CN111689994A

CN111689994A - Organic conjugated molecular material with bifluorene Aza-BODIPY as basic skeleton and preparation method and application thereof

Info

Publication number: CN111689994A
Application number: CN202010507081.XA
Authority: CN
Inventors: 陈康康; 盛万乐; 郝二宏; 焦莉娟
Original assignee: Anhui Normal University
Current assignee: Anhui Normal University
Priority date: 2020-06-05
Filing date: 2020-06-05
Publication date: 2020-09-22
Anticipated expiration: 2040-06-05
Also published as: CN111689994B

Abstract

The invention discloses an organic conjugated molecular material taking bifluorene Aza-BODIPY as a basic skeleton and a preparation method and application thereof, wherein the structure of the organic conjugated molecular material is shown as a formula I, a formula II or a formula III, wherein R1, R2, R3 and R4 in the formula are respectively and independently selected from one of hydrocarbyl of H, C1-C14 and hydrocarbyloxy of C1-C14, and n1, n2, n3 and n4 are respectively and independently positive integers of 1-5; r5 is one of H and C1-C6 alkyl, and m is a positive integer of 1-4; r6 and R7 are respectively and independently one of H and C1-C10 hydrocarbon groups, X is halogen, and the organic conjugated molecular material has novel structure, excellent near infrared spectrum selectivity and high stability, and can be applied to biological formationLike organic electronic materials and the like, and simultaneously has the advantages of mild conditions and simple and convenient operation,

Description

Organic conjugated molecular material with bifluorene Aza-BODIPY as basic skeleton and preparation method and application thereof

Technical Field

The invention relates to an organic conjugated molecular material, in particular to an organic conjugated molecular material taking bifluorene Aza-BODIPY as a basic skeleton, and a preparation method and application thereof.

Background

Near-infrared optical materials have important applications in the fields of organic electronic materials (such as light emitting diodes and organic field effect transistors) and the like; for example, the development of near-infrared fluorescent dyes with high fluorescence quantum yield is a key to fluorescence imaging technology; in addition, the long-wave dye is widely applied to cell imaging due to the advantages of high penetration, small damage, high sensitivity and the like, can prolong the absorption emission wavelength of the dye and has higher single-phase oxygen efficiency.

However, the most commonly used near-infrared fluorescent probe at present has the defects of poor stability, unstable fluorescence performance or great synthesis difficulty and the like, and the application is greatly restricted.

Disclosure of Invention

The invention aims to provide an organic conjugated molecular material taking bifluorene Aza-BODIPY as a basic skeleton, and a preparation method and application thereof.

In order to realize the purpose, the invention provides an organic conjugated molecular material taking bifluorene Aza-BODIPY as a basic skeleton, the structure of the organic conjugated molecular material is shown as formula I, formula II or formula III,

wherein R1, R2, R3 and R4 in the formula are respectively and independently selected from H, C1-C14 alkyl and C1-C14 alkoxy, and n1, n2, n3 and n4 are respectively and independently positive integers of 1-5; r5 is one of H and C1-C6 alkyl, and m is a positive integer of 1-4; r6 and R7 are each independently one of H and C1-C10 hydrocarbyl, and X is halogen.

The invention also provides a preparation method of the organic conjugated molecular material with the structure shown in the formula I, which comprises the following steps:

1) under an alkaline condition, carrying out a first contact reaction on a compound with a structure shown as a formula 3, a fluorenyl boric acid compound and a palladium catalyst in a solvent to obtain a compound with a structure shown as a formula 9;

2) carrying out first oxidation reaction on a compound with a structure shown as a formula 9 and an oxidant in a solvent to prepare an organic conjugated molecular material with a structure shown as a formula I,

wherein R1, R2, R3 and R4 in the formula are respectively and independently selected from H, C1-C14 alkyl and C1-C14 alkoxy, n1, n2, n3 and n4 are respectively and independently positive integers of 1-5, and X is halogen; the structure of the fluorenyl boric acid compound is shown as a formula 13-1 or a formula 13-2.

The invention also provides a preparation method of the organic conjugated molecular material with the structure shown in the formula II, which comprises the following steps:

1) under an alkaline condition, carrying out a second contact reaction on a compound with a structure shown as a formula 5, a fluorenyl boric acid compound and a palladium catalyst in a solvent to obtain a compound with a structure shown as a formula 10;

2) carrying out a second oxidation reaction on a compound with a structure shown as a formula 10 and an oxidant in a solvent to prepare an organic conjugated molecular material with a structure shown as a formula II;

wherein R1, R2, R3 and R4 in the formula are respectively and independently selected from H, C1-C14 alkyl and C1-C14 alkoxy, and n1, n2, n3 and n4 are respectively and independently positive integers of 1-5; r5 is a hydrocarbon group of H, C1-C6, and m is a positive integer of 1-4; r6 and R7 are each independently one of H and C1-C10 hydrocarbyl, X is halogen; the structure of the fluorenyl boric acid compound is shown as a formula 13-1 or a formula 13-2.

The invention further provides a preparation method of the organic conjugated molecular material with the structure shown in the formula III, which comprises the following steps:

1) under an alkaline condition, carrying out a third contact reaction on a compound with a structure shown as a formula 2, a fluorenyl boric acid compound and a palladium catalyst in a solvent to obtain a compound with a structure shown as a formula 11;

2) carrying out a fourth contact reaction on a compound with a structure shown as a formula 11 and a halogen source in a solvent to prepare an organic conjugated molecular material with a structure shown as a formula 12;

3) carrying out a third oxidation reaction on a compound with a structure shown as a formula 12 and an oxidant in a solvent to prepare an organic conjugated molecular material with a structure shown as a formula II;

The invention further provides application of the organic conjugated molecular material taking bifluorene Aza-BODIPY as a basic skeleton in biological imaging and organic electronic materials.

The inventors found that the main causes of the decrease in fluorescence of the dye include the following: 1) the energy gap is narrowed, so that non-radiative transition of excited state electrons among energy levels is facilitated; 2) long-wave compounds are usually accompanied with a larger framework structure, and the framework vibration and the transformation of the excited state configuration cause great energy loss; 3) the larger molecular structure increases intermolecular force, so that the dye is easier to gather to quench fluorescence; 4) the narrowing of the energy gap allows for increased nonradiative decay of the excited state due to interaction between the multiple energy levels of the excited state.

In the technical scheme, the compound shown in the formulas I, II and III prepared in the invention has a larger conjugated system and larger molecular rigidity, so that the compound has longer near infrared absorption wavelength and fluorescence emission wavelength and higher fluorescence quantum yield, and can be applied to the fields of biological imaging, organic electronic materials and the like.

Additional features and advantages of the invention will be set forth in the detailed description which follows.

Drawings

The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:

FIG. 1 is a graph showing an absorption emission spectrum of II-1 in test example 1;

FIG. 2 is an absorption emission spectrum of II-2 in test example 2;

FIG. 3 is a graph showing III-1 absorption emission spectra in test example 3;

FIG. 4 is a graph showing III-2 absorption emission spectra in test example 4;

FIG. 5 is a graph showing the degradation of DPBF by III-1 and III-2 in test example 5.

Detailed Description

The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

The invention provides an organic conjugated molecular material with bifluorene Aza-BODIPY as a basic skeleton, the structure of the organic conjugated molecular material is shown as formula I, formula II or formula III,

In the above organic conjugated molecular material, the kind and number of each substituent may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the material, preferably, R1, R2, R3, R4 are each independently selected from one of an alkyl group of H, C1-C14 and an alkoxy group of C1-C14, R5 is one of a hydrocarbon group of C1-C6, R6 and R7 are each independently one of H and an alkyl group of C1-C10, and X is bromine or iodine; more preferably, R1, R2, R3 and R4 are respectively and independently selected from H and one of alkoxy of C1-C12, R5 is one of hydrocarbyl of C4-C6, R6 and R7 are respectively and independently one of alkyl of C8-C10, and X is bromine or iodine; further preferably, R1, R2, R3 and R4 are each independently selected from methoxy group or n-dodecyloxy group, R5 is tert-butyl group, R6 and R7 are both methyl group or n-octyl group, X is bromine or iodine, m, n1, n2, n3 and n4 are all 1, m, n1, n2, n3 and n4 are 1 to represent a mono-substitution, and when m, n1, n2, n3 and n4 are more than 1 to represent a multi-substitution.

Still more preferably, the structure of the organic conjugated molecular material is shown as formula I-1, formula I-2, formula II-1, formula II-2, formula III-1 or formula III-2,

wherein, C in the formula₈H₁₇Is n-octyl, C₁₂H₂₅O is n-dodecyloxy. Hereinafter C₈H₁₇Are all n-octyl, C₁₂H₂₅O is n-dodecyloxy.

In the above method for preparing the material having the structure represented by formula I, the kind and number of each substituent can be selected in a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the prepared material, preferably, R1, R2, R3 and R4 are each independently selected from one of alkyl groups of H, C1-C14 and alkoxy groups of C1-C14, and X is bromine or iodine; more preferably, R1, R2, R3 and R4 are respectively and independently selected from H and one of alkoxy of C1-C12, and X is bromine or iodine; further preferably, R1, R2, R3 and R4 are each independently selected from methoxy or n-dodecyloxy, X is bromine or iodine, and n1, n2, n3 and n4 are all 1.

In the above method for preparing the material having the structure shown in formula I, the amount of the raw material may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and the fluorescence quantum yield of the prepared material, it is preferable that in step 1), the compound having the structure shown in formula 3, the fluorenyl boronic acid compound and the palladium catalyst are used in a molar ratio of 1: 2-4: 0.05-0.1.

In the above method for preparing a material having a structure represented by formula I, the conditions of the first contact reaction can be selected within a wide range, but in order to further improve the near-infrared absorption wavelength and fluorescence quantum yield of the prepared material, it is preferable that the first contact reaction at least satisfies the following conditions: the reaction temperature is 90-120 ℃, and the reaction time is 24-36 h.

In the above method for preparing the material having the structure shown in formula I, the pH of the reaction system can be selected within a wide range, but in order to further improve the yield of the product, preferably, in step 1), the pH of the reaction system is controlled by carbonate, and the molar ratio of the compound having the structure shown in formula 3 to the carbonate is 1: 2-6; further preferably, the carbonate is at least one selected from the group consisting of sodium carbonate, potassium carbonate, and cesium carbonate.

In the above method for preparing the material having the structure shown in formula I, the amount and kind of the oxidizing agent can be selected within a wide range, but in order to further improve the near infrared absorption wavelength and the fluorescence quantum yield of the prepared material, it is preferable that in step 2), the compound having the structure shown in formula 9 and the oxidizing agent are used in a molar ratio of 1: 4-15; more preferably, in step 2), the oxidizing agent is selected from at least one of anhydrous ferric chloride, molybdenum pentachloride and dichlorodicyanobenzoquinone;

in the above method for preparing a material having a structure represented by formula I, the conditions of the first oxidation reaction can be selected within a wide range, but in order to further improve the near-infrared absorption wavelength and fluorescence quantum yield of the prepared material, it is preferable that in step 2), the first oxidation reaction at least satisfies the following conditions: the reaction temperature is 0-45 ℃ and the reaction time is 10-30 min.

In the above-mentioned method for preparing a material having a structure represented by formula I, the kind of the palladium catalyst may be selected within a wide range, but in order to further improve the near-infrared absorption wavelength and the fluorescence quantum yield of the obtained material, it is preferable that the palladium catalyst is selected from at least one of tetrakistriphenylphosphine palladium, palladium acetate, palladium chloride, bis (triphenylphosphine) palladium dichloride, and tris (dibenzylideneacetone) dipalladium.

In the above method for preparing a material having a structure represented by formula I, the kind of the fluorenyl boronic acid compound can be selected within a wide range, but in order to further improve the near infrared absorption wavelength and the fluorescence quantum yield of the prepared material, it is preferable that the fluorenyl boronic acid compound is 9, 9-dioctylfluorene-2, 7-bisboronic acid or 9, 9-dioctylfluorene-2, 7-bis (boronic acid pinacol ester).

In the above method for preparing the material having the structure shown in formula I, the kind of the compound having the structure shown in formula 3 can be selected within a wide range, but in order to further improve the near infrared absorption wavelength and the fluorescence quantum yield of the prepared material, preferably, the structure of the compound having the structure shown in formula 3 is shown in formula 3-1 or formula 3-2,

In the above method for preparing the material having the structure represented by formula II, the kind and number of each substituent may be selected within a wide range, but in order to further improve the near-infrared absorption wavelength and fluorescence quantum yield of the prepared material, preferably, R1, R2, R3 and R4 are each independently selected from one of an alkyl group of H, C1 to C14 and an alkoxy group of C1 to C14, R5 is a hydrocarbon group of C1 to C6, R6 and R7 are each independently one of H and an alkyl group of C1 to C10, and X is bromine or iodine; more preferably, R1, R2, R3 and R4 are respectively and independently selected from H and one of alkoxy of C1-C12, R5 is a hydrocarbon group of C4-C6, R6 and R7 are respectively and independently one of alkyl of C8-C10, and X is bromine or iodine; further preferably, R1, R2, R3 and R4 are each independently selected from methoxy or n-dodecyloxy, R5 is tert-butyl, R6 and R6 are both methyl or n-octyl, X is bromine or iodine, preferably, m, n1, n2, n3 and n4 are all 1, m, n1, n2, n3 and n4 are 1 to represent mono-substitution, and when m, n1, n2, n3 and n4 are greater than 1 to represent multi-substitution.

In the above method for preparing the material having the structure shown in formula II, the amount of the raw material may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and the fluorescence quantum yield of the prepared material, it is preferable that in step 1), the compound having the structure shown in formula 5, the fluorenyl boronic acid compound, and the palladium catalyst are used in a molar ratio of 1: 0.4-0.6: 0.05-0.1.

In the above method for preparing a material having a structure represented by formula II, the conditions of the second contact reaction can be selected within a wide range, but in order to further improve the near-infrared absorption wavelength and fluorescence quantum yield of the prepared material, it is preferable that the second contact reaction at least satisfies the following conditions: the reaction temperature is 90-120 ℃, and the reaction time is 24-36 h.

In the above method for preparing the material having the structure shown in formula II, the conditions of the second contact reaction can be selected within a wide range, but in order to further improve the near infrared absorption wavelength and the fluorescence quantum yield of the prepared material, preferably, in step 1), the pH of the reaction system is controlled by carbonate, and the molar ratio of the compound having the structure shown in formula 5 to the carbonate is 1: 2-6; further preferably, the carbonate is selected from at least one of sodium carbonate, potassium carbonate and cesium carbonate;

in the above method for preparing the material having the structure shown in formula II, the amount and kind of the oxidizing agent can be selected within a wide range, but in order to further improve the near infrared absorption wavelength and the fluorescence quantum yield of the prepared material, it is preferable that in step 2), the compound having the structure shown in formula 10 and the oxidizing agent are used in a molar ratio of 1: 4-15; preferably, in step 2), the oxidizing agent is selected from at least one of anhydrous ferric chloride, molybdenum pentachloride and dichlorodicyanobenzoquinone.

In the above method for preparing the material having the structure represented by formula II, the conditions of the second oxidation reaction can be selected within a wide range, but in order to further improve the near-infrared absorption wavelength and the fluorescence quantum yield of the prepared material, it is preferable that in step 2), the second oxidation reaction at least satisfies the following conditions: the reaction temperature is 0-45 ℃ and the reaction time is 10-30 min.

In the above-mentioned method for preparing a material having a structure represented by formula II, the kind of the palladium catalyst may be selected within a wide range, but in order to further improve the near-infrared absorption wavelength and the fluorescence quantum yield of the obtained material, it is preferable that the palladium catalyst is selected from at least one of tetrakistriphenylphosphine palladium, palladium acetate, palladium chloride, bis (triphenylphosphine) palladium dichloride, and tris (dibenzylideneacetone) dipalladium.

In the above method for preparing a material having a structure represented by formula II, the kind of the fluorenyl boronic acid compound can be selected within a wide range, but in order to further improve the near infrared absorption wavelength and the fluorescence quantum yield of the prepared material, it is preferable that the fluorenyl boronic acid compound is 9, 9-dioctylfluorene-2, 7-bisboronic acid or 9, 9-dioctylfluorene-2, 7-bis (boronic acid pinacol ester);

in the above method for preparing the material having the structure shown in formula II, the kind of the compound having the structure shown in formula 5 can be selected within a wide range, but in order to further improve the near infrared absorption wavelength and the fluorescence quantum yield of the prepared material, preferably, the structure of the compound having the structure shown in formula 5 is shown in formula 5-1 or formula 5-2,

wherein R1, R2, R3 and R4 in the formula are respectively and independently selected from H, C1-C14 alkyl and C1-C14 alkoxy, and n1, n2, n3 and n4 are respectively and independently positive integers of 1-5; r5 is a hydrocarbon group of H, C1-C6, and m is a positive integer of 1-4; r6 and R7 are respectively and independently one of H and C1-C10 alkyl, X is halogen, and the structure of the fluorenyl boric acid compound is shown as a formula 13-1 or a formula 13-2.

In the above method for preparing the material having the structure represented by formula III, the kind and number of each substituent may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the prepared material, preferably, R1, R2, R3 and R4 are each independently selected from one of an alkyl group of H, C1-C14 and an alkoxy group of C1-C14, R5 is a hydrocarbon group of C1-C6, R6 and R7 are each independently one of H and an alkyl group of C1-C10, and X is bromine or iodine; more preferably, R1, R2, R3 and R4 are respectively and independently selected from H and one of alkoxy of C1-C12, R5 is a hydrocarbon group of C4-C6, R6 and R7 are respectively and independently one of alkyl of C8-C10, and X is bromine or iodine; further preferably, R1, R2, R3 and R4 are each independently selected from methoxy or n-dodecyloxy, R5 is tert-butyl, R6 and R6 are both methyl or n-octyl, X is bromine or iodine, preferably, m, n1, n2, n3 and n4 are all 1, m, n1, n2, n3 and n4 are 1 to represent mono-substitution, and when m, n1, n2, n3 and n4 are greater than 1 to represent multi-substitution.

In the above method for preparing the material having the structure shown in formula III, the amount of the raw material may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and the fluorescence quantum yield of the prepared material, it is preferable that in step 1), the compound having the structure shown in formula 2, the fluorenyl boronic acid compound and the palladium catalyst are used in a molar ratio of 1: 0.4-0.6: 0.05-0.1.

In the above method for preparing a material having a structure represented by formula III, the conditions of the third contact reaction can be selected within a wide range, but in order to further improve the near-infrared absorption wavelength and the fluorescence quantum yield of the prepared material, it is preferable that in step 1), the third contact reaction at least satisfies the following conditions: the reaction temperature is 90-120 ℃, and the reaction time is 24-36 h.

In the above-mentioned method for preparing a material having a structure represented by formula III, the pH of the reaction system may be selected within a wide range, but in order to further improve the near-infrared absorption wavelength and fluorescence quantum yield of the obtained material, it is preferable that in step 1); more preferably, in step 1), the pH of the reaction system is controlled by carbonate, and the molar ratio of the compound having the structure shown in formula 2 to the carbonate is 1: 2-6; further preferably, the carbonate is at least one selected from the group consisting of sodium carbonate, potassium carbonate, and cesium carbonate.

In the above method for preparing the material having the structure shown in the formula III, the amount and kind of the halogen source can be selected within a wide range, but in order to further improve the near infrared absorption wavelength and the fluorescence quantum yield of the prepared material, it is preferable that in the step 2), the molar ratio of the compound having the structure shown in the formula 11 to the halogen source is 1: 1.8-2.4; preferably, the halogen source is selected from at least one of liquid bromine, N-bromosuccinimide and elemental iodine.

In the above method for preparing a material having a structure represented by formula III, the conditions of the fourth contact reaction can be selected within a wide range, but in order to further improve the near-infrared absorption wavelength and fluorescence quantum yield of the prepared material, it is preferable that in step 3), the fourth contact reaction at least satisfies the following conditions: the reaction temperature is 0-45 ℃ and the reaction time is 1-6 h.

In the above method for preparing the material having the structure shown in formula III, the amount and kind of the oxidizing agent can be selected within a wide range, but in order to further improve the near infrared absorption wavelength and the fluorescence quantum yield of the prepared material, it is preferable that in step 3), the compound having the structure shown in formula 12 and the oxidizing agent are used in a molar ratio of 1: 4-15; preferably, in step 3), the oxidizing agent is selected from at least one of anhydrous ferric chloride, molybdenum pentachloride and dichlorodicyanobenzoquinone.

In the above method for preparing a material having a structure represented by formula III, the conditions of the third oxidation reaction can be selected within a wide range, but in order to further improve the near infrared absorption wavelength and fluorescence quantum yield of the prepared material, it is preferable that in step 3), the third oxidation reaction at least satisfies the following conditions: the reaction temperature is 0-45 ℃ and the reaction time is 10-30 min.

In the above-mentioned method for preparing a material having a structure represented by formula III, the kind of the palladium catalyst may be selected within a wide range, but in order to further improve the near-infrared absorption wavelength and the fluorescence quantum yield of the obtained material, it is preferable that the palladium catalyst is selected from at least one of tetrakistriphenylphosphine palladium, palladium acetate, palladium chloride, bis (triphenylphosphine) palladium dichloride, and tris (dibenzylideneacetone) dipalladium.

In the above method for preparing a material having a structure represented by formula III, the kind of the fluorenyl boronic acid compound can be selected within a wide range, but in order to further improve the near infrared absorption wavelength and the fluorescence quantum yield of the prepared material, it is preferable that the fluorenyl boronic acid compound is 9, 9-dioctylfluorene-2, 7-bisboronic acid or 9, 9-dioctylfluorene-2, 7-bis (boronic acid pinacol ester);

in the above preparation method of the material having the structure shown in the formula III, the kind of the structure of the compound having the structure shown in the formula 2 can be selected within a wide range, preferably, the structure of the compound having the structure shown in the formula 2 is shown in the formula 2-1 or the formula 2-2,

in the above preparation methods of the materials with the structures shown in the formulas I, II and III, the raw materials used for the compound with the structure shown in the formula 2, the compound with the structure shown in the formula 3 and the compound with the structure shown in the formula 5 can be commercially available products or can be synthesized by self, and in order to improve the purity and reduce the cost, the invention also discloses a preparation method of the compound with the structure shown in the formula 2, the compound with the structure shown in the formula 3 and the compound with the structure shown in the formula 5, which specifically comprises the following steps:

1) carrying out a fifth contact reaction on the compound shown as the formula 1 and a halogen source in a solvent to obtain a compound shown as a formula 2;

2) carrying out a sixth contact reaction on the compound shown as the formula 1 and a halogen source in a solvent to obtain a compound shown as a formula 3;

3) under the alkaline condition, carrying out a seventh contact reaction on a compound shown as a formula 2, a phenylboronic acid compound shown as a formula 14 and a palladium catalyst in a solvent to obtain a compound shown as a formula 4;

4) carrying out an eighth contact reaction on the compound shown as the formula 4 and a halogen source in a solvent to obtain a compound shown as a formula 5;

wherein R1, R2, R3 and R4 in the formula are respectively and independently selected from H, C1-C14 alkyl and C1-C14 alkoxy, and n1, n2, n3 and n4 are respectively and independently positive integers of 1-5; r5 is a hydrocarbon group of H, C1-C6, and m is a positive integer of 1-4; preferably, each of the R1, R2, R3 and R4 is independently selected from one of an alkyl group of H, C1-C14 and an alkoxy group of C1-C14, and the R5 is a hydrocarbon group of C1-C6; more preferably, R1, R2, R3 and R4 are respectively and independently selected from H and one of alkoxy of C1-C12, and R5 is a hydrocarbon group of C4-C6; preferably, m, n1, n2, n3 and n4 are all 1.

Further preferably, the structure of the compound shown in the formula 1 is shown in a formula 1-1 or a formula 1-2,

in the fifth contact reaction, the amount of each raw material may be selected within a wide range, but in order to improve the yield, it is preferable that the compound represented by formula 1 is used in a molar ratio of 1: 0.9-1.2.

In the sixth contact reaction, the amount of each raw material may be selected within a wide range, but in order to improve the yield, it is preferable that the molar ratio of the compound represented by formula 1 to the halogen source is 1: 1.8-2.4.

In the seventh contact reaction, the amount of each raw material may be selected within a wide range, but in order to improve the yield, it is preferable that the compound represented by formula 2 is used in a molar ratio of 1: 1-4: 0.05-0.1.

In the eighth contact reaction, the amount of each raw material may be selected within a wide range, but in order to improve the yield, it is preferable that the molar ratio of the compound represented by formula 4 to the halogen source is 1: 0.9-1.2.

In the seventh contact reaction, the reaction temperature may be selected within a wide range, but in order to improve the yield, it is preferable that the reaction temperature of the third contact reaction is 90 to 120 ℃.

In the fifth contact reaction, the sixth contact reaction and the seventh contact reaction, the reaction temperature may be selected within a wide range, but in order to improve the yield, it is preferable that the reaction temperature of each of the first contact reaction, the second contact reaction and the fourth contact reaction is independently 0 to 45 ℃.

In the fifth contact reaction, the sixth contact reaction and the eighth contact reaction, the contact reaction time of each step may be selected from a wide range, but in order to achieve sufficient reaction and improve the yield, it is preferable that the fifth contact reaction time is 0.5 to 1 hour, the sixth contact reaction time is 0.5 to 2 hours, the seventh contact reaction time is 12 to 36 hours and the eighth contact reaction time is 0.5 to 1 hour.

In the seventh contact reaction, the pH of the reaction system may be selected within a wide range, but in order to further improve the near infrared absorption wavelength and the fluorescence quantum yield of the obtained material, preferably, in step 1), the pH of the reaction system is controlled by carbonate, and the molar ratio of the compound having the structure shown in formula 2 to the carbonate is 1: 2-6; further preferably, the carbonate is at least one selected from the group consisting of sodium carbonate, potassium carbonate, and cesium carbonate.

In the fifth contact reaction, the sixth contact reaction and the eighth contact reaction, the kind of the halogen source may be selected from a wide range, but in order to further improve the near-infrared absorption wavelength and the fluorescence quantum yield of the obtained material, it is preferable that the halogen source is selected from at least one of liquid bromine, N-bromosuccinimide and iodine.

In the above method for preparing a material having a structure represented by formula III, the conditions of the eighth contact reaction can be selected within a wide range, but in order to further improve the near-infrared absorption wavelength and the fluorescence quantum yield of the prepared material, it is preferable that, in step 3), the eighth contact reaction at least satisfies the following conditions: the reaction temperature is 0-45 ℃ and the reaction time is 1-6 h.

In the seventh contact reaction described above, the kind of the palladium catalyst may be selected from a wide range, but in order to further improve the near infrared absorption wavelength and the fluorescence quantum yield of the obtained material, it is preferable that the palladium catalyst is selected from at least one of tetrakistriphenylphosphine palladium, palladium acetate, palladium chloride, bis (triphenylphosphine) palladium dichloride, and tris (dibenzylideneacetone) dipalladium.

In the seventh contact reaction, the kind of the phenylboronic acid-based compound may be selected from a wide range, but in order to further improve the near infrared absorption wavelength and the fluorescence quantum yield of the produced material, it is preferable that the phenylboronic acid-based compound is at least one selected from the group consisting of 4-tert-butylbenzene boronic acid, 3, 5-dimethoxy phenylboronic acid, and 3,4, 5-trimethoxy phenylboronic acid.

In each of the production processes of the present invention, the kind of the solvent may be selected from a wide range, and may be a halogenated hydrocarbon solvent such as one or more of dichloromethane, trichloromethane, trichloroethylene and 1, 2-dichloroethane; and may also be an aromatic hydrocarbon solvent such as one or more of toluene, xylene, chlorobenzene, and o-dichlorobenzene. The amount of the solvent to be used is not particularly limited as long as the reaction raw materials can be sufficiently dispersed.

The present invention will be described in detail below by way of examples. In the following examples, the compounds represented by the formula 1-1 and the compounds represented by the formula 3-1 are described in the literature "Sheng, w.; zheng, y.; wu, q.; wu, y.; yu, c.; hao, e.; jiao, l.; wang, j.; pei, j.; synthesized, Properties, and semiconductor diagnostics of BF2Complexes of β, β -Bisphenanthrene-Fused Azadipyrromethenes, org. Lett.2017,19, 2893-.

Chemical reagents (liquid bromine, N-bromosuccinimide, iodine, iodic acid, glacial acetic acid, tetratriphenylphosphine palladium, 9, 9-dioctylfluorene-2, 7-bis (boronic acid pinacol ester), 9, 9-dioctylfluorene-2, 7-bisboronic acid, sodium carbonate, sodium chloride, anhydrous ferric chloride, dichloromethane, trichloromethane, tetrahydrofuran, toluene, N-hexane) are analytically pure reagents and are generally used without further treatment unless otherwise specified.

The reaction was followed using a 0.25 mm thick fluorescent TLC plate and a model ZF-1 three-way UV analyzer. 1H NMR and 13C NMR A Bruker AVANCE III Spectrometers 300MHz, 400MHz or 500MHz NMR spectrometer was used with CDCl3 as solvent. Mass spectrometry was performed using a Bruker Apex IV Fourier Transform Ion cyclone Resonance Mass Spectrometer. The instrument used for absorption spectroscopy was a UV-2450 type UV spectrophotometer, the instrument used for fluorescence spectroscopy was Edinburgh instruments FLS 1000, and the reference compounds used for fluorescence quantum yield were 1, 7-diphenyl-3, 5-di-p-methoxyphenyl azaBODIPY (chloroform, Φ ═ 0.36) and indocyanine green (ICG) (dimethylsulfoxide, Φ ═ 0.12).

Preparation example 1

Preparation of a compound represented by formula 1-2:

the compound shown as the formula S1 adopts the literature "Other sourceby Ahipa, T.N.; adhikari, AirodyVasudeva.Synthesis and mesomorphism of new 2-method-3-cyanopyridinemogenins.proceedings of SPIE, 20128279,827915, page 827915-2, paragraph IV.

Placing the compound shown as the formula S1, nitromethane and diethylamine in ethanol, and reacting at 65 ℃ for 12h to obtain a compound shown as the formula S2; the dosage ratio of the compound shown as the formula S1 to the nitromethane, the diethylamine and the ethanol is 1 mmol: 8 mmol: 8 mmol: 10 mL;

characterization data for the compound of formula S2 is:¹H NMR(300MHz,CDCl₃)7.88(d,J＝8.7Hz,2H),7.17(d,J＝8.4Hz,2H),6.90(d,J＝8.7Hz,2H),6.83(d,J＝8.5Hz,2H),4.82-4.76(m,1H),4.66-4.59(m,1H),4.20-4.09(m,1H),4.00(t,J＝6.5Hz,2H),3.90(t,J＝6.5Hz,2H),3.36-3.32(m,2H),1.84-1.70(m,4H),1.45-1.21(m,36H),0.92-0.80(m,6H).¹³C NMR(75MHz,CDCl₃)195.46,163.44,158.63,130.91,130.33,129.26,128.44,114.91,114.29,79.93,68.32,67.98,41.27,38.80,31.92,29.64,29.36,26.05,25.96,22.70,14.13.HRMS(APCI)Calcd.for C₄₀H₆₄NO₅[M+H]⁺:638.4780,found 638.4760.

putting the compound shown as the formula S2 and ammonium acetate into ethanol, and reacting for 24h at 65 ℃, wherein the use ratio of the compound shown as the formula S2, ammonium acetate, triethylamine, boron trifluoride diethyl etherate and ethanol is 1 mmol: 15 mmol: 25mmol of: 25mmol of: 10 mL; purifying to obtain a compound shown as a formula 1-2;

the characterization data for the compounds of formulas 1-2 are:¹H NMR(300MHz,CDCl₃)8.04(d,J＝8.9Hz,8H),6.97(d,J＝9.0Hz,8H),6.92(s,2H),4.06-4.00(m,8H),1.86-1.78(m,8H),1.44–1.26(m,72H),0.88(t,J＝6.6Hz,12H).¹³C NMR(75MHz,CDCl₃)161.34,160.28,157.71,145.14,142.64,131.47,130.71,128.29,125.3,124.17,116.97,114.61,68.16,31.94,30.33,29.65,29.47,29.38,29.31,29.22,26.09,22.71,14.13.MS(MALDI)Calcd.forC₈₀H₁₁₈BF₂N₃O₄[M]⁺:1233.9191,found 1233.9194.

example 1

a. Mixing a compound shown as a formula 1-1 with N-bromosuccinimide according to the proportion of 1: mixing the mixture in dichloromethane at a molar ratio of 0.9, and carrying out contact reaction at 0 ℃ for 1h to obtain a compound shown as a formula 2-1;

b. reacting a compound represented by the formula 1-1 with liquid bromine according to the following ratio of 1:1.8, mixing the mixture in dichloromethane, and carrying out contact reaction for 2h at 0 ℃ to obtain a compound shown as a formula 3-1;

c. mixing the compound shown as the formula 2-1 with p-tert-butylboronic acid, palladium tetratriphenylphosphine and sodium carbonate in toluene, and carrying out contact reaction for 36h at 90 ℃ to obtain a compound shown as the formula 4-1; wherein the molar ratio of the compound shown as the formula 2-1 to the p-tert-butylboronic acid, the tetratriphenylphosphine palladium and the sodium carbonate is 1: 1: 0.05: 2;

d. mixing a compound shown as a formula 4-1 with N-bromosuccinimide according to the proportion of 1: mixing the mixture in dichloromethane with a molar ratio of 0.9, and carrying out contact reaction for 1h at 25 ℃ to obtain a compound shown as a formula 5-1;

e. dispersing a compound shown as a formula 3-1, 9-dioctyl fluorene-2, 7-bis (boric acid pinacol ester), palladium tetratriphenylphosphine and sodium carbonate in toluene, and carrying out contact reaction for 36h at 90 ℃ to obtain a compound shown as a formula 9-1; wherein the molar ratio of the compound shown as the formula 3-1 to 9, 9-dioctylfluorene-2, 7-bis (boronic acid pinacol ester), tetratriphenylphosphine palladium and sodium carbonate is 1: 2: 0.05: 2;

f. mixing a compound shown as a formula 9-1 with anhydrous ferric trichloride according to the proportion of 1: 10 in a molar ratio, and carrying out an oxidation reaction for 15min at 25 ℃ to obtain a compound shown as a formula I-1;

g. dispersing a compound shown as a formula 5-1, 9-dioctyl fluorene-2, 7-bis (boric acid pinacol ester), palladium tetratriphenylphosphine and sodium carbonate in toluene, and carrying out contact reaction for 36h at 90 ℃ to obtain a compound shown as a formula 10-1; wherein the molar ratio of the compound shown as the formula 5-1 to 9, 9-dioctylfluorene-2, 7-bis (boronic acid pinacol ester), tetratriphenylphosphine palladium and sodium carbonate is 1: 0.5: 0.05: 2;

h. mixing a compound shown as a formula 10-1 with anhydrous ferric trichloride according to the proportion of 1: 20, mixing the mixture in dichloromethane, and carrying out oxidation reaction for 15min at 25 ℃ to obtain a compound shown as a formula II-1;

i. mixing a compound shown as a formula 2-1, 9-dioctyl fluorene-2, 7-bis (boric acid pinacol ester), palladium tetratriphenylphosphine and sodium carbonate in toluene, and carrying out contact reaction for 36 hours at 90 ℃ to obtain a compound shown as a formula 10-1; wherein the molar ratio of the compound shown as a formula 11-1 to 9, 9-dioctylfluorene-2, 7-bis (boronic acid pinacol ester), tetratriphenylphosphine palladium and sodium carbonate is 1: 0.5: 0.05: 2;

j. reacting a compound represented by the formula 11-1 with liquid bromine according to the ratio of 1:1.8, mixing the mixture in dichloromethane, and carrying out contact reaction for 2h at the temperature of 0 ℃ to obtain a compound shown as a formula 12-1;

k. mixing a compound shown as a formula 11-1, iodic acid and iodine according to a ratio of 1: 4: 4 in the presence of dichloromethane and glacial acetic acid, and carrying out contact reaction for 2h at 45 ℃ to obtain a compound shown as a formula 12-2;

l, mixing the compound shown as the formula 12-1 with anhydrous ferric trichloride according to the proportion of 1: 10 in the molar ratio of trichloroethylene, and carrying out oxidation reaction for 15min at 25 ℃ to obtain a compound shown as a formula III-1;

m, mixing the compound shown as the formula 12-2 with ferric trichloride according to the proportion of 1: 10 in the molar ratio of 10 in dichloromethane, and carrying out oxidation reaction for 15min at 25 ℃ to obtain the compound shown in the formula III-2.

In each of the above steps, the amount of the solvent used in each step was 10mL with respect to 1mmol of the compound represented by formula 1-1, formula 2-1, formula 3-1, formula 4-1, formula 5-1, formula 9-1, formula 10-1, formula 11-1, and formula 12-1. The product characterization data for each step above is as follows:

a compound represented by the formula 2-1:¹H NMR(300MHz,CDCl₃)8.10-8.02(m,4H),7.91(d,J＝8.9,2H),7.76(d,J＝7.1Hz,2H),7.08-6.89(m,9H),3.92(d,J＝1.8Hz,3H),3.90-3.80(m,9H).¹³C NMR(101MHz,CDCl₃)162.61,161.23,160.87,160.32,152.72,146.83,145.08,142.26,139.03,132.31,132.04,130.91,12.60,124.25,122.77,117.88,114.36,114.20,113.49,113.38,55.48,55.45,55.40,55.25.HRMS(APCI)Calcd.for C₃₆H₃₀BBrF₂N₃O₄[M+H]⁺:696.1481,found 696.1468.

a compound represented by the formula 4-1:¹H NMR(400MHz,CDCl₃)8.09(d,J＝9.0Hz,2H),8.03(d,J＝9.0Hz,2H),7.46-7.43(m,4H),7.19(d,J＝8.4Hz,2H),6.98-6.89(m,7H),6.85-6.73(m,4H),3.87-3.81(m,12H),1.28(s,9H).¹³C NMR(126MHz,CDCl₃)161.90,160.80,160.46,159.72,158.92,156.70,149.96,145.97,144.45,143.22,139.59,132.56,132.41,131.59,130.73,130.22,125.11,116.95,114.18,114.10,113.25,113.13,55.40,55.26,55.15,34.53,31.32.HRMS(APCI)calcd.for C₄₆H₄₃BF₂N₃O₄[M+H]⁺:750.3315,found 750.3311.

a compound represented by the formula 5-1:¹H NMR(300MHz,CDCl₃)7.93(d,J＝8.70Hz,2H),7.74(d,J＝8.70Hz,2H),7.42(d,J＝8.31Hz,4H),7.43(m,4H),7.21(d,J＝8.19Hz,2H),7.03-6.98(m,4H),6.89(d,J＝8.13Hz,2H),6.78-6.74(m,4H),3.89(s,3H),3.86(s,3H),3.81(s,3H),3.79(s,3H),1.29(s,9H).¹³C NMR(75MHz,CDCl₃)161.37,161.17,161.03,160.41,160.13,150.52,146.19,143.04,141.88,139.93,132.54,132.30,130.12,129.91,125.31,124.17,124.08,113.49,113.42,113.35,107.36,55.35,55.23,55.18,34.57,31.28.HRMS(APCI)calcd.for C₄₆H₄₁BBrF₂N₃O₄[M+H]⁺:828.2414,found 828.2388.

a compound represented by the formula 9-1:¹H NMR(400MHz,CDCl₃)7.88-7.66(m,2H),7.54(t,J＝8.1Hz,6H),7.44(d,J＝8.8Hz,4H),7.40-7.38(m,2H),7.32-7.26(m,4H),7.00-6.95(m,2H),6.95(s,2H),6.80-6.73(m,8H),3.80(s,6H),3.73(s,6H),1.25(s,12H).¹³C NMR(101MHz,CDCl₃)160.57,159.71,157.99,153.66,153.32,145.14,139.59,138.72,137.76,132.39,132.29,129.24,126.82,125.17,122.45,119.78,119.66,113.10,55.08,54.98,46.36,26.61.HRMS(APCI)calcd.For C₆₆H₅₅BF₂N₃O₄[M+H]⁺:1002.4248,found 1002.4267.

a compound represented by the formula I-1:¹H NMR(400MHz,CDCl₃)9.48(d,J＝9.4Hz,1H),8.63(s,1H),8.15(s,1H),8.05(d,J＝2.6Hz,1H),7.89(d,J＝6.8Hz,1H),7.59(d,J＝8.7Hz,2H),7.45–7.41(m,1H),7.39–7.34(m,3H),7.02–6.98(m,2H),4.14(s,3H),3.96(s,3H),1.29(s,6H).HRMS(APCI)calcd.For C₆₆H₅₁BF₂N₃O₄[M+H]⁺:998.3935,found 998.3958.

a compound represented by the formula 10-1:¹H NMR(300MHz,CDCl₃)7.50-7.40(m,9H),7.20(d,J＝8.3Hz,2H),6.97-6.89(m,4H),6.81-6.70(m,8H),3.82(s,3H),3.78(d,J＝4.3Hz,6H),3.75(s,3H),1.55(s,5H),1.29(s,9H),1.16(s,6H),0.83(t,J＝6.8Hz,4H),0.42(s,2H).¹³C NMR(75MHz,CDCl₃)171.70,161.43,160.60,158.46,151.84,150.93,145.89,140.57,133.34,133.24,131.18,131.02,130.23,125.99,125.55,124.08,120.63,114.02,113.96,56.03,55.93,55.81,41.05,32.69,32.11,30.89,30.42,30.25,24.70,23.47,14.90.MS(MALDI)Calcd.for C121H122B2F4N6O8[M]⁺:1885.9493,found 1885.9491.

a compound represented by the formula II-1:¹H NMR(400MHz,CDCl₃)9.42(s,4H),8.77(s,2H),8.32(s,2H),8.06(s,6H),7.96(s,2H),7.60(s,8H),7.35(s,6H),6.99(s,8H),4.07(s,12H),3.95(s,12H),1.14-1.06(m,28H),0.61-0.53(m,6H).MS(MALDI)Calcd.for C121H114B2F4N6O8[M]⁺:1877.8867,found 1877.8868.

a compound represented by the formula 11-1:¹H NMR(500MHz,CDCl₃)8.11(d,J＝7.7Hz,4H),8.05(d,J＝7.9Hz,4H),7.47(d,J＝7.9Hz,10H),6.97-6.92(m,14H),6.80-6.75(m,8H),3.87(d,J＝8.5Hz,12H),3.79(d,J＝14.9Hz,12H),1.59(s,4H),1.22-1.15(m,12H),1.00(s,4H),0.90(d,J＝6.9Hz,4H),0.83(t,J＝6.8Hz,6H),0.42(s,4H).¹³C NMR(126MHz,CDCl₃)161.98,160.86,159.77,159.14,156.42,154.23,150.99,149.12,146.10,144.36,143.37,139.72,132.69,132.48,131.65,130.77,129.42,125.24,124.90,124.08,123.44,119.74,117.08,114.22,114.14,113.28,113.16,55.54,55.41,55.17,55.04,54.83,40.25,31.91,30.11,29.63,29.46,23.90,22.69,14.12.HRMS(APCI)Calcd.for C₁₀₁H₉₉B₂F₄N₆O₈[M+H]⁺:1622.7675,found 1622.7689.

a compound represented by formula 12-1:¹H NMR(300MHz,CDCl₃)7.93(d,J＝8.6Hz,4H),7.76(d,J＝8.0Hz,4H),7.50-7.43(m,10H),7.01(t,J＝7.9Hz,8H),6.92(d,J＝6.5Hz,4H),6.71(d,J＝8.5Hz,8H),3.88(d,J＝10.4Hz,12H),3.76(d,J＝6.8Hz,12H),1.57(s,4H),1.13(s,12H),0.95(s,8H),0.82(t,J＝6.6Hz,6H),0.38(s,4H).¹³C NMR(126MHz,CDCl₃)161.20,161.13,160.92,160.49,160.19,154.50,151.19,145.96,143.35,141.70,140.17,139.99,132.48,132.35,129.36,125.02,124.11,122.60,120.03,113.54,113.46,113.38,107.59,55.39,55.26,55.15,55.08,54.92,40.20,31.88,30.06,29.60,29.43,23.90,22.66,14.09.HRMS(APCI)Calcd.for C₁₀₁H₉₇B₂Br₂F₄N₆O₈[M+H]⁺:1779.5831,found 1779.5847.

a compound represented by formula 12-2:¹H NMR(300MHz,CDCl₃)7.86(d,J＝8.5Hz,4H),7.68(d,J＝8.4Hz,4H),7.49-7.40(m,10H),7.00(t,J＝9.4Hz,8H),6.91(d,J＝6.2Hz,4H),6.69(d,J＝8.5Hz,8H),3.88(d,J＝10.5Hz,12H),3.75(d,J＝6.2Hz,12H),1.56(s,4H),1.13(s,12H),0.95(s,8H),0.81(d,J＝7.1Hz,6H),0.38(s,4H).¹³C NMR(101MHz,CDCl₃)161.18,160.97,160.44,160.14,157.34,151.16,145.94,144.08,141.80,139.96,132.45,132.35,125.14,124.96,124.05,124.03,122.54,122.02,113.37,113.32,113.28,55.37,55.23,55.13,55.07,54.89,4018,31.86,30.03,29.59,29.43,2.88,22.66,14.10.HRMS(APCI)Calcd.forC₁₀₁H₉₇B₂F₄I₂N₆O₈[M+H]⁺:1874.5608,found 1874.5618.

a compound represented by the formula III-1:¹H NMR(300MHz,CDCl₃)9.09(d,J＝9.4Hz,2H),8.73(s,2H),8.11(s,2H),8.00-7.80(m,10H),7.59(d,J＝8.0Hz,4H),7.20(d,J＝8.3Hz,2H),7.11(d,J＝8.2Hz,4H),7.02(d,J＝8.0Hz,4H),6.95(d,J＝8.4Hz,4H),4.11(s,6H),3.95(s,12H),3.89(s,6H),1.57(s,4H),1.11(s,12H),0.99(s,8H),0.77(s,6H),0.52(s,4H).HRMS(APCI)Calcd.for C₁₀₁H₉₃B₂Br₂F₄N₆O₈[M+H]⁺:1775.5518,found 1775.5540.

a compound represented by the formula III-2:¹H NMR(300MHz,CDCl₃)9.07(d,J＝9.1Hz,2H),8.71(s,2H),8.11(s,2H),7.98(s,2H),7.86(d,J＝8.7Hz,4H),7.79(d,J＝8.4Hz,4H),7.58(d,J＝8.5Hz,4H),7.20(d,J＝9.4Hz,2H),7.10(d,J＝8.7Hz,4H),7.12-6.95(m,8H),4.11(s,6H),3.96(t,J＝7.4Hz,12H),3.90(s,6H),1.56-1.51(m,4H),1.11(s,12H),0.99(s,8H),0.77(t,J＝6.8Hz,6H),0.52(s,4H).HRMS(APCI)Calcd.for C₁₀₁H₉₃B₂F₄I₂N₆O₈[M+H]⁺:1869.5261,found 1869.5280.

example 2

a. The compound shown as the formula 1-2 and N-bromosuccinimide are mixed according to the proportion of 1: mixing the mixture in dichloromethane at a molar ratio of 0.9, and carrying out contact reaction at 0 ℃ for 1h to obtain a compound shown as a formula 2-2;

b. reacting a compound represented by the formula 1-2 with liquid bromine according to the following ratio of 1:1.8, mixing the mixture in dichloromethane, and carrying out contact reaction for 2 hours at the temperature of 0 ℃ to obtain a compound shown as a formula 3-2;

c. mixing the compound shown as the formula 2-2 with p-tert-butylboronic acid, palladium tetratriphenylphosphine and sodium carbonate in toluene, and carrying out contact reaction for 36h at 90 ℃ to obtain a compound shown as the formula 4-2; wherein the mol ratio of the compound shown as the formula 2-2 to the p-tert-butylboronic acid, the tetratriphenylphosphine palladium and the carbonate is 1: 1: 0.05: 2;

d. mixing a compound shown as a formula 4-2 with N-bromosuccinimide according to the proportion of 1: 0.9 molar ratio in dichloromethane, and carrying out contact reaction for 1h at 25 ℃ to obtain a compound shown as a formula 5-2);

e. mixing a compound shown as a formula 3-2, 9-dioctyl fluorene-2, 7-bis (boric acid pinacol ester), palladium tetratriphenylphosphine and sodium carbonate in toluene, and carrying out contact reaction for 36 hours at 90 ℃ to obtain a compound shown as a formula 9-2; wherein the molar ratio of the compound shown as the formula 3-2 to 9, 9-dioctylfluorene-2, 7-bis (boronic acid pinacol ester), tetratriphenylphosphine palladium and carbonate is 1: 2: 0.05: 2;

f. reacting a compound shown as a formula 9-2 with anhydrous ferric trichloride according to a ratio of 1: 10 in a molar ratio, and carrying out an oxidation reaction for 15min at 25 ℃ to obtain a compound shown as a formula I-2;

g. carrying out contact reaction on a compound shown as a formula 5-2, 9-dioctyl fluorene-2, 7-bis (boric acid pinacol ester), palladium tetratriphenylphosphine and sodium carbonate in toluene at 90 ℃ for 36h to obtain a compound shown as a formula 10-2; wherein the molar ratio of the compound shown as the formula 5-2 to 9, 9-dioctylfluorene-2, 7-bis (boronic acid pinacol ester), tetratriphenylphosphine palladium and sodium carbonate is 1: 0.5: 0.05: 2;

h. reacting a compound shown as a formula 10-2 with anhydrous ferric trichloride according to a ratio of 1: 20 in a molar ratio, and carrying out an oxidation reaction for 15min at 25 ℃ to obtain a compound shown as a formula II-2;

in each of the above steps, the amount of the solvent used in each step was 10mL relative to 1mmol of the compound represented by formula 1-2, formula 2-2, formula 3-2, formula 4-2, formula 5-2, formula 9-2, or formula 10-2. The product characterization data for each step above is as follows:

a compound represented by formula 1-2:¹H NMR(300MHz,CDCl₃)8.04(d,J＝8.9Hz,8H),6.97(d,J＝9.0Hz,8H),6.92(s,2H),4.06-4.00(m,8H),1.86-1.78(m,8H),1.44–1.26(m,72H),0.88(t,J＝6.6Hz,12H).¹³C NMR(75MHz,CDCl₃)161.34,160.28,157.71,145.14,142.64,131.47,130.71,128.29,125.3,124.17,116.97,114.61,68.16,31.94,30.33,29.65,29.47,29.38,29.31,29.22,26.09,22.71,14.13.MS(MALDI)Calcd.for C₈₀H₁₁₈BF₂N₃O₄[M]⁺:1233.9191,found 1233.9194.

a compound represented by the formula 2-2: 8.04(t, J ═ 8.0Hz,4H),7.89(d, J ═ 8.8Hz,2H),7.74(d, J ═ 8.7Hz,2H),7.05-6.89(m,9H),4.11-3.98(m,8H),1.88-1.76(m,8H),1.47-1.26(m,72H),0.88(t, J ═ 6.6Hz,12H).¹³C NMR(101MHz,CDCl₃)162.28,160.85,160.54,159.91,152.69,146.87,145.08,144.30,139.11,132.28,132.05,130.88,124.43,123.14,114.80,114.71,114.02,113.78,68.24,68.16,67.94,31.94,29.69,29.66,29.61,29.43,29.37,29.29,29.23,29.11,26.11,26.05,25.99,22.71,14.14.MS(MALDI)Calcd.for C₈₀H₁₁₇BBrF₂N₃O₄[M]⁺:1313.8271,found 1313.8270.

A compound represented by the formula 3-2:¹H NMR(300MHz,CDCl₃)7.88(d,J＝8.7Hz,4H),7.73(d,J＝8.7Hz,4H),6.98-6.94(m,8H),4.05-3.97(m,8H),1.87-1.74(m,8H),1.46-1.27(m,72H),0.87(d,J＝6.8Hz,12H).¹³C NMR(75MHz,CDCl₃)161.24,160.43,157.13,144.02,141.95,132.45,123.36,121.79,114.10,113.94,108.55,68.15,68.03,32.01,29.74,29.52,29.46,29.30,26.15,22.77,14.20.MS(MALDI)Calcd.for C₈₀H₁₁₆BBr₂F₂N₃O₄[M]⁺:1391.7373,found 1391.7390.

a compound represented by the formula 4-2:¹H NMR(400MHz,CDCl₃)8.09(d,J＝8.9Hz,2H),8.02(d,J＝8.9Hz,2H),7.45-7.41(m,4H),7.18(d,J＝8.4Hz,2H),6.97-6.89(m,7H),6.85-6.79(m,2H),6.76(d,J＝8.9Hz,2H),4.05-3.93(m,8H),1.85-1.75(m,8H),1.46-1.27(m,81H),0.88(t,J＝6.2Hz,12H).¹³C NMR(101MHz,CDCl₃)161.35,160.37,160.09,159.29,158.86,156.60,149.83,145.95,144.42,143.16,139.56,132.53,132.41,131.56,130.69,130.25,125.08,116.81,114.62,113.72,113.56,68.14,68.00,67.89,34.52,31.94,31.33,29.65,29.62,29.48,29.45,29.37,29.28,29.17,26.12,26.08,26.03,22.70,14.13.MS(MALDI)Calcd.for C₉₀H₁₃₀BF₂N₃O₄[M]⁺:1366.0131,found 1366.0135.

a compound represented by the formula 5-2:¹H NMR(400MHz,CDCl₃)7.90(d,J＝8.9Hz,2H),7.72(d,J＝8.8Hz,2H),7.42-7.37(m,4H),7.20(d,J＝8.5Hz,2H),7.00-6.95(m,4H),6.88(d,J＝8.4Hz,2H),6.73(t,J＝8.5Hz,4H),4.05-3.98(m,4H),3.95-3.89(m,4H),1.85-1.71(m,8H),1.46(d,J＝5.6Hz,8H),1.27(d,J＝4.7Hz,73H),0.88(t,J＝6.8Hz,12H).¹³C NMR(101MHz,CDCl₃)161.28,160.82,160.68,159.99,159.70,150.70,146.17,142.99,141.88,139.88,132.53,132.28,130.15,130.04,125.30,123.98,123.88,122.36,114.00,113.82,113.67,68.13,67.96,34.57,31.94,31.30,29.66,29.64,29.57,29.46,29.41,29.37,29.28,29.20,26.09,26.04,22.70,14.13.MS(MALDI)Calcd.for C₉₀H₁₂₉BBrF₂N₃O₄[M]⁺:1445.9211,found 1445.9209.

a compound represented by formula 9-2:¹H NMR(400MHz,CDCl₃)7.72(d,J＝6.8Hz,1H),7.66(t,J＝6.7Hz,2H),7.55-7.37(m,12H),7.35–7.28(m,4H),7.18(dd,J＝7.8,1.3Hz,1H),6.99(d,J＝7.8Hz,1H),6.95(s,1H),6.84–6.67(m,8H),3.96–3.85(m,8H),1.81–1.68(m,8H),1.26(s,72H),0.88(t,J＝6.2Hz,12H).¹³C NMR(101MHz,CDCl₃)160.40,160.08,159.46,158.33,158.15,153.90,153.86,153.73,153.45,149.24,145.25,132.55,132.46,132.34,130.28,129.46,127.22,126.98,122.65,122.60,119.95,114.36,113.84,113.71,113.49,68.13,68.03,67.91,67.85,58.49,46.73,46.53,31.93,29.70,29.66,29.64,29.61,29.58,29.46,29.43,29.37,,26.93,26.81,26.09,26.07,26.00,22.70,18.45,14.13.HRMS(APCI)calcd.For C₁₁₀H₁₄₃BF₂N₃O₄[M+H]⁺:1619.1134,found 1619.1146.

a compound of formula I-2:¹H NMR(400MHz,CDCl₃)9.39(d,J＝9.5Hz,2H),8.48(s,2H),8.02(s,2H),7.87(s,2H),7.80-7.78(m,2H),7.35-7.33(m,6H),7.25-7.17(m,6H),6.84(d,J＝8.4Hz,4H),4.24(t,J＝6.3Hz,4H),3.99(t,J＝6.5Hz,4H),1.97-1.88(m,4H),1.84-1.77(m,4H),1.58(d,J＝6.5Hz,4H),1.47-1.01(m,100H).¹³C NMR(101MHz,CDCl₃)161.62,159.65,153.87,152.87,150.72,148.61,138.86,138.24,138.17,137.56,132.93,127.97,127.57,127.30,127.14,126.58,125.41,124.39,124.00,123.49,122.66,120.29,119.34,117.07,115.63,114.72,113.80,108.84,68.39,68.27,46.63,31.99,30.16,29.75,29.67,29.63,29.51,29.44,27.44,26.32,26.22,22.74,14.16.HRMS(APCI)calcd.ForC₁₁₀H₁₃₉BF₂N₃O₄[M+H]⁺:1615.0821,found 1615.0811.

a compound represented by the formula 10-2:¹H NMR(500MHz,CDCl₃)7.48-7.39(m,9H),7.20(d,J＝8.1Hz,2H),6.98-6.87(m,4H),6.83-6.61(m,8H),3.97-3.88(m,8H),1.85-1.66(m,9H),1.57(d,J＝25.2Hz,5H),1.49-1.06(m,91H),1.04-0.73(m,22H),0.42(s,2H).¹³C NMR(126MHz,CDCl₃)160.31,159.44,159.41,158.41,157.70,157.70,151.02,150.05,145.32,145.14,140.27,139.95,139.81,132.87,132.55,132.46,130.29,125.18,124.63,124.55,123.11,113.74,113.62,68.01,67.93,67.83,54.93,40.26,31.94,31.34,29.67,29.65,29.48,29.37,26.12,26.08,22.70,14.11.MS(MALDI)Calcd.for C₂₀₉H₂₉₈B₂F₄N₆O₈[M]⁺:3120.3301,found 3120.3302.

a compound represented by the formula II-2:¹H NMR(300MHz,CDCl₃)9.43(d,J＝9.0Hz,4H),8.79(s,2H),8.32(s,2H),8.11(d,J＝9.3Hz,6H),7.94(s,2H),7.64-7.57(m,8H),7.35(d,J＝8.7Hz,6H),7.05-6.89(m,8H),4.24(d,J＝6.0Hz,8H),4.08(t,J＝6.2Hz,8H),1.90(d,J＝5.8Hz,15H),1.69-1.21(m,148H),1.07(d,J＝29.2Hz,20H),0.95-0.83(m,19H),0.77(t,J＝6.6Hz,6H),0.57(s,5H).¹³C NMR(126MHz,CDCl₃)161.56,161.49,159.76,150.63,149.49,148.86,148.73,140.00,138.11,137.90,137.71,132.80,132.13,128.46,127.53,127.01,126.17,125.79,125.46,125.24,120.29,119.74,117.49,117.05,115.61,115.17,114.80,114.04,109.27,109.09,68.41,68.28,54.80,40.73,32.09,31.56,29.87,29.77,29.64,29.55,26.39,22.83,22.71,14.23,14.15.MS(MALDI)Calcd.for C₂₀₉H₂₉₀B₂F₄N₆O₈[M]⁺:3112.2675,found 3112.2677.

test example 1

Weighing 1mg of the compound shown as the formula II-1, dissolving in 2mL of trichloromethane, and diluting with toluene, trichloromethane and tetrahydrofuran respectively to obtain a solution with a molar concentration of 10^-6A mol/L solution; respectively carrying out absorption spectrum and emission spectrum tests, wherein the absorption spectrum and emission spectrum test results are shown in figure 1 (the left side in the figure is an absorption spectrum, and the right side is an emission spectrum); the excitation wavelength was 808 nm.

As can be seen from FIG. 1, the maximum absorption peak of the compound II-1 can reach 840nm, the maximum emission peak can reach 870nm, both of which reach the near infrared region, and the compound II-1 has higher photoelectric conversion efficiency and wider application prospect when being used as an organic optical material.

Test example 2

Weighing 1mg of compound shown as formula II-2, dissolving in 2mL of chloroform, and diluting with toluene, chloroform and tetrahydrofuran respectively to obtain a solution with a molar concentration of 10^-6A mol/L solution; respectively carrying out absorption spectrum and emission spectrum tests, wherein the absorption spectrum and emission spectrum test results are shown in FIG. 2 (in the figure, the left side is an absorption spectrum, and the right side is an emission spectrum); the excitation wavelength was 808 nm.

As can be seen from FIG. 2, the maximum absorption peak of the compound II-2 can reach 840nm, the maximum emission peak can reach 870nm, both reach the near infrared region, and the alkyl long chain effectively improves the solubility, and is easy to prepare, high in photoelectric conversion efficiency and wide in application prospect when used as an organic optical material.

Test example 3

Weighing 1mg of compound shown as formula III-1, dissolving in 2mL of chloroform, and diluting with toluene, chloroform and tetrahydrofuran respectively to obtain a solution with a molar concentration of 10^-6A mol/L solution; respectively carrying out absorption spectrum and emission spectrum tests, wherein the absorption spectrum and emission spectrum test results are shown in FIG. 3 (the left side in the figure is an absorption spectrum, and the right side is an emission spectrum); the excitation wavelength was 730 nm.

As can be seen from FIG. 3, the absorption peak position of compound III-1 is in the near infrared region, the maximum absorption peak position is near 800nm, the maximum emission peak position is 850nm, and in the biological application aspect, the compound has less harm to the organism and strong penetrability.

Test example 4

Weighing 1mg of compound shown as formula III-2, dissolving in 2mL of chloroform, and diluting with toluene, chloroform and tetrahydrofuran respectively to obtain a solution with a molar concentration of 10^-6A mol/L solution; respectively carrying out absorption spectrum and emission spectrum tests, wherein the absorption spectrum and emission spectrum test results are shown in FIG. 4 (the left side in the figure is an absorption spectrum, and the right side is an emission spectrum); the excitation wavelength was 730 nm.

As can be seen from FIG. 4, the absorption peak position of compound III-2 is in the near infrared region, the maximum absorption peak position is near 800nm, the maximum emission peak position is 850nm, and in the biological application aspect, the compound has less harm to the organism and strong penetrability.

Test example 5

Weighing 1mg of compounds shown as formulas III-1 and III-2, dissolving the compounds in 2mL of toluene to be used as a sample solution to be tested, and then carrying out singlet oxygen test.

The singlet oxygen test uses 1, 3-diphenyl benzofuran (DPBF) as a trapping agent, and utilizes an ultraviolet spectrophotometry method to configure the concentration of the DPBF to be 4 × 10^-5mol/L, sample concentration of 1 × 10^-5mol/L, adding a capture agent DPBF into a sample solution to be detected, and placing the mixture at a wavelength of 660nm and a P value of 0.5mW/cm²The quantum yield of singlet oxygen generation (. PHI.) was calculated by a relative method using an optically matched solution by irradiating at the same intensity for the same time_Δ) The results are shown in FIG. 5, in which the left half of the graph represents the degradation curve of DPBF III-1 and the right half represents the degradation curve of DPBF III-2. And the photooxidation quantum yield of the target dye-sensitized DPBF was compared with the quantum yield of 2, 6-dibromo-3, 5- (4-methoxy) benzene-1, 7-phenylazabodipy (standard substance, noted as "S"). DPBF singlet oxygen yield Phi of standard in toluene_Δ0.77. The singlet oxygen yield of III-1 was found to be 6% and that of III-2 was found to be 37%.

As can be seen from FIG. 5, the compounds III-1 and III-2 have strong singlet oxygen efficiency, and have strong penetration performance to organisms and less damage due to absorption in the near infrared region, are not easily photolyzed, have high utilization rate, and have wide application prospects in economy and environmental protection.

The preferred embodiments of the present invention have been described in detail with reference to the accompanying drawings, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.

It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.

In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.

Claims

1. An organic conjugated molecular material with bifluorene Aza-BODIPY as a basic skeleton is characterized in that the structure of the organic conjugated molecular material is shown as a formula I, a formula II or a formula III,

2. The organic conjugated molecular material of basic skeleton according to claim 1, wherein R1, R2, R3, R4 are each independently selected from one of alkyl groups H, C1-C14 and alkoxy groups C1-C14, R5 is one of hydrocarbon groups C1-C6, R6 and R7 are each independently one of H and alkyl groups C1-C10, X is bromine or iodine;

preferably, R1, R2, R3 and R4 are respectively and independently selected from H and one of alkoxy of C1-C12, R5 is one of hydrocarbyl of C4-C6, R6 and R7 are respectively and independently one of alkyl of C8-C10, and X is bromine or iodine;

preferably, each of R1, R2, R3 and R4 is independently selected from methoxy or n-dodecyloxy, R5 is tert-butyl, R6 and R7 are both methyl or n-octyl, and X is bromine or iodine;

preferably, m, n1, n2, n3 and n4 are all 1.

3. The organic conjugated molecular material of basic skeleton according to claim 1 or 2, wherein the structure of the organic conjugated molecular material is shown as formula I-1, formula I-2, formula II-1, formula II-2, formula III-1 or formula III-2,

wherein, C in the formula₈H₁₇Is n-octyl, C₁₂H₂₅O is n-dodecyloxy.

4. A method for preparing the organic conjugated molecular material with the structure shown in formula I according to claim 1, wherein the method comprises:

wherein R1, R2, R3 and R4 in the formula are respectively and independently selected from H, C1-C14 alkyl and C1-C14 alkoxy, n1, n2, n3 and n4 are respectively and independently positive integers of 1-5, and X is halogen; the structure of the fluorenyl boric acid compound is shown as a formula 13-1 or a formula 13-2;

preferably, R1, R2, R3 and R4 are respectively and independently selected from one of alkyl groups of H, C1-C14 and alkoxy groups of C1-C14, and X is bromine or iodine;

preferably, R1, R2, R3 and R4 are respectively and independently selected from H and one of alkoxy of C1-C12, and X is bromine or iodine;

preferably, R1, R2, R3, R4 are each independently selected from methoxy or n-dodecyloxy, X is bromine or iodine;

preferably, n1, n2, n3 and n4 are all 1.

5. The preparation method according to claim 4, wherein in the step 1), the compound having the structure shown in the formula 3, the fluorenyl boric acid compound and the palladium catalyst are used in a molar ratio of 1: 2-4: 0.05-0.1;

preferably, the first contact reaction satisfies at least the following conditions: the reaction temperature is 90-120 ℃, and the reaction time is 24-36 h;

preferably, in step 1), the pH of the reaction system is controlled by carbonate, and the molar ratio of the compound having the structure shown in formula 3 to the carbonate is 1: 2-6;

preferably, the carbonate is selected from at least one of sodium carbonate, potassium carbonate and cesium carbonate;

preferably, in the step 2), the compound with the structure shown in the formula 9 and the oxidant are used in a molar ratio of 1: 4-15;

preferably, in step 2), the first oxidation reaction at least satisfies the following condition: the reaction temperature is 0-45 ℃, and the reaction time is 10-30 min;

preferably, in the step 2), the oxidant is selected from at least one of anhydrous ferric chloride, molybdenum pentachloride and dichloro dicyano benzoquinone;

preferably, the palladium catalyst is selected from at least one of tetrakistriphenylphosphine palladium, palladium acetate, palladium chloride, bis (triphenylphosphine) palladium dichloride and tris (dibenzylideneacetone) dipalladium;

preferably, the fluorenylboronic acid compound is 9, 9-dioctylfluorene-2, 7-bisboronic acid or 9, 9-dioctylfluorene-2, 7-bis (boronic acid pinacol ester);

preferably, the structure of the compound with the structure shown in the formula 3 is shown in a formula 3-1 or a formula 3-2,

6. a method for preparing the organic conjugated molecular material with the structure shown in formula II according to claim 1, wherein the method comprises:

wherein R1, R2, R3 and R4 in the formula are respectively and independently selected from H, C1-C14 alkyl and C1-C14 alkoxy, and n1, n2, n3 and n4 are respectively and independently positive integers of 1-5; r5 is a hydrocarbon group of H, C1-C6, and m is a positive integer of 1-4; r6 and R7 are each independently one of H and C1-C10 hydrocarbyl, X is halogen; the structure of the fluorenyl boric acid compound is shown as a formula 13-1 or a formula 13-2;

preferably, R1, R2, R3 and R4 are respectively and independently selected from one of an alkyl group of H, C1-C14 and an alkoxy group of C1-C14, R5 is a hydrocarbon group of C1-C6, R6 and R7 are respectively and independently one of H and an alkyl group of C1-C10, and X is bromine or iodine;

preferably, R1, R2, R3 and R4 are respectively and independently selected from H and one of alkoxy of C1-C12, R5 is a hydrocarbon group of C4-C6, R6 and R7 are respectively and independently one of alkyl of C8-C10, and X is bromine or iodine;

preferably, m, n1, n2, n3 and n4 are all 1.

7. The preparation method according to claim 6, wherein in the step 1), the compound having the structure shown in the formula 5, the fluorenyl boronic acid compound and the palladium catalyst are used in a molar ratio of 1: 0.4-0.6: 0.05-0.1;

preferably, the second contact reaction satisfies at least the following conditions: the reaction temperature is 90-120 ℃, and the reaction time is 24-36 h;

preferably, in step 1), the pH of the reaction system is controlled by carbonate, and the molar ratio of the compound having the structure shown in formula 5 to the carbonate is 1: 2-6;

preferably, in the step 2), the compound with the structure shown in the formula 10 and the oxidant are used in a molar ratio of 1: 4-15;

preferably, in step 2), the second oxidation reaction at least satisfies the following condition: the reaction temperature is 0-45 ℃, and the reaction time is 10-30 min;

preferably, the structure of the compound with the structure shown in the formula 5 is shown in a formula 5-1 or a formula 5-2,

8. a method for preparing the organic conjugated molecular material with the structure shown in formula III according to claim 1, wherein the method comprises:

preferably, m, n1, n2, n3 and n4 are all 1.

9. The preparation method according to claim 8, wherein in the step 1), the compound having the structure shown in the formula 2, the fluorenyl boronic acid compound and the palladium catalyst are used in a molar ratio of 1: 0.4-0.6: 0.05-0.1;

preferably, in step 1), the third contact reaction at least satisfies the following condition: the reaction temperature is 90-120 ℃, and the reaction time is 24-36 h;

preferably, in the step 1), the pH of the reaction system is controlled by carbonate, and the molar ratio of the compound having the structure shown in formula 2 to the carbonate is 1: 2-6;

preferably, in the step 2), the molar ratio of the compound with the structure shown in the formula 11 to the halogen source is 1: 1.8-2.4;

preferably, in step 2), the fourth contact reaction at least satisfies the following condition: the reaction temperature is 0-45 ℃, and the reaction time is 1-6 h;

preferably, the halogen source is selected from at least one of liquid bromine, N-bromosuccinimide, and elemental iodine;

preferably, in the step 3), the compound with the structure shown in the formula 12 and the oxidant are used in a molar ratio of 1: 4-15;

preferably, in the step 3), the oxidant is selected from at least one of anhydrous ferric chloride, molybdenum pentachloride and dichloro dicyano benzoquinone;

preferably, in step 3), the third oxidation reaction at least satisfies the following condition: the reaction temperature is 0-45 ℃, and the reaction time is 10-30 min;

preferably, the structure of the compound with the structure shown in the formula 2 is shown in a formula 2-1 or a formula 2-2,

10. use of the bifluorene Aza-BODIPY-based organic conjugated molecular material as claimed in any one of claims 1-3 in biological imaging and organic electronic materials.