel column chromatography to obtain compound B5 (31.3 mg, yield 41%).

[0258] Compound B5 was subjected to nuclear magnetic analysis: 1 H NMR (500 MHz, CDC13) δ 7.29 (s, 2H), 7.25-7.10 (m, 14H), 2.83-2.75 (m, 8H), 1.82-1.61 (m, 8H), 1.46-1.25 (m, 32H), 0.97-0.85 (m, 12H).

[0259] Compound B5 was subjected to elemental analysis, and the results were as follows: calculated value C, 62.27; H, 6.02; N, 4.40; S, 10.08. Experimental value C, 62.19; H, 6.04; N, 4.40; S, 10.00.

[0260] Compound B5 was subjected to MALDI-TOF analysis: theoretical value 1270.4; experimental value 1270.4.

[0261] Performance test:

[0262] The compound B5 prepared in Example 6 of the present application was subjected to photophysical performance characterization by using a UV-visible spectrophotometer. In a dilute chloroform solution, the maximum absorption peak of the material was located at 802 nm, and the molar absorption coefficient was 2.6 x 10 5 M -1 cm -1 ; under film state, the maximum absorption peak was red-shifted to 887 nm. According to the band of the absorption spectrum under film state, the optical band gap of the dimer was calculated to be 1.37 eV. The above results show that the compound B5 synthesized in the present application has strong absorption characteristics in the near-infrared region. The compound B5 has excellent photothermal stability, and the thermal decomposition temperature is 315°C, and the absorbance attenuation amplitude is about 3% after solar irradiation for 48 h.

[0263] Example 7: Synthesis of compound B6

[0264]

[0265] Under argon atmosphere, compound B1 (57.8 mg, 0.05 mmol), trimethylsilyl cyanide (20.0 mg, 0.20 mmol), tin tetrachloride (13.0 mg, 0.05 mmol) were weighed into a 50 mL round bottom flask, 4 mL of dry dichloromethane was added, and the reaction was stirred at room temperature for 5 h. After the reaction was completed, the reaction solution was poured into a large amount of distilled water, and the water phase was extracted with dichloromethane for 3 times. The organic phase was washed with distilled water, saturated brine, dried over anhydrous sodium sulfate, and concentrated. The obtained crude product was separated by silica gel column chromatography to obtain compound B6 (20.1 mg, yield 34%).

[0266] Compound B6 was subjected to nuclear magnetic analysis: 1 H NMR (500 MHz, CDCl3) δ 7.41 (s, 2H), 7.31 (s, 2H), 7.27 (s, 2H), 2.81-2.71 (m, 8H), 1.80-1.62 (m, 8H), 1.45-1.22 (m, 32H), 0.98-0.85 (m, 12H).

[0267] Compound B6 was subjected to elemental analysis, and the results were as follows: calculated value C, 58.79; H, 5.61; N, 9.46; S, 10.82. Experimental value C, 58.70; H, 5.62; N, 9.43; S, 10.79.

[0268] Compound B6 was subjected to MALDI-TOF analysis: theoretical value 1182.3; experimental value 1182.3.

[0269] Performance test:

[0270] The compound B6 prepared in Example 7 of the application was subjected to photophysical performance characterization by using a UV-visible spectrophotometer. In a dilute chloroform solution, the maximum absorption peak of the material was located at 813 nm, and the molar absorption coefficient was 2.9 x 10 5 M -1 cm -1 ; under film state, the maximum absorption peak was red-shifted to 907 nm. According to the band of the film state absorption spectrum, the optical band gap of the dimer was calculated to be 1.29 eV. The above results show that the compound B6 synthesized in the application has strong absorption characteristics in the near-infrared region. The compound B6 has excellent photothermal stability, and the thermal decomposition temperature is 332℃. After sunlight irradiation for 48 h, the absorbance attenuation amplitude is about 2%.

[0271] Example 8: synthesis of compound B7

[0272]

[0273] Compound 6 (121 mg, 0.12 mmol) was weighed into a 50 mL round-bottom flask, dichloromethane (10 mL) was added, the reaction system was kept away from light, chlorosuccinimide NCS (40 mg, 0.30 mmol) was added to the reaction system, and the reaction was carried out at room temperature for 12 hours. The reaction liquid was poured into a large amount of distilled water, the reaction liquid was extracted with dichloromethane for 3 times, the organic phases were combined, anhydrous magnesium sulfate was added for drying, and the organic phase was concentrated under reduced pressure. The obtained crude product was separated by silica gel column chromatography (eluent was a mixed solution of petroleum ether and dichloromethane, the volume ratio was 1:1) to obtain compound B7 (113 mg, yield 88%). Compound B7 was analyzed by nuclear magnetic resonance, elemental analysis and mass spectrometry, and the results were as follows:

[0274] Nuclear magnetic resonance analysis: 1 H NMR (500 MHz, CDCl3) δ 7.42 (s, 2H), 7.33 (s, 2H), 7.24 (s, 2H), 2.79-2.70 (m, 8H), 1.86-1.69 (m, 8H), 1.50-1.26 (m, 32H), 0.99-0.85 (m, 12H).

[0275] Elemental analysis: calculated value C, 60.73; H, 6.23; N, 5.25; S, 12.01. Experimental value C, 60.64; H, 6.24; N, 5.23; S, 12.00.

[0276] Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1066.4; experimental value 1066.4.

[0277] Performance test:

[0278] The photophysical performance of the near-infrared responsive material based on fused BODIPY prepared in Example 8 of the application was characterized by ultraviolet-visible spectrophotometer. In a dilute chloroform solution, the maximum absorption peak of the material was at 813 nm, and the molar absorption coefficient was 3.1 x 10 5 M -1 cm -1 ; in a film state, the maximum absorption peak was red-shifted to 912 nm. According to the sideband of the film state absorption spectrum, the optical band gap of the dimer was calculated to be 1.24 eV. The above results show that the compound B7 synthesized in the application has strong absorption characteristics in the near-infrared region. Compound B7 has excellent photothermal stability, and the thermal decomposition temperature is 335℃, and the absorbance attenuation amplitude is about 2% after solar irradiation for 48 hours.

[0279] Examples 9, 10: Synthesis of compounds B8, B12

[0280] The preparation method of compounds B8, B12 is the same as that of compound B6 prepared in Example 7, except that the initial raw material compound B1 of the reaction is replaced by compounds B7, B10, respectively. The synthesis results and material characterization data are listed in the following table.

[0281]

[0282]

[0283] Compounds B8, B12 were synthesized by Examples 9, 10, respectively. The absorption spectrum test results show that both compounds exhibit very strong near-infrared absorption characteristics, in which the molar absorption coefficient of compound B12 reaches 3.0 x 10 5 M -1 cm -1 The maximum absorption peak of the film state is 916 nm. Both compounds exhibit excellent photothermal stability, and the thermal decomposition temperature is higher than 300℃, and the absorbance decay amplitude is within 3% after 48h of solar irradiation.

[0284] Examples 11, 12: Synthesis of compounds B9, B11

[0285] The preparation method of compounds B9, B11 is the same as that of compound B4 prepared in Example 5, except that the initial raw material compound B1 of the reaction is replaced by compounds B7, B10, respectively. The synthesis results and material characterization data are listed in the following table.

[0286]

[0287] Compounds B9, B11 were synthesized by Examples 11, 12, respectively. The absorption spectrum test results show that both compounds exhibit very strong near-infrared absorption characteristics, and the molar absorption coefficient of both compounds is higher than 3.0 x 10 5 M -1 cm -1 The maximum absorption peak of the film state is more than 915 nm. Both compounds exhibit excellent photothermal stability, and the thermal decomposition temperature is higher than 300℃, and the absorbance decay amplitude is within 3% after 48h of solar irradiation.

[0288] Example 13: Synthesis of compounds B13, B14

[0289]

[0290] Synthesis of compound 10:

[0291] Compound 10-1 (3.32 g, 17.0 mmol), potassium hydroxide (5.74 g, 102.3 mmol) and ethylene glycol (90 mL) were sequentially weighed in a 250 mL round bottom flask under argon atmosphere, and the reaction system was heated to 170°C for 5 hours. After the reaction was completed, a large amount of water was added to the reaction system, and the reaction solution was extracted with dichloromethane three times, and the organic phases were combined, dried over anhydrous magnesium sulfate, and the organic phase was concentrated under reduced pressure. The obtained crude product was separated by silica gel column chromatography (eluent: a mixture of petroleum ether and ethyl acetate, volume ratio 10:1) to obtain compound 10 (1.93 g, yield 92%).

[0292] Compound 10 was subjected to nuclear magnetic analysis, and the results were as follows:

[0293] Nuclear magnetic analysis: 1 H NMR (500 MHz, CDC13) δ 8.21 (s, 1H), 7.10 (dd, J = 5.6 Hz, J = 1.2 Hz, 1H), 7.0 (m, 1H), 6.94 (d, J = 5.6 Hz, 1H), 6.48 (m, 1H).

[0294] Synthesis of compound 11:

[0295] Compound 10 (1.16 g, 9.4 mmol) was weighed in a 100 mL round bottom flask under argon atmosphere, and dry dichloromethane 60 mL was added, stirred, and m-trimethylphenylcarbonyl chloride (0.80 mL, 4.8 mmol) was added to the reaction system, and the reaction system was placed at room temperature for 5 hours, and then triethylamine (3.2 mL, 23.6 mmol) and boron trifluoride etherate (6.0 mL, 47.0 mmol) were added to the reaction system, and the reaction was continued at room temperature for 5 hours. The reaction solution was concentrated under reduced pressure, and the obtained crude product was separated by silica gel column chromatography (eluent: a mixture of petroleum ether and ethyl acetate, volume ratio 2:1) to obtain compound 11 (0.89 g, yield 45%). Compound 11 was subjected to elemental analysis and mass spectrometry analysis, and the results were as follows:

[0296] Elemental analysis: calculated value C, 62.57; H, 4.06; N, 6.63; S, 15.19. Experimental value C, 62.47; H, 4.09; N, 6.60; S, 15.11.

[0297] Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 422.1; experimental value 422.1.

[0298] Synthesis of compound 12:

[0299] Compound 11 (0.89 g, 2.1 mmol) was weighed into a 50 mL round bottom flask, dichloromethane (25 mL) was added, the reaction system was protected from light, and stirred in an ice water bath. NBS (391.6 mg, 2.2 mmol) was added to the reaction system in portions, and then the reaction was maintained at low temperature for 1 hour. The reaction solution was poured into a large amount of distilled water, the reaction solution was extracted with dichloromethane 3 times, the organic phases were combined, anhydrous magnesium sulfate was added for drying, and the organic phase was concentrated under reduced pressure. The obtained crude product was separated by silica gel column chromatography (eluent: petroleum ether: dichloromethane mixture solution, volume ratio 2:1) to obtain compound 12 (632.0 mg, yield 60%). Compound 12 was subjected to elemental analysis and mass spectrometry analysis, and the results were as follows:

[0300] Elemental analysis: calculated value C, 52.72; H, 3.22; N, 5.59; S, 12.79. Experimental value C, 52.62; H, 3.21; N, 5.59; S, 12.71.

[0301] Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 500.0; experimental value 500.0.

[0302] Synthesis of compound 13:

[0303] Compound 12 (401 mg, 0.8 mmol), hexane ditin (217 mg, 0.4 mmol), tris(dibenzylideneacetone)dipalladium (41 mg, 0.04 mmol) and tris(o-methylphenyl)phosphine (30 mg, 0.1 mmol) were weighed into a 100 mL polymerization tube under an argon atmosphere, 20 mL of dry toluene was added, the reaction system was heated to reflux under light protection, and the reaction was maintained for 12 h. After the reaction was completed, the reaction solution was concentrated under reduced pressure, and the obtained crude product was separated by silica gel column chromatography (eluent: petroleum ether: dichloromethane mixture solution, volume ratio 2:1) to obtain compound 13 (202 mg, yield 60%). Compound 13 was subjected to elemental analysis and mass spectrometry analysis, and the results were as follows:

[0304] Elemental analysis: calculated value C, 62.72; H, 3.83; N, 6.65; S, 15.22. Experimental value C, 62.65; H, 3.83; N, 6.63; S, 15.18.

[0305] Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 842.2; experimental value 842.2.

[0306] Synthesis of compound B13:

[0307] Compound 13 (118 mg, 0.14 mmol) was weighed into a 50 mL round-bottom flask, dichloromethane (10 mL) was added, the reaction system was protected from light, and stirred in an ice-water bath. NBS (53 mg, 0.29 mmol) was added to the reaction system, and then the reaction system was allowed to naturally recover to room temperature and react for 12 h. The reaction liquid was poured into a large amount of distilled water, the reaction liquid was extracted with dichloromethane 3 times, the organic phases were combined, anhydrous magnesium sulfate was added for drying, and the organic phase was concentrated under reduced pressure. The obtained crude product was separated by silica gel column chromatography (eluent: a mixture of petroleum ether and dichloromethane, volume ratio 1:1) to obtain compound B13 (130 mg, yield 93%). Compound B13 was subjected to nuclear magnetic analysis and elemental analysis, and the results were as follows:

[0308] Nuclear magnetic analysis: 1 H NMR (500 MHz, CDCl3) δ 7.34 (s, 2H), 7.21 (s, 2H), 6.81 (s, 4H), 6.67 (s, 4H), 2.35 (s, 18H).

[0309] Elemental analysis: calculated value C, 52.82; H, 3.02; N, 5.60; S, 12.82. Experimental value C, 52.75; H, 3.03; N, 5.55; S, 12.80.

[0310] Synthesis of compound B14:

[0311] Compound B13 (50.0 mg, 0.05 mmol) was weighed into a 50 mL two-necked flask under an argon atmosphere, 4 mL of dry dichloromethane was added, and stirred in an ice-water bath. A phenyl magnesium bromide THF solution (1.0 M, 0.3 mL, 0.30 mmol) was slowly added dropwise to the reaction system, and after the dropwise addition was completed, the reaction was maintained at low temperature for 5 h. After the reaction was completed, the reaction liquid was poured into a saturated aqueous ammonium chloride solution and stirred, the aqueous phase was extracted with dichloromethane 3 times, the organic phases were combined and washed with distilled water, saturated brine, dried with anhydrous sodium sulfate, and the organic phase was concentrated. The obtained crude product was separated by silica gel column chromatography to obtain compound B14 (40.1 mg, yield 65%).

[0312] Compound B14 was subjected to nuclear magnetic analysis: 1 H NMR (500 MHz, CDCl3) δ 7.24-7.15 (m, 20H), 6.83 (s, 4H), 6.69 (s, 4H), 6.20 (s, 2H), 6.07 (s, 2H), 2.33 (s, 18H).

[0313] Elemental analysis of compound B14 was performed, and the results were as follows: calculated value of C, 66.25; H, 4.09; N, 4.54; S, 10.40. Experimental value of C, 66.18; H, 4.08; N, 4.52; S, 10.36.

[0314] Performance test:

[0315] The photophysical properties of compounds B13 and B14 were characterized by using a UV-Vis spectrophotometer. In a dilute chloroform solution, the maximum absorption peaks of B13 and B14 were located at 799 nm and 803 nm, respectively, and the molar absorption coefficients were 2.8 x 10 5 M -1 cm -1 and 2.7 x 10 5 M -1 cm -1 , respectively. In a film state, the maximum absorption peaks of B13 and B14 were 890 nm and 902 nm, respectively. According to the band of the absorption spectrum in the film state, the optical band gaps of B13 and B14 were calculated to be 1.35 eV and 1.29 eV, respectively. The above results show that the synthesized compounds B13 and B14 have strong absorption characteristics in the near-infrared region. Both compounds exhibit excellent photothermal stability, and the thermal decomposition temperatures are higher than 300℃. After 48 h of solar irradiation, the absorbance decay amplitudes are within 3%.

[0316] Examples 14-16: Synthesis of compounds B15, B16 and B17

[0317] The preparation method of compounds B15, B16 and B17 is the same as that of compound B14 prepared in Example 13, except that the initial raw materials and acyl chloride reagents are different. The synthesis results and material characterization data are listed in the following table.

[0318]

[0319]

[0320] Through Examples 14-16, compounds B15, B16 and B17 were synthesized, respectively. The absorption spectrum test results show that the three compounds all exhibit very strong near-infrared absorption characteristics, in which the molar absorption coefficient of compound B15 is as high as 3.2 x 10 5 M -1 cm -1 , and the maximum absorption peak in a film state is 928 nm. The three compounds all exhibit excellent photothermal stability, and the thermal decomposition temperatures are higher than 300℃. After 48 h of solar irradiation, the absorbance decay amplitudes are within 3%.

[0321] Example 17: Synthesis of compound B18

[0322]

[0323] The synthesis of compound 14 was performed according to the published patent (CN114249758A).

[0324] Synthesis of compound 15:

[0325] Compound 14 (11.0 g, 0.03 mol), potassium hydroxide (10.5 g, 0.18 mol) and ethylene glycol (150 mL) were sequentially added into a 250 mL round-bottom flask under argon atmosphere, and the reaction system was heated to 170°C for 5 hours. After the reaction was completed, a large amount of water was added to the reaction system, and the reaction solution was extracted with diethyl ether for 3 times. The organic phases were combined, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The obtained crude product was separated by silica gel column chromatography (eluent: a mixture of petroleum ether and dichloromethane with a volume ratio of 2:1) to obtain compound 15 (7.9 g, yield 93%). Compound 15 was subjected to elemental analysis and mass spectrometry analysis, and the results were as follows:

[0326] Elemental analysis: calculated value C, 76.28; H, 7.47; N, 4.94; S, 11.31. Experimental value C, 76.22; H, 7.45; N, 4.93; S, 11.29.

[0327] Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 283.1; experimental value 283.1.

[0328] Synthesis of compound 16:

[0329] Compound 15 (4.0 g, 0.01 mol) and a mixed solution of acetic acid / acetic anhydride (50 mL / 25 mL) were added into a 250 mL round-bottom flask, and the reaction system was stirred in an ice water bath. Sodium nitrite (0.7 g, 0.01 mol) and pyrrole (3.4 g, 0.01 mol) were added to the reaction system, and the reaction was maintained at low temperature for 0.5 hours. Then the reaction system was heated to 80°C for 0.5 hours. The reaction solution was filtered, and the obtained filter cake was washed with ethanol for 3 times and dried under vacuum. The filter cake was added into a 250 mL round-bottom flask under argon atmosphere, and triethylamine (5 mL, 36.9 mmol), boron trifluoride etherate (10 mL, 78.4 mmol) and dry toluene (120 mL) were added. The reaction system was heated to 80°C for 1 hour. The solvent was removed by distillation under reduced pressure, and the obtained crude product was separated by silica gel column chromatography (eluent: a mixture of petroleum ether and dichloromethane with a volume ratio of 2:1) to obtain compound 16 (1.3 g, yield 41%). Compound 16 was subjected to elemental analysis and mass spectrometry analysis, and the results were as follows:

[0330] Elemental analysis: Calculated C, 69.11 ; H, 6.12; N, 6.72; S, 10.25. Found C, 69.03; H, 6.10; N, 6.70; S, 10.23.

[0331] MALDI-TOF analysis: Theoretical value 625.3; experimental value 625.3.

[0332] Synthesis of compound 17:

[0333] Compound 16 (1.2 g, 1.9 mmol) was weighed into a 50 mL round bottom flask, dichloromethane (30 mL) was added, the reaction system was kept away from light, and stirred in an ice water bath. NBS (0.35 g, 2.0 mmol) was added to the reaction system in batches, and then the reaction was maintained at low temperature for 1 hour. The reaction liquid was poured into a large amount of distilled water, the reaction liquid was extracted with dichloromethane for 3 times, the organic phase was combined, anhydrous magnesium sulfate was added for drying, and the organic phase was concentrated under reduced pressure. The obtained crude product was separated by silica gel column chromatography (eluent was a mixed solution of petroleum ether and dichloromethane, volume ratio was 1:1) to obtain compound 17 (0.56 g, yield 43%). Compound 17 was subjected to elemental analysis and mass spectrum analysis, and the results were as follows:

[0334] Elemental analysis: Calculated C, 61.37; H, 5.29; N, 5.96; S, 9.10. Found C, 61.30; H, 5.30; N, 5.92; S, 9.07.

[0335] MALDI-TOF analysis: Theoretical value 703.2; experimental value 703.2.

[0336] Synthesis of compound 18:

[0337] Compound 17 (560 mg, 0.8 mmol), hexa-n-butyl ditin (217 mg, 0.4 mmol), tris(dibenzylideneacetone)dipalladium (41 mg, 0.04 mmol) and tris(o-methylphenyl)phosphine (30 mg, 0.1 mmol) were weighed into a 100 mL polymerization tube under an argon atmosphere, 20 mL of dry toluene was added, the reaction system was heated to reflux under light shielding condition, and the reaction was maintained for 12 h. After the reaction was completed, the reaction liquid was concentrated under reduced pressure, and the obtained crude product was separated by silica gel column chromatography (eluent was a mixed solution of petroleum ether and dichloromethane, volume ratio was 2:1) to obtain compound 18 (290 mg, yield 58%). Compound 18 was subjected to elemental analysis and mass spectrum analysis, and the results were as follows:

[0338] Elemental analysis: Calculated value C, 69.22; H, 5.97; N, 6.73; S, 10.27. Experimental value C, 69.13; H, 5.98; N, 6.69; S, 10.25.

[0339] Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: Theoretical value 1248.5; experimental value 1248.5.

[0340] Synthesis of compound B18:

[0341] Compound 18 (175 mg, 0.14 mmol) was weighed into a 50 mL round-bottom flask, dichloromethane (10 mL) was added, the reaction system was kept away from light, and was stirred in an ice water bath. NBS (53 mg, 0.29 mmol) was added to the reaction system, and then the reaction system was allowed to naturally restore room temperature and react for 12 hours. The reaction liquid was poured into a large amount of distilled water, the reaction liquid was extracted with dichloromethane for 3 times, the organic phase was combined, anhydrous magnesium sulfate was added for drying, and the organic phase was concentrated under reduced pressure. The obtained crude product was separated by silica gel column chromatography (eluent was a mixed solution of petroleum ether and dichloromethane, volume ratio was 1:1) to obtain compound B18 (175 mg, yield 89%). Compound B18 was subjected to nuclear magnetic analysis and elemental analysis, and the results were as follows:

[0342] Nuclear magnetic analysis: 1 H NMR (500 MHz, CDCl3) δ 7.45-7.39 (m, 18H), 7.24 (s, 2H), 2.76-2.64 (m, 8H), 1.71-1.58 (m, 8H), 1.45-1.26 (m, 24H), 0.98-0.87 (m, 12H).

[0343] Elemental analysis: Calculated value C, 61.46; H, 5.16; N, 5.97; S, 9.12. Experimental value C, 61.39; H, 5.13; N, 5.90; S, 9.09.

[0344] Performance test:

[0345] The compound B18 prepared in Example 17 of the application was subjected to photophysical performance characterization by using a UV-visible spectrophotometer. In a dilute chloroform solution, the maximum absorption peak of the material was located at 830 nm, and the molar absorption coefficient was 2.6 x 10 5 M -1 cm -1; the maximum absorption peak of the film state is red-shifted to 923 nm. According to the band of the absorption spectrum of the film state, the optical band gap of the dimer is calculated to be 1.21 eV. The above results show that the compound B19 synthesized in the application has strong absorption characteristics in the near-infrared region. The compound B18 has excellent photothermal stability, and the thermal decomposition temperature is 336℃, and the absorbance attenuation amplitude is about 2% after 48 h of sunlight irradiation.

[0346] Example 18: Synthesis of compound B19

[0347]

[0348] Synthesis of compound 19:

[0349] Compound 6 (280 mg, 0.28 mmol) was weighed into a 50 mL round-bottom flask, dichloromethane (20 mL) was added, the reaction system was shielded from light, and the reaction system was stirred in an ice water bath. NBS (51 mg, 0.28 mmol) was added to the reaction system, and then the reaction system was allowed to naturally recover to room temperature and react for 12 hours. The reaction liquid was poured into a large amount of distilled water, the reaction liquid was extracted with dichloromethane for 3 times, the organic phases were combined, anhydrous magnesium sulfate was added for drying, and the organic phase was concentrated under reduced pressure. The obtained crude product was separated by silica gel column chromatography (eluent: a mixed solution of petroleum ether and dichloromethane, volume ratio 1:1) to obtain compound 19 (184 mg, yield 61%). Compound 19 was subjected to elemental analysis and mass spectrum analysis, and the results were as follows:

[0350] Elemental analysis: calculated value C, 60.17; H, 6.27; N, 5.20; S, 11.90. Experimental value C, 60.10; H, 6.26; N, 5.18; S, 11.88.

[0351] Matrix-assisted laser desorption time-of-flight mass spectrometry (MALDI-TOF) analysis: theoretical value 1076.4; experimental value 1076.4.

[0352] Synthesis of compound B19:

[0353] Compound 19 (162 mg, 0.15 mmol) was weighed into a 50 mL round-bottom flask, dichloromethane (10 mL) was added, the reaction system was shielded from light, chlorosuccinimide NCS (27 mg, 0.20 mmol) was added to the reaction system, and the reaction was carried out at room temperature for 12 hours. The reaction liquid was poured into a large amount of distilled water, the reaction liquid was extracted with dichloromethane for 3 times, the organic phases were combined, anhydrous magnesium sulfate was added for drying, and the organic phase was concentrated under reduced pressure. The obtained crude product was separated by silica gel column chromatography (eluent: a mixed solution of petroleum ether and dichloromethane, volume ratio 1:1) to obtain compound B19 (142 mg, yield 85%). Compound B7 was subjected to nuclear magnetic analysis, elemental analysis and mass spectrum analysis, and the results were as follows:

[0354] NMR analysis: 1 H NMR (500 MHz, CDCI3) δ 7.41 (s, 1 H), 7.34 (s, 2H), 7.28 (s, 1 H), 7.24 (s, 2H), 2.80-2.70 (m, 8H), 1.88-1.71 (m, 8H), 1.50-1.25 (m, 32H), 0.98-0.83 (m, 12H).

[0355] Elemental analysis: Calculated C, 58.31 ; H, 5.98; N, 5.04; S, 11.53. Found C, 58.22; H, 5.98; N, 5.00; S, 11.50.

[0356] MALDI-TOF analysis: Theoretical value 1110.3; experimental value 1110.3.

[0357] Performance test:

[0358] The compound B19 prepared in Example 18 of the present application was characterized by photophysical properties using a UV-Vis spectrophotometer. In a dilute chloroform solution, the maximum absorption peak of the material was at 812 nm, and the molar absorption coefficient reached 3.0 x 10 5 M -1 cm -1 ; in film state, the maximum absorption peak was red-shifted to 910 nm. According to the band of the film-state absorption spectrum, the optical band gap of the dimer was calculated to be 1.25 eV. The above results show that the compound B19 synthesized in the present application has strong absorption characteristics in the near-infrared region. The compound B19 has excellent photothermal stability, and the thermal decomposition temperature is 320°C. After 48 h of sunlight irradiation, the absorbance decay amplitude is about 2%.

[0359] Comparative example

[0360] The molar absorption coefficient of the compound provided by the present application and the compound with similar structure in the prior art (patent CN114249758A) is compared:

[0361]

[0362]

[0363]

[0364]

[0365] As can be seen from the above table, the fused BODIPY dimer compound provided by the application containing halogen atoms on the terminal aromatic heterocycle has a significantly higher molar absorption coefficient than its structural analogs, for example, the fused BODIPY dimer compound containing hydrogen atoms, aryl substituents or amino substituents on the terminal aromatic heterocycle.

[0366] In summary, the fused BODIPY dimer material provided by the application containing halogen atoms on the terminal aromatic heterocycle has a wide and strong near-infrared absorption capacity. The maximum absorption wavelength of the compound provided by the application in a film state is all more than 880 nm, and the highest can reach 928 nm, and the molar absorption coefficient is all more than 2.5*10 5 M -1 cm -1 , and the maximum can reach 3.2*10 5 M -1 cm -1 cm. At the same time, the photo-thermal stability of the compound is good. By comparison, the molar absorption coefficient of the fused BODIPY dimer compound provided by the application containing halogen atoms on the terminal aromatic heterocycle is much higher than that of the compound of the same type. In view of the excellent performance of the compound provided by the application, it is expected to have a broad application prospect in the fields of dyes, fine chemicals, optoelectronic devices and life sciences.

[0367] Obviously, the above examples are only examples for clearly illustrating, but not limitation of the embodiments. For those skilled in the art, other different forms of changes or variations can be made on the basis of the above description. Here, it is not necessary and impossible to enumerate all the embodiments. The obvious changes or variations derived therefrom are still within the protection scope of the present application.

[0368] In addition to the above examples, for other substituent groups within the range defined above for X, Y, R1, R2, R3, G1 and G2 for which the application does not give specific examples, they can be synthesized by referring to the examples given by the application, which will not be exemplified one by one here.

Claims

1. A fused BODIPY dimer compound containing halogen atoms, wherein, The compound structure is shown as formula (I): wherein, X is selected from CH, C(CF3), , or N; R4 is a methyl group, an ethyl group, a n-propyl group, an i-propyl group, a n-butyl group, a t-butyl group, a sec-butyl group, an i-butyl group, a trifluoromethyl group, or a fluorine atom; m1 is 0, 1, 2, or 3; n1 is 0 or 1; x1, y1, z1 are each independently 0, 1, 2, or 3; Y is selected from O or S; R1and R2are each independently selected from F, cyano, ; R5is fluoro, chloro, bromo, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl or t-butyl; m2 is 0, 1, 2, or 3; R3is selected from H, or ; n2 and n3 are each independently 0 or 1; x2, y2, z2, x3, y3, z3 are each independently 0, 1, 2, 3, 4, or 5; G1 and G2 are each independently selected from F, Cl, Br, or I.

2. The halogen atom-containing fused-BODIPY dimer compound according to claim 1, wherein G1 and G2 are each independently selected from Cl or Br.

3. The halogen atom-containing fused-BODIPY dimer compound according to claim 1 or 2, wherein, The compound is selected from the following structures: 。 4. A method for producing the halogen atom-containing fused-BODIPY dimer compound according to any one of claims 1 to 3, wherein, The method comprises preparing the compound of formula (I) using the dimer of formula (II) as raw material: 。 5. The method of claim 4, wherein, The method comprises preparing the compound of formula (I) using the dimer of formula (II) as raw material: When R1 and R2 are not simultaneously F, the method comprises the steps of substituting one or two fluorine atoms on the boron atom by a nucleophilic substitution reaction, and modifying the halogen atom at the end of the dimer by a halogenation reaction; or when R1 and R2 are simultaneously F, the method comprises preparing the compound of formula (I) using the dimer of formula (II) as raw material, which comprises modifying the halogen atom at the end of the dimer by a halogenation reaction.

6. The method of claim 4 or 5, wherein, The method further comprises preparing the compound of formula (II) using the compound of formula (III) as raw material: (III).

7. The method of claim 6, wherein, The compound of formula (III) is prepared by monobromination and a Stille coupling reaction.

8. The method of claim 6, wherein, The method further comprises preparing the compound of formula (III) using the compound of formula (IV) as raw material: (IV).

9. The method of claim 8, wherein, The compound of formula (IV) is prepared by hydrolysis, condensation, and boronation, or by de-esterification, condensation, and boronation.

10. Use of the halogen atom-containing fused BODIPY dimer compound according to any one of claims 1-3 in the field of organic solar cells and photodetectors.

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