Eight-membered ring parallel diisoindole heterocyclic hydrazone boron aza fused ring compound as well as preparation method and application thereof

Abstract

The invention relates to the technical field of organic synthesis and the technical field of fine chemical engineering, in particular to an eight-membered ring parallel diisoindole heterocyclic hydrazone boron aza fused ring compound as well as a preparation method and application thereof. The structure of the eight-membered ring parallel diisoindole heterocyclic hydrazone boron aza fused ring compound is as shown in a formula (I). Wherein Ar is nitrogen-containing heterocyclic aryl, and R is selected from one of aryl, heterocyclic aryl and alkyl. According to the octatomic ring parallel diisoindole heterocyclic hydrazone boron nitrogen heterocyclic fused ring compound, the solubility, the molecular energy level and the photo-physicochemical properties of the compound are respectively regulated and controlled by regulating and controlling substituent groups on boron of a molecular skeleton, peripheral heteroatoms and fused ring modification, and a series of novel boron nitrogen full fused ring molecules are constructed. Meanwhile, the preparation method of the octatomic-ring parallel diisoindole heterocyclic hydrazone boron aza fused ring compound is simple and convenient, the reaction condition is mild, the raw materials are easy to obtain, the compound is easy to amplify for industrial preparation, and the compound has a wide application prospect.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic synthesis and fine chemical technology, in particular, to an eight-membered ring parallel double isoindole heterocyclic hydrazone boron nitrogen heterocyclic fused ring compound and a preparation method and application thereof. BACKGROUND

[0002] The design and synthesis of organic optoelectronic functional materials have always been the research frontier in the field of chemistry and material science. Among them, the construction of rigid π-conjugated skeleton with unique geometric structure and electronic properties is the key to realize the breakthrough of material function. Among the many molecular skeletons, the heterocyclic fused ring system based on boron and nitrogen has attracted much attention due to its controllable energy level and unique optical properties. Although the classic BODIPY dye has been widely used, its structure is still limited to specific six-membered or five-membered ring framework, and its synthesis strategy and coordination mode are also conventional paths, which has inherent limitations in developing polycyclic aromatic hydrocarbons with novel topological structures.

[0003] In recent years, scientists have been committed to exploring new boron and nitrogen heterocyclic fused ring systems beyond the classic BODIPY structure. For example, by introducing boron and nitrogen coordination bonds to enhance molecular rigidity and adjust electronic distribution. However, most of these studies are boron and nitrogen modification of known carbon ring or heterocyclic skeletons, and the core ring system structure has not been fundamentally changed. In particular, effective strategies for constructing rigid fused rings containing eight-membered rings and above are extremely rare. Due to the existence of entropy effect and angle tension, it is a great challenge to synthesize eight-membered rings with specific geometric shapes and make them exist stably in the conjugated system. On the other hand, from the perspective of synthetic chemistry, the existing methods for constructing complex boron and nitrogen heterocyclic fused rings usually have problems such as long steps, separation of unstable intermediates, use of expensive catalysts or harsh reaction conditions. Developing a new synthesis method that is efficient, convenient and can construct complex boron and nitrogen polycyclic skeletons in one step has important scientific value and application potential.

[0004] Therefore, there is an urgent need for a completely new and innovative synthesis strategy to break through the structural limitations of existing boron and nitrogen heterocyclic fused ring systems, to add members with novel topological structures to the library of organic conjugated materials, and to provide a new material basis and platform for subsequent functional modification and application exploration. SUMMARY

[0005] In view of the problems in the prior art, the present application provides an eight-membered ring parallel double isoindole heterocyclic hydrazone boron nitrogen heterocyclic fused ring compound with a novel structure, which is capable of regulating solubility, molecular energy level and acceptor performance by regulating substituents on the boron of the molecular skeleton, peripheral heteroatoms and fused ring modification, and constructing a series of novel boron nitrogen fully fused ring molecules. The nitrogen heterocyclic skeleton of the compound comprises two two-molecular ligand substructures, which is a novel structure. The structure not only comprises two N-B-N units, but also comprises two B←N coordination bonds, forming a unique eight-membered ring parallel two five-membered ring BBN structure, and the asymmetric structure limits the rotation of the carbon-nitrogen double bond, thereby providing sufficient rigidity and stability. Meanwhile, the eight-membered ring parallel double isoindole heterocyclic hydrazone boron nitrogen heterocyclic fused ring compound has a simple and convenient preparation method, mild reaction conditions, readily available raw materials, and is easy to scale up for industrial production, and has a broad application prospect.

[0006] In order to achieve the above-mentioned purpose, in a first aspect, the present application provides an eight-membered ring parallel double isoindole heterocyclic hydrazone boron nitrogen heterocyclic fused ring compound, the structure of which is shown in formula (I); In the formula, Ar is a nitrogen-containing heterocyclic aryl group, and R is selected from one of an aryl group, a heterocyclic aryl group and an alkyl group.

[0007] Preferably, Ar is selected from one of a pyridyl group, a thiazolyl group, an imidazolyl group, a halogenated pyridyl group, a halogenated thiazolyl group and a halogenated imidazolyl group, and R is selected from one of a monocyclic aryl group, a fused ring aryl group, a halogenated aryl group, an alkyl-substituted aryl group, an alkoxy-substituted aryl group, a pyridyl group, a pyrrolyl group, a furanyl group, a thienyl group, a thiazolyl group, a C1-C16 branched alkyl group and a C1-C16 straight-chain alkyl group.

[0008] Preferably, Ar is selected from one of a 6-chloropyridyl group, a 6-bromopyridyl group, a 5-bromopyridyl group, a 4-methylbenzothiazol-2-yl group and a benzimidazolyl group, and R is selected from one of a phenyl group, a 4-methoxybenzene group, a 4-trifluoromethoxybenzene group, a 4-trifluoromethylphenyl group, a pentafluorophenyl group, a 2-naphthylphenyl group, a 4-naphthylphenyl group, a 4-bromophenyl group, a 3-thienyl group, a n-butyl group and a n-decyl group.

[0009] Preferably, the eight-membered ring parallel double isoindole heterocyclic hydrazone boron nitrogen heterocyclic fused ring compound has a structure as shown in formulae 1a-1n and 2a-2d,

[0010]

[0011] ​

[0012] Secondly, the present invention provides a method for preparing an eight-membered ring paralleled bisisoindole heterocyclic hydrazone boron nitride fused ring compound, the method comprising: 1) In the presence of a solvent and a Lewis acid, compound A and compound B undergo a condensation reaction to generate an intermediate; 2) Under alkaline conditions, the intermediate obtained in step 1) is subjected to a cyclization reaction with aromatic boric acid of formula C to obtain the compound of general formula (I); ; Wherein, Ar is a nitrogen-containing heterocyclic aryl group, and R is selected from one of aryl, heterocyclic aryl, C1-C16 branched alkyl and C1-C16 straight alkyl groups.

[0013] Preferably, Ar is selected from one of pyridinyl, thiazolyl, imidazolyl, halopyridinyl, halothiazolyl, and haloimidazolyl, and R is selected from one of monocyclic aryl, fused-ring aryl, haloaryl, alkyl-substituted aryl, alkoxy-substituted aryl, pyridinyl, pyrroleyl, furanyl, thiophenyl, thiazolyl, C1-C16 branched alkyl, and C1-C16 straight-chain alkyl.

[0014] Preferably, Ar is selected from one of 6-chloropyridinyl, 6-bromopyridinyl, 5-bromopyridinyl, 4-methylbenzothiazol-2-yl, and benzimidazolyl, and R is selected from one of phenyl, 4-methoxyphenyl, 4-trifluoromethoxyphenyl, 4-trifluoromethylphenyl, pentafluorophenyl, 2-naphthylphenyl, 4-naphthylphenyl, 4-bromophenyl, 3-thienyl, n-butyl, and n-decyl.

[0015] Preferably, in step 1), the Lewis acid is selected from one or more of acetic acid, p-toluenesulfonic acid, hydrochloric acid, and sulfuric acid; preferably acetic acid.

[0016] Preferably, in step 1), the solvent is selected from one or more of chlorobenzene, toluene, o-dichlorobenzene, acetonitrile, and dichloromethane; preferably chlorobenzene.

[0017] Preferably, in step 1), the molar ratio of compound A, compound B and Lewis acid is 1:1 to 1.1:0.01 to 0.3.

[0018] Preferably, in step 1), the conditions for the condensation reaction include: a reaction temperature of 80~170℃, preferably 140~150℃; and a reaction time of 0.5~50 hours, preferably 0.5~2 hours.

[0019] Preferably, in step 2), the alkaline condition is provided by an alkaline substance selected from one or more of potassium phosphate, sodium carbonate, sodium bicarbonate and sodium hydroxide; preferably potassium phosphate.

[0020] Preferably, the molar ratio of the alkaline substance to the compound of formula A is 3 to 8:1.

[0021] Preferably, the molar ratio of the aromatic boric acid of formula C to the compound of formula A is 4 to 20:1.

[0022] Preferably, in step 2), the conditions for the cyclization reaction include: reacting under reflux, reacting at a temperature of 100~200℃, and reacting for 2~100 hours, preferably 6~10 hours.

[0023] Thirdly, the present invention provides an eight-membered ring parallel bisisoindole heterocyclic hydrazone boron nitrogen heterocyclic compound prepared by the preparation method described in the present invention.

[0024] Fourthly, the present invention provides a use of the eight-membered ring parallel bisisoindole heterocyclic hydrazone-boron-nitrogen heterocyclic compound as described in the present invention, the use including for preparing fluorescent sensors, organic field-effect transistors or photoactive layer materials.

[0025] In the above technical solution, this invention pioneers a boric acid template-mediated intermolecular dehydration cyclization strategy, constructing a stable eight-membered ring BN skeleton through multi-level BN bond synergy. This strategy utilizes the specific interaction between boric acid and nitrogen-containing ligands to achieve precise construction of the eight-membered ring through a (3+1)×2 cyclization mode. A BBN core skeleton containing four BN covalent bonds and two B←N coordinate bonds is designed, providing an eight-membered ring parallel to a bisisoindole heterocyclic hydrazone-boron-nitrogen heterofused ring compound. Solubility, molecular energy levels, and acceptor properties are controlled by regulating the substituents on the boron of the molecular skeleton, the peripheral heteroatoms, and the fused ring modification, respectively, to construct a series of novel boron-nitrogen fully fused ring molecules. This type of nitrogen-containing heterofused ring skeleton is a novel structure constructed from two bimolecular ligands. This structure not only contains two NBN units but also two B←N coordinate bonds, forming a unique eight-membered ring BBN structure with two five-membered rings in parallel. Its asymmetric structure restricts the rotation of the carbon-nitrogen double bond, thus providing sufficient rigidity and stability.

[0026] Meanwhile, the preparation method of this invention uses readily available commercial raw material 1-amino-1H-isoindole-3-amine, which is condensed with 2-hydrazino-heterocyclic compounds to generate imine isoindolepyridine hydrazinohydrazone Schiff base ligands. Then, through two key steps of precise condensation and cyclization, a highly efficient synthetic method for constructing boron-nitrogen fully fused ring molecules is developed. The preparation method of this invention is a one-pot tandem reaction, starting from commercially available raw materials, with simple steps, mild reaction conditions, and high yield, which is beneficial for large-scale commercial preparation.

[0027] Furthermore, the eight-membered ring parallel bisisoindole heterocyclic hydrazone-boron-nitrogen heterocyclic fused ring compound of the present invention has a large Stokes shift, exhibiting good excitation-emission separation characteristics, and has good application prospects in the fields of fluorescent sensors, organic field-effect transistors or photoactive layer materials.

[0028] Other features and advantages of the present invention will be described in detail in the following detailed description section. Attached Figure Description

[0029] The accompanying drawings are provided to further illustrate the invention and form part of the specification. They are used together with the following detailed description to explain the invention, but do not constitute a limitation thereof. In the drawings: Figure 1 The X-ray single crystal structure diagram (front view and side view) of compound 1h of the present invention is shown.

[0030] Figure 2 The X-ray single crystal structure diagram (front view and side view) of compound 2k of the present invention is shown.

[0031] Figure 3 The X-ray single crystal structure diagram (front view and side view) of compound 2n of the present invention is shown.

[0032] Figure 4 The X-ray single crystal structure diagram (front view and side view) of compound 2c of the present invention is shown. Detailed Implementation

[0033] The following provides a detailed description of specific embodiments of the present invention. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit the scope of the invention.

[0034] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0035] In a first aspect, the present invention provides an eight-membered ring parallel bisisoindole heterocyclic hydrazone boron nitride fused ring compound, the structure of which is shown in formula (I); ; Wherein, Ar is a nitrogen-containing heterocyclic aryl group, and R is selected from aryl, heterocyclic aryl, and alkyl groups.

[0036] In a preferred embodiment of the present invention, Ar is selected from one of pyridinyl, thiazolyl, imidazolyl, halopyridinyl, halothiazolyl, and haloimidazolyl, and R is selected from one of monocyclic aryl, fused-ring aryl, haloaryl, alkyl-substituted aryl, alkoxy-substituted aryl, pyridinyl, pyrroleyl, furanyl, thiophenyl, thiazolyl, C1-C16 branched alkyl, and C1-C16 straight-chain alkyl.

[0037] This invention pioneers a boric acid template-mediated intermolecular dehydration cyclization strategy, constructing a stable eight-membered ring BN skeleton through multi-level BN bond synergy. This strategy utilizes the specific interaction between boric acid and nitrogen-containing ligands to achieve precise eight-membered ring construction via a (3+1)×2 cyclization mode. A BBN core skeleton containing four BN covalent bonds and two B←N coordinate bonds is designed, providing an eight-membered ring parallel to a bisisoindole heterocyclic hydrazone-boron-nitrogen heterofused ring compound. Solubility, molecular energy levels, and acceptor properties are controlled by adjusting the substituents on the boron of the molecular skeleton, the peripheral heteroatoms, and the fused ring modification, respectively, to construct a series of novel boron-nitrogen fully fused ring molecules. This type of nitrogen-containing heterofused ring skeleton is a novel structure constructed from two bimolecular ligands. This structure not only contains two NBN units but also two B←N coordinate bonds, forming a unique eight-membered ring BBN structure with two five-membered rings in parallel. Its asymmetric structure restricts the rotation of the carbon-nitrogen double bond, thus providing sufficient rigidity and stability.

[0038] In a preferred embodiment of the present invention, Ar is selected from one of 6-chloropyridinyl, 6-bromopyridinyl, 5-bromopyridinyl, 4-methylbenzothiazol-2-yl, and benzimidazolyl, and R is selected from one of phenyl, 4-methoxyphenyl, 4-trifluoromethoxyphenyl, 4-trifluoromethylphenyl, pentafluorophenyl, 2-naphthylphenyl, 4-naphthylphenyl, 4-bromophenyl, 3-thiophene, n-butyl, and n-decyl.

[0039] In a preferred embodiment of the present invention, the structure of the eight-membered ring parallel bisisoindole heterocyclic hydrazone boron nitrogen heterofused ring compound is shown in formulas 1a-1n and 2a-2d.

[0040] Secondly, the present invention provides a method for preparing an eight-membered ring paralleled bisisoindole heterocyclic hydrazone boron nitride fused ring compound, the method comprising: 1) In the presence of a solvent and a Lewis acid, compound A and compound B undergo a condensation reaction to generate an intermediate; 2) Under alkaline conditions, the intermediate obtained in step 1) is subjected to a cyclization reaction with aromatic boric acid of formula C to obtain the compound of general formula (I); ; Wherein, Ar is a nitrogen-containing heterocyclic aryl group, and R is selected from one of aryl, heterocyclic aryl, C1-C16 branched alkyl and C1-C16 straight alkyl groups.

[0041] Meanwhile, the preparation method of this invention uses readily available commercial raw material 1-amino-1H-isoindole-3-amine, which is condensed with 2-hydrazino-heterocyclic compounds to generate imine isoindolepyridine hydrazinohydrazone Schiff base ligands. Then, through two key steps of precise condensation and cyclization, a highly efficient synthetic method for constructing boron-nitrogen fully fused ring molecules is developed. The preparation method of this invention is a one-pot tandem reaction, starting from commercially available raw materials, with simple steps, mild reaction conditions, and high yield, which is beneficial for large-scale commercial preparation.

[0042] In a preferred embodiment of the present invention, Ar is selected from one of pyridinyl, thiazolyl, imidazolyl, halopyridinyl, halothiazolyl, and haloimidazolyl, and R is selected from one of monocyclic aryl, fused-ring aryl, haloaryl, alkyl-substituted aryl, alkoxy-substituted aryl, pyridinyl, pyrroleyl, furanyl, thiophenyl, thiazolyl, C1-C16 branched alkyl, and C1-C16 straight-chain alkyl.

[0043] In a preferred embodiment of the present invention, Ar is selected from one of 6-chloropyridinyl, 6-bromopyridinyl, 5-bromopyridinyl, 4-methylbenzothiazol-2-yl, and benzimidazolyl, and R is selected from one of phenyl, 4-methoxyphenyl, 4-trifluoromethoxyphenyl, 4-trifluoromethylphenyl, pentafluorophenyl, 2-naphthylphenyl, 4-naphthylphenyl, 4-bromophenyl, 3-thiophene, n-butyl, and n-decyl.

[0044] In a preferred embodiment of the present invention, in step 1), the Lewis acid is selected from one or more of acetic acid, p-toluenesulfonic acid, hydrochloric acid and sulfuric acid; preferably acetic acid.

[0045] In a preferred embodiment of the present invention, in step 1), the solvent is selected from one or more of chlorobenzene, toluene, o-dichlorobenzene, acetonitrile and dichloromethane; preferably chlorobenzene.

[0046] In a preferred embodiment of the present invention, in step 1), the molar ratio of the compound of formula A, the compound of formula B and the Lewis acid is 1:1 to 1.1:0.01 to 0.3.

[0047] In a preferred embodiment of the present invention, in step 1), the conditions for the condensation reaction include: a reaction temperature of 80~170℃, preferably 140~150℃; and a reaction time of 0.5~50 hours, preferably 0.5~2 hours.

[0048] In a preferred embodiment of the present invention, in step 2), the alkaline condition is provided by an alkaline substance selected from one or more of potassium phosphate, sodium carbonate, sodium bicarbonate and sodium hydroxide; preferably potassium phosphate.

[0049] In a preferred embodiment of the present invention, the molar ratio of the alkaline substance to the compound of formula A is 3 to 8:1.

[0050] In a preferred embodiment of the present invention, the molar ratio of the aromatic boric acid of formula C to the compound of formula A is 4 to 20:1.

[0051] In a preferred embodiment of the present invention, in step 2), the conditions for the cyclization reaction include: reacting under reflux, reacting at a temperature of 100~200℃, and reacting for 2~100 hours, preferably 6~10 hours.

[0052] In a preferred embodiment of the present invention, the preparation method further includes separation and purification, wherein the separation is a conventional method in the art, and the purification is performed by silica gel column chromatography to purify the crude product.

[0053] In a preferred embodiment of the present invention, the developing solvent used in the silica gel column chromatography is a conventional developing solvent formulation in the art. For example, it can be obtained by mixing petroleum ether and dichloromethane in a volume ratio of 2:1, or by mixing hexane and ethyl acetate in a volume ratio of 9:1, or by mixing n-hexane and dichloromethane in a volume ratio of 1:1.

[0054] Thirdly, the present invention provides an eight-membered ring parallel bisisoindole heterocyclic hydrazone boron nitrogen heterocyclic compound prepared by the preparation method described in the present invention.

[0055] Fourthly, the present invention provides a use of the eight-membered ring parallel bisisoindole heterocyclic hydrazone-boron-nitrogen heterocyclic compound as described in the present invention, the use including for preparing fluorescent sensors, organic field-effect transistors or photoactive layer materials.

[0056] The eight-membered ring parallel double isoindole heterocyclic hydrazone-boron-nitrogen heterofused ring compound of the present invention has a large Stokes shift, exhibiting good excitation-emission separation characteristics, and has good application prospects in the field of optoelectronic materials.

[0057] In this invention, the room temperature is 15~35℃.

[0058] The present invention will be described in detail below through examples. In the following examples, the pharmaceuticals and agents are all conventional commercially available products.

[0059] Example 1 This example illustrates the synthesis of an eight-membered ring parallel-connected diisoindole heterocyclic hydrazone-boron-nitrogen fused-ring aromatic hydrocarbon 1a: Chlorobenzene (20 mL) was placed in a pressure flask, and 1-amino-1H-isoindole-3-amine (145 mg, 1.0 mmol), 2-chloro-6-hydrazinopyridine (145 mg, 1.0 mmol, 1 equiv.), and glacial acetic acid (0.2 mL) were added. The mixture was heated to 145°C in a sand bath and maintained for 0.5 hours. Then, K3PO4 (230 mg, 1.0 mmol, 1 equiv.) and phenylboronic acid (121 mg, 1.0 mmol, 1 equiv.) were added to the solution. The reaction mixture was refluxed for another 8 hours. After cooling to room temperature, the reaction mixture was poured into water (100 mL) and extracted with dichloromethane (3 × 60 mL). The organic layers were combined and dried over anhydrous Na2SO4, and the solvent was removed under vacuum. The crude product was further purified by silica gel column chromatography using a mixture of dichloromethane and petroleum ether (silica gel, petroleum ether / dichloromethane = 2 / 1, volume ratio) as the eluent to give the desired yellow solid 1a (302 mg, 84%).

[0060] The 1a NMR and high-resolution mass spectrometry data are as follows: 1 H NMR (400 MHz, CDCl3) δ 10.20 (s, 2H), 8.01 (t, J = 8.0 Hz, 4H), 7.73(t, J = 7.4 Hz, 2H), 7.66 (t, J = 7.5 Hz, 2H), 7.39 (t, J = 7.9 Hz, 2H), 7.22 (d, J =8.3 Hz, 2H), 6.86 – 6.84 (m, 4H), 6.79 (t, J = 7.2 Hz, 2H), 6.71 (t, J = 7.3 Hz, 4H), 6.60 (d, J = 7.4 Hz, 2H). 13C NMR (126 MHz, CDCl3) δ 158.3, 157.1, 149.7,148.1, 139.9, 133.9, 132.6, 131.2, 129.8, 129.7, 129.6, 128.6, 126.9, 126.6,126.4, 122.1, 121.8, 112.8, 107.4. 11 B NMR (160 MHz, CDCl3) δ 3.88. HRMS (ESI):calcd C 38 H 27 B2Cl2N 10 [M+H] + m / z =715.1978, found 715.1985. Example 2 This example illustrates the synthesis of an eight-membered ring parallel bisisoindole heterocyclic hydrazone boron azeotropic fused ring aromatic hydrocarbon 1b: Chlorobenzene (20 mL) was placed in a pressure flask, and 1-amino-1H-isoindole-3-amine (145 mg, 1.0 mmol), 2-chloro-6-hydrazinopyridine (145 mg, 1.0 mmol, 1 equiv.), and glacial acetic acid (0.2 mL) were added. The mixture was heated to 145°C in a sand bath and maintained for 0.5 hours. Then, K3PO4 (690 mg, 3.0 mmol, 3 equiv.) and 4-methoxy-phenylboronic acid (608 mg, 4.0 mmol, 4 equiv.) were added to the solution. The reaction mixture was refluxed for another 8 hours. After cooling to room temperature, the reaction mixture was poured into water (100 mL) and extracted with dichloromethane (3 × 60 mL). The organic layers were combined and dried over anhydrous Na2SO4, and the solvent was removed under vacuum. The crude product was further purified by silica gel column chromatography using a mixture of dichloromethane and petroleum ether (silica gel, petroleum ether / dichloromethane = 2 / 1, volume ratio) as the eluent to give the desired yellow solid 1b (242 mg, 62%).

[0061] The 1b NMR and high-resolution mass spectrometry data are as follows: 1 H NMR (500 MHz, CDCl3) δ 10.09 (s, 2H), 7.98 (dd, J = 7.7, 3.5 Hz, 4H), 7.70 (t, J = 7.5 Hz, 2H), 7.64 (t, J= 7.5 Hz, 2H), 7.40 – 7.36 (m, 2H), 7.22 (d, J = 8.3 Hz, 2H), 6.76 (d, J = 8.6 Hz, 4H), 6.59 (d, J = 7.4 Hz, 2H), 6.27 (d, J =8.6 Hz, 4H), 3.63 (s, 6H). 13 C NMR (126 MHz, CDCl3) δ 158.4, 158.3, 157.1,149.7, 148.3, 140.0, 133.9, 132.7, 132.6, 130.0, 129.6, 122.1, 121.9, 112.9,112.6, 107.5, 54.6. 11 B NMR (128 MHz, CDCl3) δ 2.79. HRMS (ESI): calcd forC 40 H 30 B₂Cl₂NaO₂[M+Na] + : 797.2009; found 797.2011. Example 3 This embodiment illustrates the synthesis of 1c, an eight-membered ring parallel diisoindole heterocyclic hydrazone boron nitride heterocyclic aromatic hydrocarbon: Chlorobenzene (20 mL) was placed in a pressure flask, and 1-amino-1H-isoindole-3-amine (145 mg, 1.0 mmol), 2-chloro-6-hydrazinopyridine (145 mg, 1.0 mmol, 1 equiv.), and glacial acetic acid (0.2 mL) were added. The mixture was heated to 145°C in a sand bath and maintained for 0.5 hours. Then, K3PO4 (230 mg, 1.0 mmol, 1 equiv.) and 4-trifluoromethoxy-phenylboronic acid (206 mg, 1.0 mmol, 1 equiv.) were added to the solution. The reaction mixture was refluxed for another 8 hours. After cooling to room temperature, the reaction mixture was poured into water (100 mL) and extracted with dichloromethane (3 × 60 mL). The organic layers were combined and dried over anhydrous Na2SO4, and the solvent was removed under vacuum. The crude product was further purified by silica gel column chromatography using a mixture of dichloromethane and petroleum ether (silica gel, petroleum ether / dichloromethane = 2 / 1, volume ratio) as the eluent to give the desired yellow solid 1c (301 mg, 81%).

[0062] The 1C NMR and high-resolution mass spectrometry data are as follows: 1 H NMR (400 MHz, CDCl3) δ 10.08 (s, 2H), 7.97 (t, J = 6.7 Hz, 4H), 7.73– 7.63 (m, 4H), 7.41 (t, J = 7.9 Hz, 2H), 7.34 – 7.21 (m, 4H), 6.85 (d, J = 8.3Hz, 4H), 6.61 (dd, J = 18.2, 7.8 Hz, 6H). 13 C NMR (101 MHz, CDCl3) δ 158.0,157.3, 149.3, 148.4, 148.1, 140.1, 134.2, 133.5, 132.9, 132.4, 129.7, 129.7,128.6, 126.4, 122.1, 121.9, 120.4 (q, J F-C = 257.6 Hz), 118.7, 113.2, 107.4. 11 BNMR (128 MHz, CDCl3) δ 1.25. 19 F NMR (376 MHz, CDCl3) δ -57.55. HRMS (ESI):calcd for C 40 H 25 B2Cl2F6N 10 O2[M+H] + : 883.1629; found 883.1634. Example 4 This example illustrates the synthesis of an eight-membered ring parallel bisisoindole heterocyclic hydrazone boron nitride fused ring aromatic hydrocarbon 1d: Chlorobenzene (20 mL) was placed in a pressure flask, and 1-amino-1H-isoindole-3-amine (145 mg, 1.0 mmol), 2-chloro-6-hydrazinopyridine (145 mg, 1.0 mmol, 1 equiv.), and glacial acetic acid (0.2 mL) were added. The mixture was heated to 145°C in a sand bath and maintained for 0.5 hours. Then, 4-trifluoromethyl-phenylboronic acid (190 mg, 1.0 mmol, 1 equiv.) was added to the solution. The reaction mixture was refluxed for another 8 hours. After cooling to room temperature, the reaction mixture was poured into water (100 mL) and extracted with dichloromethane (3 × 60 mL). The organic layers were combined and dried over anhydrous Na₂SO₄, and the solvent was removed under vacuum. The crude product was further purified by silica gel column chromatography using a mixture of dichloromethane and petroleum ether (silica gel, n-hexane / dichloromethane = 2 / 1, volume ratio) as the eluent to give the desired yellow solid 1d (355 mg, 87%).

[0063] The 1-day NMR and high-resolution mass spectrometry data are as follows: 1 H NMR (500 MHz, CDCl3) δ 10.02 (s, 2H), 8.03 (d, J = 7.7 Hz, 2H), 7.99(d, J = 7.8 Hz, 2H), 7.77 (t, J = 7.5 Hz, 2H), 7.69 (t, J = 7.5 Hz, 2H), 7.42 (t, J =7.9 Hz, 2H), 7.22 (d, J = 8.3 Hz, 2H), 6.97 (d, J = 8.1 Hz, 4H), 6.92 (d, J = 8.0Hz, 4H), 6.64 (d, J = 7.5 Hz, 2H). 13 C NMR (126 MHz, CDCl3) δ 157.9, 157.5,149.5, 148.1, 140.2, 133.4, 133.0, 131.3, 129.8, 129.6, 128.6 (q, J F-C = 34.0Hz), 125.4, 125.3 (q, J F-C= 272.2 Hz), 123.5, 123.5, 123.2, 122.2, 122.0,113.3, 107.4. 11 B NMR (128 MHz, CDCl3) δ 2.76. 19 F NMR (376 MHz, CDCl3) δ -62.77.HRMS (ESI): calcd C 40 H 24 B2Cl2F6N 10 [M+H] + : 850.1723, found 850.1702. Example 5 This example illustrates the synthesis of an eight-membered ring parallel bisisoindole heterocyclic hydrazone boron nitride fused ring aromatic hydrocarbon 1e: Chlorobenzene (20 mL) was placed in a pressure flask, and 1-amino-1H-isoindole-3-amine (143 mg, 1.0 mmol), 2-hydrazino-5-chloropyridine (148 mg, 1.0 mmol, 1 equiv.), and glacial acetic acid (0.2 mL) were added. The mixture was heated to 145 °C in a sand bath and maintained for 0.5 h. Then, K3PO4 (230 mg, 1.0 mmol, 1 equiv.) and 2,3,4,5,6-pentafluoro-phenylboronic acid (189 mg, 1.0 mmol, 1 equiv.) were added to the solution. The reaction was continued under reflux for 6 h. After cooling to room temperature, the solvent was poured into water, and the mixture was extracted with dichloromethane (3 times × 60 mL). The organic layer was separated and dried over anhydrous Na2SO4, and the solvent was evaporated under vacuum. The crude product was further purified by silica gel column chromatography using a mixture of dichloromethane and petroleum ether (silica gel, dichloromethane / petroleum ether = 1 / 2, volume ratio) as the eluent to give the desired orange solid 1e (272 mg, 61%).

[0064] The 1e NMR and high-resolution mass spectrometry data are as follows: 1 H NMR (400 MHz, CDCl3) δ 10.10 (s, 2H), 8.15 (d, J = 7.3 Hz, 2H), 7.95– 7.89 (m, 6H), 7.80 – 7.71 (m, 4H), 7.64 (t, J = 7.9 Hz, 2H), 7.55 – 7.46 (m,6H), 6.89 (d, J = 7.5 Hz, 2H).13 C NMR (126 MHz, CDCl3) δ 170.0, 169.0, 168.0,158.1, 155.4, 149.3 (d, J = 19.0 Hz), 140.5, 137.5 (d, J = 43.2 Hz), 136.7,134.3, 133.9, 133.3, 130.6, 130.5, 128.6, 124.2, 123.6, 123.5, 122.2, 120.2,116.3, 105.9. 11 B NMR (128 MHz, CDCl3) δ 1.44. HRMS (ESI): calcdC 38 H 16 B2Cl2F 10 N 10 N a [M+Na] + : 917.0904, found 917.0929. Example 6 This example illustrates the synthesis of an eight-membered ring parallel-connected diisoindole heterocyclic hydrazone-boron-aza-fused aromatic hydrocarbon 1f: Chlorobenzene (20 mL) was placed in a pressure flask, and 1-amino-1H-isoindole-3-amine (145 mg, 1.0 mmol), 2-bromo-6-hydrazinopyridine (188 mg, 1.0 mmol, 1 equiv.), and glacial acetic acid (0.2 mL) were added. The mixture was heated to 145°C in a sand bath and maintained for 0.5 hours. Then, 2-naphthylboronic acid (172 mg, 1.0 mmol, 1 equiv.) was added to the solution. The reaction mixture was refluxed for another 6 hours. After cooling to room temperature, the reaction mixture was poured into water (100 mL) and extracted with dichloromethane (3 × 60 mL). The organic layers were combined and dried over anhydrous Na₂SO₄, and the solvent was removed under vacuum. The crude product was further purified by silica gel column chromatography using a mixture of dichloromethane and petroleum ether (silica gel, petroleum ether / dichloromethane = 2 / 1, volume ratio) as the eluent to give the desired yellow solid 1f (659 mg, 81%).

[0065] The 1f NMR and high-resolution mass spectrometry data are as follows: 1 H NMR (400 MHz, CDCl3) δ 10.11 (s, 2H), 8.06 (d, J= 7.6 Hz, 4H), 7.79– 7.69 (m, 4H), 7.35 – 7.30 (m, 4H), 7.22 – 7.15 (m, 6H), 7.04 – 6.96 (m,6H), 6.85 (d, J = 8.3 Hz, 2H), 6.72 (d, J = 8.2 Hz, 2H), 6.55 (d, J = 7.4 Hz, 2H). 13 C NMR (101 MHz, CDCl3) δ 166.1, 165.0, 158.3, 157.3, 148.26, 149.8, 148.3,140.0, 133.9, 132.8, 132.5, 131.1, 130.0, 129.7, 128.7, 127.5, 127.1, 125.8,124.5, 124.4, 122.3, 122.1, 113.1, 107.4. 11 B NMR (128 MHz, CDCl3) δ 2.53. HRMS(ESI): calcd C 46 H 31 B2Cl2N 10 [M+H] + : 815.2296, found 872.2288. Example 7 This example illustrates the synthesis of 1g of an eight-membered ring parallel bisisoindole heterocyclic hydrazone boron azeotropic fused ring aromatic hydrocarbon: Chlorobenzene (20 mL) was placed in a pressure flask, and 1-amino-1H-isoindole-3-amine (143 mg, 1.0 mmol), 2-hydrazino-5-chloropyridine (148 mg, 1.0 mmol, 1 equiv.), and HOAc (0.2 mL) were added. The mixture was heated to 145 °C in a sand bath and maintained for 0.5 h. Then, 2-naphthyl-phenylboronic acid (248 mg, 1.0 mmol, 1 equiv.) was added to the solution. The reaction was continued under reflux for 6 h. After cooling to room temperature, the solvent was poured into water, and the mixture was extracted with dichloromethane (3 times × 60 mL). The organic layer was separated and dried over anhydrous Na₂SO₄, and the solvent was evaporated under vacuum. The crude product was further purified by silica gel column chromatography using a mixture of dichloromethane and petroleum ether (silica gel, dichloromethane / petroleum ether = 1 / 2, volume ratio) as the eluent to give 1 g (381 mg, 82%) of the desired yellow solid.

[0066] The 1g NMR and high-resolution mass spectrometry data are as follows: 1 H NMR (400 MHz, CDCl3) δ 10.41 (s, 2H), 8.10 (d, J = 7.6 Hz, 2H), 8.04(d, J = 7.6 Hz, 2H), 7.92 – 7.86 (m, 4H), 7.77 – 7.74 (m, 4H), 7.71 – 7.66 (m,4H), 7.55 – 7.41 (m, 16H), 7.32 (d, J = 8.3 Hz, 2H), 7.22 (t, J = 7.5 Hz, 2H), 7.08 (d, J = 7.8 Hz, 4H), 7.03 (t, J = 7.6 Hz, 2H), 6.97 (d, J = 7.9 Hz, 4H), 6.85– 6.80 (m, 4H), 6.67 (d, J = 7.4 Hz, 2H). 13 C NMR (126 MHz, CDCl3) δ 151.3,149.0, 147.7, 147.1, 146.8, 142.9, 135.1, 134.2, 134.0, 133.4, 130.6, 130.0,129.8, 129.5, 129.3, 129.0, 128.9, 128.5, 128.2, 127.7, 126.8, 126.7, 126.2,125.5, 124.4, 123.3, 120.1, 118.8, 116.8. 11 B NMR (128 MHz, CDCl3) δ 2.85. HRMS(ESI): calcd C 58 H 39 B2Cl2N 10 [M+H] + : 967.2922, found 967.2931. Example 8 This example illustrates the synthesis of an eight-membered ring parallel bisisoindole heterocyclic hydrazone boron nitride fused ring aromatic hydrocarbon in 1h: Chlorobenzene (20 mL) was placed in a pressure flask, and 1-amino-1H-isoindole-3-amine (145 mg, 1.0 mmol), 2-bromo-6-hydrazinopyridine (145 mg, 1.0 mmol, 1 equiv.), and glacial acetic acid (0.2 mL) were added. The mixture was heated to 145°C in a sand bath and maintained for 0.5 hours. Then, K3PO4 (230 mg, 1.0 mmol, 1 equiv.) and 3-thiopheneboronic acid (256 mg, 2.0 mmol, 2 equiv.) were added to the solution. The reaction mixture was refluxed for another 8 hours. After cooling to room temperature, the reaction mixture was poured into water (100 mL) and extracted with dichloromethane (3 × 60 mL). The organic layers were combined and dried over anhydrous Na2SO4, and the solvent was removed under vacuum. The crude product was further purified by silica gel column chromatography using a mixture of dichloromethane and petroleum ether (silica gel, n-hexane / dichloromethane = 2 / 1, volume ratio) as the eluent to give the desired yellow solid for 1 h (479 mg, 59%).

[0067] The 1-hour NMR and high-resolution mass spectrometry data are as follows: 1 H NMR (400 MHz, DMSO- d 6) δ 10.36 (s, 2H), 8.10 (s, 2H), 7.97 (d, J =7.6 Hz, 2H), 7.77 – 7.61 (m, 4H), 7.44 (t, J = 7.9 Hz, 2H), 7.24 (s, 2H), 6.92– 6.80 (m, 2H), 6.74 (s, 2H), 6.72 – 6.62 (m, 4H). 13 C NMR (126 MHz, DMSO- d 6) δ158.2, 156.9, 149.3, 148.0, 140.1, 133.8, 132.7, 130.1, 129.8, 129.6, 128.6,127.3, 124.1, 122.1, 121.8, 112.8, 107.4. 11 B NMR (128 MHz, DMSO- d 6) δ 2.77.HRMS (ESI): calcd C 34 H 23 B2B2Cl2N 10 S2[M+H] +: 727.1112, found 727.1148. Example 9 This example illustrates the synthesis of an eight-membered ring parallel bisisoindole heterocyclic hydrazone boron nitride fused ring aromatic hydrocarbon 1i: Chlorobenzene (20 mL) was placed in a pressure flask, and 1-amino-1H-isoindole-3-amine (145 mg, 1.0 mmol), 2-bromo-6-hydrazinopyridine (188 mg, 1.0 mmol, 1 equiv.), and glacial acetic acid (0.2 mL) were added. The mixture was heated to 145°C in a sand bath and maintained for 0.5 hours. Then, 4-trifluoromethyl-phenylboronic acid (190 mg, 1.0 mmol, 1 equiv.) was added to the solution. The reaction mixture was refluxed for another 8 hours. After cooling to room temperature, the reaction mixture was poured into water (100 mL) and extracted with dichloromethane (3 × 60 mL). The organic layers were combined and dried over anhydrous Na₂SO₄, and the solvent was removed under vacuum. The crude product was further purified by silica gel column chromatography using a mixture of dichloromethane and petroleum ether (silica gel, n-hexane / dichloromethane = 2 / 1, volume ratio) as the eluent to give the desired yellow solid 1i (327 mg, 81%).

[0068] The 1i NMR and high-resolution mass spectrometry data are as follows: 1 H NMR (400 MHz, CDCl3) δ 9.98 (s, 2H), 8.06 – 8.02 (m, 4H), 7.77 (t, J = 7.2 Hz, 2H), 7.70 (t, J = 7.6 Hz, 2H), 7.34 – 7.30 (m, 2H), 7.26 – 7.24 (m, 2H), 6.98 – 6.96 (m, 4H), 6.92 – 6.90 (m, 4H), 6.79 (dd, J = 7.4, 0.8 Hz, 2H). 13 C NMR (101 MHz, CDCl3) δ 163.7, 158.0, 157.5, 149.6, 140.1, 138.6, 133.4,133.0, 131.2, 129.9, 129.6, 128.7 (q, J F-C = 32.3 Hz), 128.2, 125.6, 124.3 (q, J F-C= 272.2 Hz), 123.5, 122.9, 122.2, 122.0, 120.3, 117.1, 107.7. 11 B NMR (128MHz, CDCl3) δ 2.76. HRMS (ESI): calcd C 40 H 26 B2Br2F6N 10 [M+H] + : 939.0721, found940.0736. Example 10 This embodiment illustrates the synthesis of an eight-membered ring parallel bisisoindole heterocyclic hydrazone boron nitride fused ring aromatic hydrocarbon 1j: Chlorobenzene (20 mL) was placed in a pressure flask, and 1-amino-1H-isoindole-3-amine (143 mg, 1 mmol), 2-bromo-5-hydrazinopyridine (188 mg, 1 mmol, 1 equiv.), and glacial acetic acid (HOAc, 0.2 mL) were added. The mixture was heated to 145°C in a sand bath and maintained for 0.5 h. Then, K3PO4 (230 mg, 1.0 mmol, 1 equiv.) and 4-trifluoromethyl-phenylboronic acid (190 mg, 1.0 mmol, 1 equiv.) were added to the solution. The reaction mixture was refluxed for 6 h. After cooling to room temperature, the reaction mixture was poured into water (50 mL) and extracted with dichloromethane (3 × 30 mL). The organic layers were combined and dried over anhydrous Na2SO4, and the solvent was removed under vacuum. The crude product was further purified by silica gel column chromatography using a mixture of dichloromethane and petroleum ether (silica gel, petroleum ether / dichloromethane = 2 / 1, volume ratio) as the eluent to give the desired yellow solid 1j (254 mg, 63%).

[0069] The 1J NMR and high-resolution mass spectrometry data are as follows: 1 H NMR (400 MHz, CDCl3) δ 9.65 (s, 2H), 8.11 (s, 2H), 8.02 (d, J = 7.5Hz, 2H), 7.81 – 7.74 (m, 4H), 7.65 (t, J = 7.4 Hz, 2H), 7.55 (dd, J = 9.0, 2.1Hz, 2H), 7.30 (d, J = 8.8 Hz, 2H), 6.93 (d, J= 7.9 Hz, 4H), 6.87 (d, J = 7.8 Hz, 4H). 13 C NMR (126 MHz, CDCl3) δ 159.0, 151.3, 145.8, 141.8, 141.7, 141.3,139.2, 132.7, 132.4, 131.6, 129.6 (q, J = 288.5 Hz), 127.7, 127.6, 125.8,123.9, 123.5, 123.2 (q, J = 34.0 Hz), 111.8, 106.8, 106.6. 11 B NMR (128 MHz, CDCl3) δ 2.34. 19 F NMR (376 MHz, CDCl3) δ -62.76. HRMS (ESI): calcdC 40 H 25 B2Br2F6N 10 [M+H] + : 939.0721, found m / z 939.0719. Example 11 This example illustrates the synthesis of an eight-membered ring parallel bisisoindole heterocyclic hydrazone boron nitride fused ring aromatic hydrocarbon 1k: Chlorobenzene (20 mL) was placed in a pressure flask, and 1-amino-1H-isoindole-3-amine (145 mg, 1.0 mmol), 4-methyl-2-hydrazinobenzothiazole (179 mg, 1.0 mmol, 1 equiv.), and glacial acetic acid (0.2 mL) were added. The mixture was heated to 145°C in a sand bath and maintained for 0.5 h. Then, K3PO4 (230 mg, 1.0 mmol, 1 equiv.) and 4-trifluoromethyl-phenylboronic acid (190 mg, 1.0 mmol, 1 equiv.) were added to the solution. The reaction mixture was refluxed for another 8 h. After cooling to room temperature, the reaction mixture was poured into water (100 mL) and extracted with dichloromethane (3 × 60 mL). The organic layers were combined and dried over anhydrous Na2SO4, and the solvent was removed under vacuum. The crude product was further purified by silica gel column chromatography using a mixture of dichloromethane and petroleum ether (silica gel, petroleum ether / dichloromethane = 2 / 1, volume ratio) as the eluent to give the desired yellow solid 1k (396 mg, 49%).

[0070] The 1k NMR and high-resolution mass spectrometry data are as follows: 1 H NMR (400 MHz, CDCl3) δ 10.07 (s, 2H), 8.10 (d, J = 7.7 Hz, 2H), 7.90(d, J = 4.8 Hz, 2H), 7.80 (t, J = 7.5 Hz, 2H), 7.68 (t, J = 7.4 Hz, 2H), 7.48 (d, J =7.6 Hz, 2H), 7.16 (d, J = 7.3 Hz, 2H), 7.06 – 6.70 (m, 10H), 2.70 (s, 6H). 13 CNMR (126 MHz, CDCl3) δ 165.4, 158.4, 151.1, 150.7, 133.5, 133.3, 131.4,130.5, 130.4, 129.4, 129.0, 128.6, 126.6, 126.5 (q, J F-C = 273.4 Hz), 125.2,123.7, 122.9 (q, J F-C = 31.5 Hz), 121.9, 119.9, 118.7, 18.6. 11 B NMR (128 MHz, CDCl3) δ 0.71. 19 F NMR (376 MHz, CDCl3) δ -62.92 – 63.16 (m). HRMS (ESI): calcdfor C 46 H 31 B2F6N 10 S2[M+H] + : 923.2265, found m / z 923.2246. Example 12 This example illustrates the synthesis of an eight-membered ring parallel bisisoindole heterocyclic hydrazone boron nitride fused ring aromatic hydrocarbon 11: Chlorobenzene (20 mL) was placed in a pressure flask, and 1-amino-1H-isoindole-3-amine (143 mg, 1.0 mmol), 2-hydrazino-1,3-benzimidazole (148 mg, 1.0 mmol, 1 equiv.), and HOAc (0.2 mL) were added. The mixture was heated to 145 °C in a sand bath and maintained for 0.5 h. Then, K3PO4 (230 mg, 1.0 mmol, 1 equiv.) and 4-trifluoromethyl-phenylboronic acid (189 mg, 1.0 mmol, 1 equiv.) were added to the solution. The reaction was continued under reflux for 6 h. After cooling to room temperature, the solvent was poured into water, and the mixture was extracted with dichloromethane (3 times × 60 mL). The organic layer was separated and dried over anhydrous Na2SO4, and the solvent was evaporated under vacuum. The crude product was further purified by silica gel column chromatography using a mixture of dichloromethane and petroleum ether (silica gel, dichloromethane / petroleum ether = 1 / 2, volume ratio) as eluent to give 1 liter (271 mg, 49%) of the desired orange solid. The 1L NMR and high-resolution mass spectrometry data are as follows: 1 H NMR (400 MHz, DMSO- d 6) δ 8.05 (t, J = 7.8 Hz, 4H), 7.92 (t, J = 7.6 Hz, 2H), 7.84 (t, J = 7.6 Hz, 2H), 7.44 (d, J = 7.8 Hz, 2H), 7.19 (d, J = 7.7 Hz, 2H),7.06 – 6.99 (m, 10H), 6.95 (t, J = 7.5 Hz, 2H). 13 C NMR (126 MHz, DMSO- d 6) δ158.1, 152.5, 149.6, 148.2, 142.7, 133.8, 133.2, 133.0, 131.5, 130.5, 128.6,127.2 (q, J F-C = 30.4 Hz), 124.3 (q, J F-C = 273.4 Hz), 123.1, 121.7, 120.8, 119.6,116.0, 109.6. 11B NMR (128 MHz, DMSO- d 6) δ 4.33. 19 F NMR (376 MHz, DMSO- d 6) δ -62.66. HRMS (ESI): calcd for C 40 H 29 B2F6N 12 [M+H] + : 861.2728, found 861.2729. Example 13 This example illustrates the synthesis of the eight-membered ring parallel diisoindole heterocyclic hydrazone boron nitride fused ring aromatic hydrocarbon 1m: Chlorobenzene (20 mL) was placed in a pressure flask, and 1-amino-1H-isoindole-3-amine (145 mg, 1.0 mmol), 2-bromo-6-hydrazinopyridine (145 mg, 1.0 mmol, 1 equiv.), and glacial acetic acid (0.2 mL) were added. The mixture was heated to 145 °C in a sand bath and maintained for 0.5 h. Then, K3PO4 and n-butylboronic acid (200 mg, 2.0 mmol, 2 equiv.) were added to the solution. The reaction mixture was refluxed for another 8 h. After cooling to room temperature, the reaction mixture was poured into water (100 mL) and extracted with dichloromethane (3 × 60 mL). The organic layers were combined, dried, and then the solvent was removed under vacuum. The crude product was further purified by silica gel column chromatography using a 1 / 1 volume ratio of dichloromethane and petroleum ether as the eluent to obtain the desired yellow solid 1m (301 mg, 79%).

[0071] The 1m NMR and high-resolution mass spectrometry data are as follows: 1 H NMR (400 MHz, CDCl3) δ 9.62 (s, 2H), 7.89 (t, J = 8.6 Hz, 4H), 7.61(t, J = 7.4 Hz, 2H), 7.56 (t, J = 7.4 Hz, 2H), 7.44 – 7.39 (m, 4H), 6.84 (dd, J =6.1, 2.0 Hz, 2H), 1.24 – 1.15 (m, 4H), 1.13 – 1.07 (m, 4H), 1.02 – 0.88 (m,4H), 0.74 (t, J = 7.3 Hz, 6H).13 C NMR (101 MHz, CDCl3) δ 159.1, 155.8, 150.1,139.9, 138.8, 133.9, 132.0, 129.5, 129.3, 121.7, 121.5, 116.1, 107.5, 27.3,25.6, 21.1, 14.1. 11 B NMR (128 MHz, CDCl3) δ 5.34. HRMS (ESI): calcd forC 34 H 35 B2Br2N 10 [M+H] + : 763.1599, found 763.1602. Example 14 This example illustrates the synthesis of an eight-membered ring parallel bisisoindole heterocyclic hydrazone boron nitride fused ring aromatic hydrocarbon 1n: Chlorobenzene (20 mL) was placed in a pressure flask, and 1-amino-1H-isoindole-3-amine (145 mg, 1.0 mmol), 2-bromo-6-hydrazinopyridine (145 mg, 1.0 mmol, 1 equiv.), and glacial acetic acid (0.2 mL) were added. The mixture was heated to 145 °C in a sand bath and maintained for 0.5 h. Then, K3PO4 and n-decylboronic acid (234 mg, 2.0 mmol, 2 equiv.) were added to the solution. The reaction mixture was refluxed for another 8 h. After cooling to room temperature, the reaction mixture was poured into water (100 mL) and extracted with dichloromethane (3 × 60 mL). The organic layers were combined and dried over anhydrous Na2SO4, and the solvent was removed under vacuum. The crude product was further purified by silica gel column chromatography using a mixture of dichloromethane and petroleum ether (silica gel, petroleum ether / dichloromethane = 1 / 1, volume ratio) as the eluent to give the desired yellow solid 1n (396 mg, 85%).

[0072] The 1n NMR and high-resolution mass spectrometry data are as follows: 1 H NMR (400 MHz, CDCl3) δ 9.62 (s, 2H), 7.92 – 7.87 (m, 4H), 7.62 –7.53 (m, 4H), 7.44 – 7.38 (m, 4H), 6.84 (dd, J = 6.2, 1.9 Hz, 2H), 1.26 – 1.06(m, 34H), 0.90 – 0.86 (m, 2H), 0.84 (t,J = 7.0 Hz, 6H). 13 C NMR (101 MHz, CDCl3)δ 159.1, 155.9, 150.1, 139.9, 138.8, 133.9, 132.0, 129.5, 129.3, 121.7,121.5, 116.1, 107.5, 32.6, 31.9, 31.6, 29.8, 29.7, 29.6, 29.4, 25.0, 22.7,14.1. 11 B NMR (128 MHz, CDCl3) δ 4.82. HRMS (ESI): calcd for C 46 H 59 B2Br2N 10 [M+H] + :931.3477, found 931.3485. Example 15 This example illustrates the synthesis of an eight-membered ring parallel-connected diisoindole heterocyclic hydrazone-boron-aza-fused aromatic hydrocarbon 2a: BBN1i (155 mg, 0.16 mmol) was added to a Schlenk flask, followed by Pd(PPh3)4 (7 mg) and tributyltin (75 mg, 0.2 mmol) in toluene (20 mL). The mixture was then stirred in a 110 °C metal bath for 48 hours under sealed conditions. The reaction mixture was cooled to room temperature, poured into water (100 mL), and extracted with dichloromethane (3 × 60 mL). The organic layers were combined and dried over anhydrous Na2SO4. The crude product was further purified by silica gel column chromatography using a mixture of dichloromethane and petroleum ether (silica gel, petroleum ether / dichloromethane = 1 / 1, v / v) as eluent to give the desired orange solid 2a (94 mg, 75%).

[0073] The 2a NMR and high-resolution mass spectrometry data are as follows: 1 H NMR (400 MHz, CDCl3) δ 9.98 (s, 1H), 9.85 (s, 1H), 8.06 – 7.99 (m,3H), 7.78 – 7.66 (m, 3H), 7.54 – 7.49 (m, 3H), 7.38 (d, J = 5.0 Hz, 1H), 7.33 –7.24 (m, 2H), 7.14 (t, J= 4.4 Hz, 1H), 7.06 – 7.00 (m, 5H), 6.96 – 6.90 (m,4H), 6.77 (d, J = 7.2 Hz, 1H). 13 C NMR (126 MHz, CDCl3) δ 158.1, 158.0, 157.6,149.6, 140.0, 138.8, 138.7, 133.4, 133.3, 132.9, 132.8, 131.5, 131.2, 129.8,129.6, 128.7, 128.5, 128.4, 126.9, 125.5, 125.4, 124.4, 123.5, 123.3 (q, J F-C =273.2 Hz), 122.1, 121.9, 121.8, 117.0, 109.4, 107.6. 11 B NMR (128 MHz, CDCl3) δ3.43. 19 F NMR (376 MHz, CDCl3) δ -62.65 – 62.73 (m). HRMS (ESI) calcd forC 44 H 28 B2BrF6N 10 S [M+H] + : 943.1493, found 943.1521. Example 16 This example illustrates the synthesis of 2b, an eight-membered ring parallel diisoindole heterocyclic hydrazone boron azeotropic fused ring aromatic hydrocarbon: BBN1i (155 mg, 0.16 mmol) was added to a Schlenk flask. Pd(PPh3)4 (7 mg) and tributyltin (226 mg, 0.6 mmol) were then added using toluene (20 mL) as solvent. The mixture was then stirred in a 110 °C metal bath for 48 hours under sealed conditions. The reaction mixture was cooled to room temperature, poured into water (100 mL), and extracted with dichloromethane (3 × 60 mL). The organic layers were combined and dried over anhydrous Na2SO4. The crude product was further purified by silica gel column chromatography using a mixture of dichloromethane and petroleum ether (silica gel, petroleum ether / dichloromethane = 1.5 / 1, v / v) as eluent to give the desired orange solid 2b (121 mg, 78%).

[0074] The 2b NMR and high-resolution mass spectrometry data are as follows: 1 H NMR (400 MHz, CDCl3) δ 10.41 (s, 2H), 8.01 (d, J = 7.8 Hz, 2H), 7.90(d, J = 7.1 Hz, 2H), 7.64 (t, J = 7.8 Hz, 2H), 7.59 (t, J = 7.9 Hz, 2H), 7.51 –7.48 (m, 4H), 7.45 – 7.37 (m, 4H), 7.20 (d, J = 7.5 Hz, 2H), 7.11 – 7.00 (m,10H). 13 C NMR (126 MHz, CDCl3) δ 158.0, 157.9, 157.3, 149.5, 148.8, 145.4,138.6, 137.1, 133.3, 132.8, 132.7, 131.4, 131.2, 129.8, 129.2, 128.3, 126.7,124.4 (q, J F-C = 273.2 Hz), 124.3, 124.1, 124.0, 123.9, 123.4, 122.6, 121.9,121.7, 121.1, 117.0, 109.2, 107.7. 11 B NMR (128 MHz, CDCl3) δ 0.88. 19 F NMR (376MHz, CDCl3) δ -62.65, -62.73. HRMS (ESI) calcd for C 48 H 31 B2F6N 10 S2[M+H] + :947.2265, found 947.2290. Example 17 This example illustrates the synthesis of 2c, an eight-membered ring parallel diisoindole heterocyclic hydrazone boron azeotropic fused ring aromatic hydrocarbon: BBN1i (155 mg, 0.16 mmol) was added to a Schlenk flask, followed by Pd(PPh3)4 (7 mg) and tributyltin (75 mg, 0.2 mmol) in toluene (20 mL). The mixture was then stirred in a 110 °C metal bath for 48 hours under sealed conditions. The reaction mixture was cooled to room temperature, poured into water (100 mL), and extracted with dichloromethane (3 × 60 mL). The organic layers were combined and dried over anhydrous Na2SO4. The crude product was further purified by silica gel column chromatography using a mixture of dichloromethane and petroleum ether (silica gel, petroleum ether / dichloromethane = 2 / 1, v / v) as eluent to give the desired orange solid 2c (173 mg, 83%).

[0075] The 2c NMR and high-resolution mass spectrometry data are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.03 (d, J = 7.7 Hz, 2H), 7.71 (t, J = 7.6 Hz,2H), 7.55 – 7.47 (m, 4H), 7.35 (s, 2H), 7.24 (d, J = 8.2 Hz, 4H), 7.05 – 6.92(m, 12H), 2.63 (t, J = 7.7 Hz, 4H), 1.69 – 1.61 (m, 4H), 1.39 – 1.26 (m, 12H), 0.90 (t, J = 6.8 Hz, 6H). 13 C NMR (126 MHz, CDCl3) δ 158.0, 144.6, 138.6, 133.3,132.7, 131.5, 129.7, 129.4, 129.3, 129.2, 125.8, 125.6, 125.5, 123.4, 121.7,109.1, 109.0, 108.9, 107.8, 107.7, 107.6, 107.6, 31.7, 30.7, 30.4, 29.0,22.60, 14.1. 11 B NMR (128 MHz, CDCl3) δ 1.36. 19F NMR (376 MHz, CDCl3) δ -62.65,62.73.HRMS (ESI) calcd for C 60 H 55 B2F6N 10 S2[M+H] + : 1115.4143, found 1115.4167. Example 18 This example illustrates the synthesis of 2d eight-membered ring parallel diisoindole heterocyclic hydrazone boron nitride fused ring aromatic hydrocarbons: BBN1i (155 mg, 0.16 mmol) was added to a Schlenk flask. Using toluene (20 mL) as solvent, Pd(PPh3)4 (10 mg), triphenylamine 3-borate (578 mg, 2.00 mmol), and a saturated solution of Na2CO3 (5 mL) were added. The mixture was then stirred in a 110 °C metal bath for 48 hours under sealed conditions. The reaction mixture was cooled to room temperature, poured into water (100 mL), and extracted with dichloromethane (3 × 60 mL). The organic layers were combined and dried over anhydrous Na2SO4. The crude product was further purified by silica gel column chromatography using a mixture of dichloromethane and petroleum ether (silica gel, petroleum ether / dichloromethane = 3 / 1, v / v) as eluent to give the desired orange solid 2d (132 mg, 79%).

[0076] The 2D NMR and high-resolution mass spectrometry data are as follows: 1 H NMR (400 MHz, CDCl3) δ 10.47 (s, 2H), 8.03 (d, J = 8.0 Hz, 2H), 7.81(d, J = 6.9 Hz, 4H), 7.71 (t, J = 7.4 Hz, 2H), 7.55 (t, J = 7.4 Hz, 2H), 7.38 -7.26 (m, 12H), 7.14 (d, J = 7.5 Hz, 14H), 7.07 (t, J = 7.3 Hz, 6H). 7.01 (d, J = 6.9Hz, 4H), 6.94 (d, J = 6.9 Hz, 4H). 13C NMR (126 MHz, CDCl3) δ 158.0, 157.9,155.7, 154.1, 151.6, 148.6, 148.5, 147.5, 144.5, 144.3, 142.1, 141.1, 140.8,138.8, 138.8, 133.5, 133.2, 131.2, 129.8, 129.4, 128.7, 127.4, 126.0, 125.5,124.8, 124.7, 123.5, 123.3, 121.8, 121.7, 119.4, 115.6, 112.7, 110.5, 107.6, 107.4, 107.3. 11 B NMR (128 MHz, CDCl3) δ 1.78. 19 F NMR (376 MHz, CDCl3) δ 62.69.HRMS (ESI) calcd for C 76 H 53 B2F6N 12 [M+H] + : 1269.4606, found 1269.4610. Detection Example 1 X-ray single-crystal diffraction characterization was performed on the representative eight-membered ring parallel bisisoindole heterocyclic hydrazone-boron-nitrogen fused-ring aromatic hydrocarbons 1h, 1k, 1m, and 2c prepared in Examples 8, 11, 14, and 17. The results are as follows: Figures 1-4 As shown.

[0077] Figures 1-4 Single-crystal X-ray diffraction structures of representative eight-membered ring parallel double isoindole heterocyclic hydrazone boron nitride fused ring aromatic hydrocarbons 1h, 1k, 1m, and 2c are shown, verifying the successful synthesis and structural stability of the eight-membered ring parallel double isoindole heterocyclic hydrazone boron nitride fused ring structure constructed in this invention.

[0078] As can be seen from the crystal structure, these eight-membered ring parallel bisisoindole heterocyclic hydrazone-boron-nitrogen heterocyclic fused-ring aromatics all exhibit highly rigid fused-ring skeletons. The core structure contains two NBN units and two B←N coordinate bonds, forming a stable eight-membered ring structure. This structure effectively fixes the molecular geometry through the four-coordinate configuration of boron atoms, restricts intramolecular rotation, helps improve structural stability, and may affect its photophysical properties.

[0079] Furthermore, the crystal structure reveals a degree of planarity in the overall molecule, particularly in the central fused ring region, which facilitates the delocalization of π electrons and charge transport. Different substituents (such as thiophene, trifluoromethyl, and alkyl chains) extend at different angles within the crystal, influencing the molecular packing and intermolecular interactions. For example, the longer alkyl side chain in compound 2c may lead to a looser packing in the solid state, which improves solubility but may hinder charge migration.

[0080] These crystal structure data not only confirmed the accuracy of the target molecular structure, but also provided an important basis for subsequent research on the structure-property relationship and material design.

[0081] Detection Example 2 The eight-membered ring parallel bisisoindole heterocyclic hydrazone borazine heterocyclic fused rings 1a-n prepared in Examples 1-13 were measured in toluene solvent at their maximum absorption wavelengths (λ). abs max / nm), maximum emission wavelength (λ) em max / nm), molar absorptivity (lgε) max ), maximum emission wavelength (λ) em max / nm), Stokes shift (cm) -1 The fluorescence quantum yield (φ) and fluorescence lifetime (ns) were obtained, and the results are shown in Table 1.

[0082] Table 1

[0083] As shown in Table 1, the eight-membered ring parallel diisoindole heterocyclic hydrazone-boron-aza-fused condensed ring aromatic hydrocarbons synthesized in this invention exhibit significant visible light absorption and emission behavior in organic solvents, possessing a large Stokes shift and demonstrating good excitation-emission separation characteristics, which is beneficial for their application in optoelectronic materials. The maximum absorption wavelength (λ) of these compounds in toluene is [not specified in the table]. abs,max The emission wavelengths are mainly concentrated in the range of 430~446 nm, belonging to π-π* electronic transitions, while the maximum emission wavelength (λ) em,max The fluorescence quantum yield (Φ) is located at 465–599 nm, with a Stokes shift ranging from 49–153 nm, indicating significant geometric relaxation or charge rearrangement in the excited state. Compound 1l exhibits the largest Stokes shift (153 nm), suggesting stronger intramolecular charge transfer (ICT) properties or more significant excited-state structural rearrangement. FThe overall fluorescence lifetime (τ) is relatively low (0.001~0.027), which may be related to the large degree of rotational freedom within the molecule or the abundance of non-radiative transition pathways. The fluorescence lifetime (τ) is generally in the range of 0.27~3.13 ns, which is typical of the timescale of organic fluorescent materials.

[0084] Detection Example 3 The representative eight-membered ring parallel bisisoindole heterocyclic hydrazone-boron-nitrogen fused rings prepared in Examples 1-13 exhibit maximum absorption wavelengths (λ) in different organic solvents. abs max / nm), maximum emission wavelength (λ) em max / nm), molar absorptivity (lgε) max ), maximum emission wavelength (λ) em max / nm), Stokes shift (cm) -1 The results for the fluorescence quantum yield (Φ) are shown in Table 2.

[0085] Table 2

[0086] As can be seen from the spectral data in different solvents in Table 2, solvent polarity has a significant impact on absorption and emission wavelengths. For example, compound 1d showed a significant redshift (647 nm) in acetonitrile, indicating that its excited state has strong polar characteristics, further supporting the existence of the ICT mechanism. In addition, some compounds exhibited multiple emission peaks in different solvents (such as 1e and 1g), which may be related to the competition between different conformations or excited state pathways within the molecule.

[0087] In summary, the eight-membered ring parallel bisisoindole heterocyclic hydrazone-boron-nitrogen heterocyclic fused ring compounds of the present invention are constructed through two key steps: condensation of the commercially available raw material 1-amino-1H-isoindole-3-amine with a 2-hydrazino-heterocyclic compound to generate an imine isoindolepyridine hydrazone-Schiff base ligand; then, through fixation with two boron molecules, a series of novel boron-nitrogen fully fused ring molecules are constructed. This type of nitrogen heterocyclic fused ring skeleton is a novel structure constructed from two two-molecule ligands. This structure not only contains two NBN units but also two B←N coordinate bonds, forming a unique BBN structure consisting of an eight-membered ring parallel to two five-membered rings. Its asymmetric structure restricts the rotation of the carbon-nitrogen double bond, thus providing sufficient rigidity and stability. Furthermore, the eight-membered ring parallel bisisoindole heterocyclic hydrazone-boron-nitrogen heterocyclic fused ring compounds of the present invention exhibit a large Stokes shift, demonstrating good excitation-emission separation characteristics, which is beneficial for their application in the fields of fluorescent sensors, organic field-effect transistors, and photoactive layer materials.

[0088] The preferred embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details of the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0089] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable way without contradiction. In order to avoid unnecessary repetition, the present invention will not describe the various possible combinations separately.

[0090] Furthermore, various different embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention, they should also be regarded as the content disclosed by the present invention.

Claims

1. An eight-membered ring fused compound of a parallel bisheteroindole hydrazone boron-nitrogen heterocycle, characterized in that, The structure of the eight-membered ring parallel double isoindole heterocyclic hydrazone boron nitrogen hetero-fused ring compound is shown as formula (I). ； Wherein, Ar is a nitrogen-containing heterocyclic aromatic group, and R is selected from one of aryl, heterocyclic aryl and alkyl.

2. The eight-membered ring fused parallel-bisisoindole heterocyclic hydrazone boron-nitrogen heterocyclic compound according to claim 1, characterized by, The Ar is selected from one of pyridyl, thiazolyl, imidazolyl, halogenated pyridyl, halogenated thiazolyl and halogenated imidazolyl, and R is selected from one of monocyclic aryl, fused ring aryl, halogenated aryl, alkyl-substituted aryl, alkoxy-substituted aryl, pyridyl, pyrrolyl, furanyl, thienyl, thiazolyl, C1-C16 branched alkyl and C1-C16 straight-chain alkyl. Preferably, the Ar is selected from one of 6-chloropyridyl, 6-bromopyridyl, 5-bromopyridyl, 4-methylbenzothiazol-2-yl and benzimidazolyl, and R is selected from one of phenyl, 4-methoxybenzene, 4-trifluoromethoxybenzene, 4-trifluoromethylphenyl, pentafluorophenyl, 2-naphthylphenyl, 4-naphthylphenyl, 4-bromophenyl, 3-thienyl, n-butyl and n-decyl.

3. The eight-membered ring fused bicyclic isatine hydrazone boron-nitrogen heterocycle compound according to claim 1 or 2, characterized in that, The structure of the eight-membered ring parallel double isoindole heterocyclic hydrazone boron nitrogen hetero-fused ring compound is shown as formula 1a-1n and 2a-2d, 。 4. A method for preparing a fused ring compound of an eight-membered ring parallel bisisoindole heterocyclic hydrazone boron-nitrogen, characterized by, The preparation method comprises: 1) condensation reaction of a compound of formula A with a compound of formula B in the presence of a solvent and a Lewis acid to generate an intermediate; 2) ring-closing reaction of the intermediate obtained in step 1) with an aromatic boronic acid of formula C under basic conditions to obtain the compound of general formula (I); ； Wherein, Ar is a nitrogen-containing heterocyclic aromatic group, and R is selected from one of aryl, heterocyclic aryl, C1-C16 branched alkyl and C1-C16 straight-chain alkyl.

5. The production method according to claim 4, characterized by, The Ar is selected from one of pyridyl, thiazolyl, imidazolyl, halogenated pyridyl, halogenated thiazolyl and halogenated imidazolyl, and R is selected from one of monocyclic aryl, fused ring aryl, halogenated aryl, alkyl-substituted aryl, alkoxy-substituted aryl, pyridyl, pyrrolyl, furanyl, thienyl, thiazolyl, C1-C16 branched alkyl and C1-C16 straight-chain alkyl. Preferably, the Ar is selected from one of 6-chloropyridyl, 6-bromopyridyl, 5-bromopyridyl, 4-methylbenzothiazol-2-yl and benzimidazolyl, and R is selected from one of phenyl, 4-methoxybenzene, 4-trifluoromethoxybenzene, 4-trifluoromethylphenyl, pentafluorophenyl, 2-naphthylphenyl, 4-naphthylphenyl, 4-bromophenyl, 3-thienyl, n-butyl and n-decyl.

6. The production method according to claim 4 or 5, characterized by, In step 1), the Lewis acid is selected from one or two or more of acetic acid, p-toluenesulfonic acid, hydrochloric acid and sulfuric acid; preferably acetic acid; The solvent is selected from one or two or more of chlorobenzene, toluene, o-dichlorobenzene, acetonitrile and dichloromethane; preferably chlorobenzene; The molar ratio of the compound of formula A, the compound of formula B and the Lewis acid is 1:1-1.1:0.01-0.

3.

7. The production method according to claim 4 or 5, characterized by, In step 1), the condensation reaction conditions include: the reaction temperature is 80-170°C, preferably 140-150°C; and the reaction time is 0.5-50 hours, preferably 0.5-2 hours.

8. The production method according to claim 4 or 5, characterized by, In step 2), The basic condition is provided by a basic substance selected from one or more of potassium phosphate, sodium carbonate, sodium bicarbonate and sodium hydroxide; preferably potassium phosphate; The molar ratio of the basic substance to the compound of formula A is 3-8:1; The molar ratio of the aromatic boronic acid of formula C to the compound of formula A is 4-20:1; The conditions of the cyclization reaction include: reacting in the form of reflux, the reaction temperature is 100-200℃, and the reaction time is 2-100 hours, preferably 6-10 hours.

9. An eight-membered ring fused compound of a parallel bisheteroindole hydrazone boron-nitrogen heterocycle prepared by the preparation method of claims 4-8.

10. Use of the eight-membered ring fused parallel bisheteroindole hydrazone boron-nitrogen heterocyclic compound according to claims 1 to 3 or 9, characterized in that, The use includes use for preparing a fluorescent sensor, an organic field effect transistor or a photoactive layer material.

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