Preparation method, product and application of a multi-dentate organic ligand and its transition metal coordination polymer

Abstract

This invention relates to the field of functional molecular materials technology, and in particular to a method for preparing a multidentate organic ligand and its transition metal coordination polymer, as well as its products and applications. The structural formula of the multidentate organic ligand is shown in Formula I. The transition metal coordination polymer is obtained by complexing the multidentate organic ligand with a metal salt. This invention provides a multidentate (tridentate) organic ligand containing a "triphenylamine-pyridine-benzotriazole" structure, and uses this multidentate organic ligand to synthesize a novel transition metal coordination polymer containing a "triphenylamine-pyridine-benzotriazole" structure. By introducing an electron-donating group at the para-position of the triphenylamine benzene ring, this invention not only effectively reduces the redox potential but also further improves the solubility of the organic ligand. Compared with the monodentate and bidentate ligands in the prior art, the tridentate ligand prepared by this invention has a stronger binding to the metal, higher stability of the complex, and correspondingly superior electrochromic cycling stability.

Description

Technical Field

[0001] This invention relates to the field of functional molecular materials technology, and in particular to a method for preparing a multidentate organic ligand and its transition metal coordination polymer, as well as its products and applications. Background Technology

[0002] Transition metal coordination polymers, as a branch of metal supramolecular polymers, combine the advantages of both inorganic and organic materials. Their photoelectric properties can be easily modulated through changes in ligand molecular tailoring, metal ions, and coordination modes. Furthermore, coordination polymers based on variable-valence transition metals possess excellent redox properties and abundant electronic transition behaviors, making them a class of high-performance electrochromic materials with advantages such as high optical contrast, fast response time, and multiple color changes.

[0003] Pyridine, polypyridine, and other nitrogen-containing heterocyclic molecules, due to the lone pair of electrons on the nitrogen atom in their structures, readily coordinate with metal ions and possess large π-electron conjugated structures, typically exhibit strong electrochromic properties in their complexes. In particular, when transition metal ions form alternating arrangements with organic molecules containing polypyridine or multiple nitrogen-containing heterocyclic structures, polymeric organometallic complexes with polymer-like structures can be obtained, thus exhibiting even more prominent electrochromic properties. However, these structures containing multiple heterocycles often have poor solubility, which is detrimental to further processing.

[0004] Therefore, how to improve the solubility of transition metal coordination polymers while ensuring electrochromic properties is a technical problem that urgently needs to be solved in the field of functional molecular materials. Summary of the Invention

[0005] Based on the above, this invention provides a method for preparing multidentate organic ligands and their transition metal coordination polymers, as well as their products and applications.

[0006] To achieve the above objectives, the present invention provides the following solution:

[0007] One of the technical solutions of this invention is a multidentate organic ligand with the structural formula shown in Formula I;

[0008]

[0009] In Equation I, R is one of the following structural formulas:

[0010]

[0011] The second technical solution of the present invention is a method for preparing the above-mentioned multidentate organic ligand, comprising the following steps:

[0012] Bis(4-bromophenyl)amine and iodide were subjected to the Ullmann reaction to prepare dibromo-substituted diphenylamine compounds;

[0013] The dibromo-containing diphenylamine-substituted compound is reacted with bis(pinacolyl)diboron via a Suzuki reaction to prepare a 4,4'-diboronic acid pinacolyl triphenylamine compound;

[0014] The 4,4'-diboronic acid pineneol ester triphenylamine compound was reacted with 2,6-dibromo-4-iodopyridine via a Suzuki reaction to obtain 2,6-dibromopyridine-substituted triphenylamine compounds;

[0015] The 2,6-dibromopyridine-substituted triphenylamine compound was reacted with benzotriazole via an Ullmann reaction to obtain the polydentate organic ligand.

[0016] The structural formula of the dibromo-containing diphenylamine-substituted compound is as follows:

[0017] The structural formula of the 4,4'-diboronic acid pineneol ester triphenylamine compound is as follows:

[0018]

[0019] The structural formula of the 2,6-dibromopyridine-substituted triphenylamine compound is as follows:

[0020]

[0021] In the structural formulas of the dibromo-containing diphenylamine-substituted compounds, 4,4'-diboronic acid pinene ester triphenylamine compounds, and 2,6-dibromopyridine-substituted triphenylamine compounds, R independently represents one of the following structural formulas:

[0022]

[0023] In some embodiments of the present invention, the molar ratio of the bis(4-bromophenyl)amine to the iodide is 1:(1-3);

[0024] The molar ratio of the dibromo-containing diphenylamine-substituted compound to the bis(pinacol)diboron is 1:(1.5-4);

[0025] The molar ratio of the 4,4'-diboronic acid pinene ester triphenylamine compound to the 2,6-dibromo-4-iodopyridine is 1:(1.5-4);

[0026] The molar ratio of the 2,6-dibromopyridine-substituted triphenylamine compound to the benzotriazole is 1:(3-7).

[0027] In some embodiments of the present invention, the iodide is 4-iodotoluene, 4-iodoanisole, 9-iodophenanthrene, iodobenzene, 4-iodopropylbenzene, 4-iodobiphenyl, 4-iodocyanobenzene, 1-iodo-4-(1-methylpropyl)benzene, 1-iodonaphthalene, or 4-iodo-tert-butylbenzene.

[0028] The third technical solution of the present invention is the application of the above-mentioned multidentate organic ligands in the preparation of transition metal coordination polymers or electrochromic materials.

[0029] The fourth technical solution of the present invention is a method for preparing a transition metal coordination polymer, comprising the following steps:

[0030] The above-mentioned polydentate organic ligands were complexed with metal salts to obtain the transition metal coordination polymer.

[0031] In some embodiments of the present invention, the molar ratio of the multidentate organic ligand to the metal salt is (2-3):1; the metal salt is an iron salt, cobalt salt, nickel salt, or zinc salt; the temperature of the complexation reaction is 60-100°C, and the time is 10-20 h.

[0032] The fifth technical solution of the present invention is a transition metal coordination polymer prepared by the above-mentioned method for preparing transition metal coordination polymers.

[0033] The sixth technical solution of this invention is the application of the aforementioned transition metal coordination polymer in the preparation of electrochromic materials.

[0034] The seventh technical solution of the present invention is an electrochromic material, the raw materials of which include the above-mentioned multidentate organic ligands or transition metal coordination polymers.

[0035] The present invention discloses the following technical effects:

[0036] This invention provides a multidentate (tridentate) organic ligand containing a "triphenylamine-pyridine-benzotriazole" structure, and uses this multidentate organic ligand to synthesize a novel transition metal coordination polymer containing a "triphenylamine-pyridine-benzotriazole" structure.

[0037] This invention introduces an electron-donating group at the para position of the triphenylamine benzene ring, which not only effectively reduces the redox potential but also further improves the solubility of the organic ligand.

[0038] Compared with the monodentate and bidentate ligands in the prior art, the tridentate ligands prepared by this invention have a stronger binding to metals, higher stability of the complexes, and correspondingly better electrochromic cycling stability. Attached Figure Description

[0039] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0040] Figure 1 The hydrogen nuclear magnetic resonance spectrum of the multidentate organic ligand prepared in Example 1 of this invention.

[0041] Figure 2 The hydrogen nuclear magnetic resonance spectrum of the multidentate organic ligand prepared in Example 4 of this invention.

[0042] Figure 3 The X-ray photoelectron spectrum of the transition metal coordination polymer prepared in Example 11 of this invention is shown.

[0043] Figure 4 The image shows the electrochromatogram of the transition metal coordination polymer film (film 1) prepared in Example 11 of this invention.

[0044] Figure 5 This is a cyclic voltammogram of the transition metal coordination polymer film (film 1) prepared in Example 11 of the present invention.

[0045] Figure 6 The electrochromic response time spectrum of the transition metal coordination polymer film (film 1) prepared in Example 11 of the present invention is shown.

[0046] Figure 7 The hydrogen nuclear magnetic resonance spectrum of the multidentate organic ligand prepared in Example 8 of this invention. Detailed Implementation

[0047] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0048] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Any stated value or intermediate value within a stated range, as well as each smaller range between any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0049] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0050] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0051] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0052] To overcome the poor solubility of transition metal coordination polymers, this invention introduces a triphenylamine group, which also possesses excellent electrochromic properties, into the organic ligand backbone. Its unique helical flexible structure improves the solubility of transition metal coordination polymers. Simultaneously, the excellent electron acceptor benzotriazole introduced into the polydentate ligand further enhances the material's solubility.

[0053] This invention aims to synthesize a class of multidentate ligands based on the "triphenylamine-pyridine-benzotriazole" structure, and to synthesize a series of transition metal coordination polymers through coordination with metal ions. The transition metal coordination polymers prepared by this invention exhibit stable electroactivity, low start-up voltage, fast color conversion speed, and excellent electrochromic properties.

[0054] The first aspect of this invention provides a multidentate organic ligand with the structural formula shown in Formula I;

[0055]

[0056] In Formula I, R is one of the following structural formulas:

[0057]

[0058] A second aspect of the present invention provides a method for preparing the above-mentioned multidentate organic ligand, comprising the following steps:

[0059] Bis(4-bromophenyl)amine and iodide were subjected to the Ullmann reaction to prepare dibromo-substituted diphenylamine compounds;

[0060] The dibromo-containing diphenylamine-substituted compound is reacted with bis(pinacolyl)diboron via a Suzuki reaction to prepare a 4,4'-diboronic acid pinacolyl triphenylamine compound;

[0061] The 4,4'-diboronic acid pineneol ester triphenylamine compound was reacted with 2,6-dibromo-4-iodopyridine via a Suzuki reaction to obtain 2,6-dibromopyridine-substituted triphenylamine compounds;

[0062] The 2,6-dibromopyridine-substituted triphenylamine compound was reacted with benzotriazole via an Ullmann reaction to obtain the polydentate organic ligand.

[0063] In some embodiments of the present invention, the method for preparing the multidentate organic ligand includes the following steps:

[0064] (1) Ullmann reaction

[0065] The bis(4-bromophenyl)amine, iodide, cuprous iodide, o-phenanthroline, and potassium hydroxide were added to a Schlenk flask in a molar ratio of 1:(1-3):(0.04-0.06):(0.04-0.06):(6-10). Three vacuum-nitrogen cycles were then applied to the reaction system using a double-row tube. After the solid reactants were fully immersed in the nitrogen atmosphere, anhydrous toluene (5 ml solvent / mmol diamine monomer) was added using a syringe, and three more vacuum-nitrogen cycles were applied to the system. The system was allowed to react at 100-130°C under a nitrogen atmosphere for 10-40 h. After the reaction was complete, the catalyst was removed by filtration, and the product adhering to the catalyst was washed with dichloromethane (3 x 10 ml). The filtrate was collected and deionized water (V...) was added. 二氯甲烷 V 去离子水 The product was extracted multiple times using a ratio of 2:2 to 1. The organic phases were combined and dried over anhydrous sodium sulfate. The mixture was filtered and the organic solvent in the filtrate was removed by vacuum distillation. Dichloromethane / petroleum ether was used as the eluent (V... 二氯甲烷 V 石油醚 =2 to 10:1), the crude product was purified by silica gel chromatography to obtain N-aryl-4,4'-dibromodiphenylamine (a dibromodiphenylamine-substituted compound).

[0066] The reaction route is as follows:

[0067]

[0068] (2) Suzuki reaction

[0069] N-aryl-4,4'-dibromodiphenylamine substituted compound, bis(pinacolyl)diboron, potassium acetate, and [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride (catalyst) were added to a Schlenk flask in a molar ratio of 1:(1.5–4):(5–8):(0.04–0.06). After three cycles of vacuum-nitrogen circulation, 1,4-dioxane was added as a solvent using a syringe (10 ml 1,4-dioxane / mmol 4,4'-dibromotriphenylamine compound), followed by three more cycles of nitrogen-vacuum circulation. The reaction was carried out at 80–110 °C under a nitrogen atmosphere for 10–40 h. After the reaction, the catalyst was removed by filtration, the filtrate was collected, and the product was extracted multiple times with dedichloromethane and deionized water (Vdichloromethane:Vdeionized water = 2:2–1). The organic phases were combined and dried over anhydrous sodium sulfate. After filtration and rotary evaporation to remove the solvent, 4,4'-diboronic acid pineneol ester triphenylamine compound (boronic acid ester) was obtained.

[0070] The reaction route is as follows:

[0071]

[0072] The 4,4'-diboronic acid pinene ester triphenylamine compound, 2,6-dibromo-4-iodopyridine, potassium carbonate, and tetrakis(triphenylphosphine)palladium prepared above were added to a Schlenk flask in a molar ratio of 1:(1.5–4):(5–8):(0.04–0.06). After three cycles of vacuum-nitrogen circulation, 1,4-dioxane (10 ml 1,4-dioxane / mmol 2,6-dibromo-4-iodopyridine) and water were added as solvents (V 1,4-二氧六环 :V 水 =2~4:1), and three nitrogen-vacuum cycles were continued. After the cycles were completed, the reaction was carried out under a nitrogen atmosphere at 80-110℃ for 10h-40h. After the reaction was complete, the product was discharged into deionized water, filtered, dried, and then washed with methanol. 2,6-Dibromopyridine-substituted triphenylamine compounds were obtained.

[0073] The reaction route is as follows:

[0074]

[0075] (3) Ullmann reaction

[0076] A triphenylamine compound substituted with dibromopyridine, benzotriazole, cuprous iodide, N,N'-dimethylethylenediamine, and potassium carbonate were added to a Schlenk flask in a molar ratio of 1:(3–7):(0.1–0.3):(0.2–0.6):(1–3). After three cycles of vacuum-nitrogen circulation, dimethyl sulfoxide (DMSO) was added as a solvent (10 mL DMSO / mmol 4,4'-dibromotriphenylamine compound) using a syringe, followed by three more cycles of nitrogen-vacuum circulation. The reaction was carried out at 80–120 °C for 36–72 h under a nitrogen atmosphere. After the reaction was complete, 20 mL of deionized water was slowly added to the reaction mixture, and extraction was performed with ethyl acetate (3 x 20 mL). The organic phase was collected, dried over anhydrous sodium sulfate, filtered, and the organic solvent in the filtrate was removed by vacuum distillation. Ethyl acetate / petroleum ether was used as the eluent (V... 乙酸乙酯 V 石油醚 The crude product was purified by column chromatography with a ratio of 10 to 20:1 to obtain the target product (multidentate organic ligand) containing the structure "triphenylamine-pyridine-benzotriazole".

[0077] The reaction route is as follows:

[0078]

[0079] In some embodiments of the present invention, the iodide is 4-iodotoluene, 4-iodoanisole, 9-iodophenanthrene, iodobenzene, 4-iodopropylbenzene, 4-iodobiphenyl, 4-iodocyanobenzene, 1-iodo-4-(1-methylpropyl)benzene, 1-iodonaphthalene, or 4-iodo-tert-butylbenzene.

[0080] The third aspect of this invention provides the application of the above-described polydentate organic ligands in the preparation of transition metal coordination polymers or electrochromic materials.

[0081] A fourth aspect of this invention provides a method for preparing a transition metal coordination polymer, comprising the following steps:

[0082] The above-mentioned polydentate organic ligands were complexed with metal salts to obtain the transition metal coordination polymer.

[0083] In some embodiments of the present invention, the molar ratio of the polydentate organic ligand to the metal salt is (2-3):1.

[0084] In some embodiments of the present invention, the metal salt is a transition metal salt, such as an iron salt, cobalt salt, nickel salt, or zinc salt; more specifically, it can be a bromide, iodide, nitrate, sulfate, phosphate, acetate, etc. of iron, cobalt, nickel, or zinc.

[0085] In some embodiments of the present invention, the temperature of the complexation reaction is 60-100°C and the time is 10-20 hours.

[0086] The fifth aspect of the present invention provides a transition metal coordination polymer prepared by the above-described method for preparing transition metal coordination polymers.

[0087] The sixth aspect of the present invention provides the application of the above-described transition metal coordination polymer in the preparation of electrochromic materials.

[0088] The seventh aspect of the present invention provides an electrochromic material, the raw materials of which include the above-mentioned multidentate organic ligands or transition metal coordination polymers.

[0089] The technical solutions provided by the present invention will be described in detail below with reference to the embodiments, but they should not be construed as limiting the scope of protection of the present invention.

[0090] Example 1

[0091] The structure of the multidentate organic ligand is shown below:

[0092]

[0093] (1) In a Schlenk flask, add 16.35 g (50.0 mmol) bis(4-bromophenyl)amine, 10.9 g (50.0 mmol) 4-iodotoluene, 0.38 g (2.0 mmol) cuprous iodide, 0.36 g (2.0 mmol) o-phenanthroline, and 16.83 g (0.3 mol) potassium hydroxide, and apply three nitrogen-vacuum cycles. Finally, add 250 mL of anhydrous toluene as solvent, and perform three more vacuum-nitrogen cycles. Heat to 110 °C under a nitrogen atmosphere and react for 10 h. After the reaction is complete, filter, wash the catalyst (cuprous iodide) with dichloromethane (3 × 10 mL), collect the filtrate, and wash with dichloromethane (3 × 10 mL) and deionized water (3 × 10 mL). Combine the organic phases and dry with anhydrous sodium sulfate. Filter under vacuum and remove the organic solvent from the filtrate by vacuum distillation. Use dichloromethane / petroleum ether as the eluent (V 二氯甲烷 V 石油醚 The crude product was purified by silica gel column chromatography (r = 3:1) to obtain 5.84 g of dibromo-containing diphenylamine-substituted compound (dibromo compound), with a yield of 28%.

[0094] (2) 5.84 g (14 mmol) of dibromo compound, 5.33 g (21 mmol) of bis(pinacolyl)diboron, 6.87 g (70 mmol) of potassium acetate and 0.41 g (0.56 mmol) of [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride were placed in a Schlenk flask and three vacuum-nitrogen cycles were applied. Then, 140 mL of 1,4-dioxane was added as a solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 80 °C for 10 h under a nitrogen atmosphere. After the reaction was completed, the mixture was extracted with dichloromethane (3 × 10 mL) and deionized water (3 × 10 mL). The organic phases were combined and dried over anhydrous sodium sulfate. After evaporating the organic solvent, 2.86 g of borate ester was obtained, with a yield of 40%.

[0095] 2.86 g (5.6 mmol) of the borate ester prepared above, 3.05 g (8.4 mmol) of 2,6-dibromo-4-iodopyridine, 3.87 g (28 mmol) of potassium carbonate, and 0.26 g (0.22 mmol) of tetrakis(triphenylphosphine)palladium were placed in a Schlenk flask, and three vacuum-nitrogen cycles were applied. 56 mL of 1,4-dioxane and 18 mL of water were added as solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 80 °C for 10 h under a nitrogen atmosphere. After the reaction was complete, the product was discharged into deionized water, filtered, dried, and washed with methanol. 1.76 g of dibromopyridine-substituted triphenylamine compounds were obtained, with a yield of 43%.

[0096] (3) 1.76 g (2.41 mmol) of dibromopyridine-substituted triphenylamine compound, 0.86 g (7.23 mmol) of benzotriazole, 45 mg (0.24 mmol) of cuprous iodide, 42 mg (0.48 mmol) of N,N'-dimethylethylenediamine, and 0.33 g (2.41 mmol) of potassium carbonate were placed in a Schlenk flask, and three vacuum-nitrogen cycles were applied. 24 mL of dimethyl sulfoxide was added as a solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 80 °C for 36 h under a nitrogen atmosphere. After the reaction was complete, 20 mL of deionized water was slowly added to the reaction mixture, and extraction was performed with ethyl acetate (3 × 20 mL). The organic phase was collected and dried over anhydrous sodium sulfate, filtered, and the organic solvent in the filtrate was removed by vacuum distillation. Ethyl acetate / petroleum ether was used as the eluent (V... 乙酸乙酯 V 石油醚 The crude product was purified by column chromatography at a ratio of 12:1 to obtain 0.78 g of the target product (multidentate organic ligand) containing the structure "triphenylamine-pyridine-benzotriazole", with a yield of 37%.

[0097] Example 2

[0098] The structure of the multidentate organic ligand is shown below:

[0099]

[0100] (1) In a Schlenk flask, add 16.35 g (50.0 mmol) bis(4-bromophenyl)amine, 11.7 g (50.0 mmol) 4-iodoanisole, 0.38 g (2.0 mmol) cuprous iodide, 0.36 g (2.0 mmol) o-phenanthroline, and 16.83 g (0.3 mol) potassium hydroxide, and apply three vacuum-nitrogen cycles. Finally, add 250 mL of anhydrous toluene as solvent, and perform three more vacuum-nitrogen cycles. Heat to 110 °C under a nitrogen atmosphere and react for 10 h. After the reaction is complete, filter, wash the catalyst with dichloromethane (3 × 10 mL), collect the filtrate, and wash with dichloromethane (3 × 10 mL) and deionized water (3 × 10 mL). Combine the organic phases and dry with anhydrous sodium sulfate. Filter under vacuum, and remove the organic solvent from the filtrate by vacuum distillation. Use dichloromethane / petroleum ether as eluent (V 二氯甲烷 V 石油醚 The crude product was purified by silica gel chromatography (r = 2:1) to obtain 6.71 g of a dibromo-containing diphenylamine-substituted compound (dibromo compound), with a yield of 31%.

[0101] (2) 6.71 g (15.5 mmol) of dibromo compound, 5.90 g (23.25 mmol) of bis(pinacolyl)diboron, 7.61 g (77.5 mmol) of potassium acetate and 0.45 g (0.62 mmol) of [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride were placed in a Schlenk flask and three vacuum-nitrogen cycles were applied. Then, 155 ml of 1,4-dioxane was added as a solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 80 °C for 10 h under a nitrogen atmosphere. After the reaction was completed, the mixture was extracted with dichloromethane (3 × 10 ml) and deionized water (3 × 10 ml). The organic phases were combined and dried over anhydrous sodium sulfate. After evaporating the organic solvent, 3.60 g of borate ester was obtained, with a yield of 44%.

[0102] 3.60 g (6.82 mmol) of the borate ester prepared above, 3.71 g (10.23 mmol) of 2,6-dibromo-4-iodopyridine, 4.71 g (34.10 mmol) of potassium carbonate, and 0.31 g (0.27 mmol) of tetrakis(triphenylphosphine)palladium were placed in a Schlenk flask, and three vacuum-nitrogen cycles were applied. 68 mL of 1,4-dioxane and 23 mL of water were added as solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 80 °C for 10 h under a nitrogen atmosphere. After the reaction was complete, the product was discharged into deionized water, filtered, dried, and washed with methanol. 1.94 g of dibromopyridine-substituted triphenylamine compounds were obtained, with a yield of 38%.

[0103] (3) 1.94 g (2.6 mmol) of dibromopyridine-substituted triphenylamine, 0.93 g (7.8 mmol) of benzotriazole, 50 mg (0.26 mmol) of cuprous iodide, 46 mg (0.52 mmol) of N,N'-dimethylethylenediamine, and 0.36 g (2.6 mmol) of potassium carbonate were placed in a Schlenk flask, and three vacuum-nitrogen cycles were applied. 26 ml of dimethyl sulfoxide was added as a solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 80 °C for 36 h under a nitrogen atmosphere. After the reaction was complete, 20 ml of deionized water was slowly added to the reaction mixture, and extraction was performed with ethyl acetate (3 × 20 ml). The organic phase was collected and dried over anhydrous sodium sulfate, filtered, and the organic solvent in the filtrate was removed by vacuum distillation. Ethyl acetate / petroleum ether was used as the eluent (V... 乙酸乙酯 V 石油醚 The crude product was purified by column chromatography at a ratio of 10:1 to obtain 0.79 g of the target product (multidentate organic ligand) containing the structure "triphenylamine-pyridine-benzotriazole", with a yield of 34%.

[0104] Example 3

[0105] The structure of the multidentate organic ligand is shown below:

[0106]

[0107] (1) In a Schlenk flask, add 16.35 g (50.0 mmol) bis(4-bromophenyl)amine, 15.20 g (50.0 mmol) 9-iodophenanthrene, 0.38 g (2.0 mmol) cuprous iodide, 0.36 g (2.0 mmol) o-phenanthroline, and 16.83 g (0.3 mol) potassium hydroxide, and apply three vacuum-nitrogen cycles. Finally, add 250 mL of anhydrous toluene as solvent, and perform three more vacuum-nitrogen cycles. Heat to 110 °C under a nitrogen atmosphere and react for 10 h. After the reaction is complete, filter, wash the catalyst with dichloromethane (3 × 10 mL), collect the filtrate, and wash with dichloromethane (3 × 10 mL) and deionized water (3 × 10 mL). Combine the organic phases and dry with anhydrous sodium sulfate. Filter under vacuum and remove the organic solvent from the filtrate by vacuum distillation. Use dichloromethane / petroleum ether as eluent (V 二氯甲烷 V 石油醚 The crude product was purified by silica gel column chromatography (5:1) to obtain 6.01 g of dibromo-containing diphenylamine-substituted compound (dibromo compound), with a yield of 24%.

[0108] (2) 6.01 g (12 mmol) of dibromo compound, 4.57 g (18 mmol) of bis(pinacolyl)diboron, 5.89 g (60 mmol) of potassium acetate and 0.35 g (0.48 mmol) of [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride were placed in a Schlenk flask and three vacuum-nitrogen cycles were applied. Then, 120 mL of 1,4-dioxane was added as a solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 80 °C for 10 h under a nitrogen atmosphere. After the reaction was completed, the mixture was extracted with dichloromethane (3 × 10 mL) and deionized water (3 × 10 mL). The organic phases were combined and dried over anhydrous sodium sulfate. After evaporating the organic solvent, 2.80 g of borate ester was obtained, with a yield of 39%.

[0109] 2.80 g (4.68 mmol) of the borate ester prepared above, 2.55 g (7.02 mmol) of 2,6-dibromo-4-iodopyridine, 3.23 g (23.4 mmol) of potassium carbonate, and 0.22 g (0.19 mmol) of tetrakis(triphenylphosphine)palladium were placed in a Schlenk flask, and three vacuum-nitrogen cycles were applied. 46 mL of 1,4-dioxane and 15 mL of water were added as solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 80 °C for 10 h under a nitrogen atmosphere. After the reaction was complete, the product was discharged into deionized water, filtered, dried, and washed with methanol. 1.63 g of dibromopyridine-substituted triphenylamine compounds were obtained, with a yield of 43%.

[0110] (3) 1.63 g (2.01 mmol) of dibromopyridine-substituted triphenylamine compound, 0.72 g (6.03 mmol) of benzotriazole, 38 mg (0.20 mmol) of cuprous iodide, 35 mg (0.40 mmol) of N,N'-dimethylethylenediamine, and 0.28 g (2.01 mmol) of potassium carbonate were placed in a Schlenk flask, and three vacuum-nitrogen cycles were applied. 20 mL of dimethyl sulfoxide was added as a solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 80 °C for 36 h under a nitrogen atmosphere. After the reaction was complete, 20 mL of deionized water was slowly added to the reaction mixture, and extraction was performed with ethyl acetate (3 × 20 mL). The organic phase was collected and dried over anhydrous sodium sulfate, filtered, and the organic solvent in the filtrate was removed by vacuum distillation. Ethyl acetate / petroleum ether was used as the eluent (V... 乙酸乙酯 V 石油醚 The crude product was purified by column chromatography at a ratio of 15:1 to obtain 0.87 g of the target product (multidentate organic ligand) containing the structure "triphenylamine-pyridine-benzotriazole", with a yield of 45%.

[0111] Example 4

[0112] The structure of the multidentate organic ligand is shown below:

[0113]

[0114] (1) In a Schlenk flask, add 16.35 g (50.0 mmol) bis(4-bromophenyl)amine, 20.40 g (100.0 mmol) iodobenzene, 0.48 g (2.5 mmol) cuprous iodide, 0.45 g (2.5 mmol) o-phenanthroline, and 22.45 g (0.4 mol) potassium hydroxide, and apply three vacuum-nitrogen cycles. Finally, add 250 mL of anhydrous toluene as solvent, and perform three more vacuum-nitrogen cycles. Heat to 120 °C under a nitrogen atmosphere and react for 25 h. After the reaction is complete, filter, wash the catalyst with dichloromethane (3 × 10 mL), collect the filtrate, and wash with dichloromethane (3 × 10 mL) and deionized water (3 × 7.5 mL). Combine the organic phases and dry with anhydrous sodium sulfate. Filter under vacuum, and remove the organic solvent from the filtrate by vacuum distillation. Use dichloromethane / petroleum ether as the eluent (V 二氯甲烷 V 石油醚 The crude product was purified by silica gel chromatography (r = 4:1) to obtain 10.48 g of a dibromo-containing diphenylamine-substituted compound (dibromo compound), with a yield of 52%.

[0115] (2) 10.28 g (26 mmol) of dibromo compound, 19.81 g (78 mmol) of bis(pinacolyl)diboron, 15.31 g (156 mmol) of potassium acetate and 0.95 g (1.3 mmol) of [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride were placed in a Schlenk flask and three vacuum-nitrogen cycles were applied. Then, 260 mL of 1,4-dioxane was added as a solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 100 °C for 25 h under a nitrogen atmosphere. After the reaction was completed, the mixture was extracted with dichloromethane (3 × 10 mL) and deionized water (3 × 7.5 mL). The organic phases were combined and dried over anhydrous sodium sulfate. After evaporating the organic solvent, 6.21 g of borate ester was obtained, with a yield of 48%.

[0116] 6.21 g (12.48 mmol) of the borate ester prepared above, 13.58 g (37.44 mmol) of 2,6-dibromo-4-iodopyridine, 10.35 g (74.88 mmol) of potassium carbonate, and 0.72 g (0.62 mmol) of tetrakis(triphenylphosphine)palladium were placed in a Schlenk flask, and three vacuum-nitrogen cycles were applied. 125 mL of 1,4-dioxane and 42 mL of water were added as solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 100 °C for 25 h under a nitrogen atmosphere. After the reaction was complete, the product was discharged into deionized water, filtered, dried, and washed with methanol. 3.84 g of dibromopyridine-substituted triphenylamine compounds were obtained, with a yield of 43%.

[0117] (3) 3.84 g (5.4 mmol) of dibromopyridine-substituted triphenylamine, 3.21 g (27 mmol) of benzotriazole, 0.21 g (1.08 mmol) of cuprous iodide, 0.19 g (2.16 mmol) of N,N'-dimethylethylenediamine, and 1.49 g (10.8 mmol) of potassium carbonate were placed in a Schlenk flask, and three vacuum-nitrogen cycles were applied. 54 mL of dimethyl sulfoxide was added as a solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 100 °C for 48 h under a nitrogen atmosphere. After the reaction was complete, 20 mL of deionized water was slowly added to the reaction mixture, and extraction was performed with ethyl acetate (3 × 20 mL). The organic phase was collected and dried over anhydrous sodium sulfate, filtered, and the organic solvent in the filtrate was removed by vacuum distillation. Ethyl acetate / petroleum ether was used as the eluent (V... 乙酸乙酯 V 石油醚 The crude product was purified by column chromatography at a ratio of 10:1 to obtain 2.53 g of the target product (multidentate organic ligand) containing the structure "triphenylamine-pyridine-benzotriazole", with a yield of 54%.

[0118] Example 5

[0119] The structure of the multidentate organic ligand is shown below:

[0120]

[0121] (1) In a Schlenk flask, add 16.35 g (50.0 mmol) bis(4-bromophenyl)amine, 24.60 g (100.0 mmol) 4-iodopropylbenzene, 0.48 g (2.5 mmol) cuprous iodide, 0.45 g (2.5 mmol) o-phenanthroline, and 22.45 g (0.4 mol) potassium hydroxide, and apply three vacuum-nitrogen cycles. Finally, add 250 mL of anhydrous toluene as solvent, and perform three more vacuum-nitrogen cycles. Heat to 120 °C under a nitrogen atmosphere and react for 25 h. After the reaction is complete, filter, wash the catalyst with dichloromethane (3 × 10 mL), collect the filtrate, and wash with dichloromethane (3 × 10 mL) and deionized water (3 × 7.5 mL). Combine the organic phases and dry with anhydrous sodium sulfate. Filter under vacuum, and remove the organic solvent from the filtrate by vacuum distillation. Use dichloromethane / petroleum ether as eluent (V 二氯甲烷 V 石油醚 The crude product was purified by silica gel chromatography (r = 3:1) to obtain 10.85 g of a dibromo-containing diphenylamine-substituted compound (dibromo compound), with a yield of 49%.

[0122] (2) 10.85 g (24.5 mmol) of dibromo compound, 18.66 g (73.5 mmol) of bis(pinacolyl)diboron, 14.43 g (147 mmol) of potassium acetate and 0.90 g (1.225 mmol) of [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride were placed in a Schlenk flask and three vacuum-nitrogen cycles were applied. Then, 245 ml of 1,4-dioxane was added as a solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 100 °C for 25 h under a nitrogen atmosphere. After the reaction was completed, the mixture was extracted with dichloromethane (3 × 10 ml) and deionized water (3 × 7.5 ml). The organic phases were combined and dried over anhydrous sodium sulfate. After evaporating the organic solvent, 6.74 g of borate ester was obtained, with a yield of 51%.

[0123] 6.74 g (12.5 mmol) of the borate ester prepared above, 13.60 g (37.5 mmol) of 2,6-dibromo-4-iodopyridine, 10.37 g (75 mmol) of potassium carbonate, and 0.72 g (0.625 mmol) of tetrakis(triphenylphosphine)palladium were placed in a Schlenk flask, and three vacuum-nitrogen cycles were applied. 125 mL of 1,4-dioxane and 42 mL of water were added as solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 100 °C for 25 h under a nitrogen atmosphere. After the reaction was complete, the product was discharged into deionized water, filtered, dried, and washed with methanol. 4.32 g of dibromopyridine-substituted triphenylamine compounds were obtained, with a yield of 46%.

[0124] (3) 4.32 g (5.75 mmol) of dibromopyridine-substituted triphenylamine, 3.42 g (28.75 mmol) of benzotriazole, 0.22 g (1.15 mmol) of cuprous iodide, 0.20 g (2.3 mmol) of N,N'-dimethylethylenediamine, and 1.59 g (11.5 mmol) of potassium carbonate were placed in a Schlenk flask, and three vacuum-nitrogen cycles were applied. 58 mL of dimethyl sulfoxide was added as a solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 100 °C for 48 h under a nitrogen atmosphere. After the reaction was complete, 20 mL of deionized water was slowly added to the reaction mixture, and extraction was performed with ethyl acetate (3 × 20 mL). The organic phase was collected and dried over anhydrous sodium sulfate, filtered, and the organic solvent in the filtrate was removed by vacuum distillation. Ethyl acetate / petroleum ether was used as the eluent (V... 乙酸乙酯 V 石油醚 The crude product was purified by column chromatography at a ratio of 12:1 to obtain 2.51 g of the target product (multidentate organic ligand) containing the structure "triphenylamine-pyridine-benzotriazole", with a yield of 48%.

[0125] Example 6

[0126] The structure of the multidentate organic ligand is shown below:

[0127]

[0128] (1) In a Schlenk flask, add 16.35 g (50.0 mmol) bis(4-bromophenyl)amine, 28.00 g (100.0 mmol) 4-iodobiphenyl, 0.48 g (2.5 mmol) cuprous iodide, 0.45 g (2.5 mmol) o-phenanthroline, and 22.45 g (0.4 mol) potassium hydroxide, and apply three vacuum-nitrogen cycles. Finally, add 250 mL of anhydrous toluene as solvent, and perform three more vacuum-nitrogen cycles. Heat to 120 °C under a nitrogen atmosphere and react for 25 h. After the reaction is complete, filter, wash the catalyst with dichloromethane (3 × 10 mL), collect the filtrate, and wash with dichloromethane (3 × 10 mL) and deionized water (3 × 7.5 mL). Combine the organic phases and dry with anhydrous sodium sulfate. Filter under vacuum, and remove the organic solvent from the filtrate by vacuum distillation. Use dichloromethane / petroleum ether as the eluent (V 二氯甲烷 V 石油醚 The crude product was purified by silica gel chromatography (5:1) to obtain 12.45 g of a dibromo-containing diphenylamine-substituted compound (dibromo compound), with a yield of 52%.

[0129] (2) 12.45 g (26 mmol) of dibromo compound, 19.81 g (78 mmol) of bis(pinacolyl)diboron, 15.31 g (156 mmol) of potassium acetate and 0.95 g (1.3 mmol) of [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride were placed in a Schlenk flask and three vacuum-nitrogen cycles were applied. Then, 260 mL of 1,4-dioxane was added as a solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 100 °C for 25 h under a nitrogen atmosphere. After the reaction was completed, the mixture was extracted with dichloromethane (3 × 10 mL) and deionized water (3 × 7.5 mL). The organic phases were combined and dried over anhydrous sodium sulfate. After evaporating the organic solvent, 6.41 g of borate ester was obtained, with a yield of 43%.

[0130] 6.41 g (11.18 mmol) of the borate ester prepared above, 12.17 g (33.54 mmol) of 2,6-dibromo-4-iodopyridine, 9.27 g (67.08 mmol) of potassium carbonate, and 0.65 g (0.56 mmol) of tetra(triphenylphosphine)palladium were placed in a Schlenk flask, and three vacuum-nitrogen cycles were applied. 112 mL of 1,4-dioxane and 37 mL of water were added as solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 100 °C for 25 h under a nitrogen atmosphere. After the reaction was complete, the product was discharged into deionized water, filtered, dried, and washed with methanol. 4.15 g of dibromopyridine-substituted triphenylamine compounds were obtained, with a yield of 47%.

[0131] (3) 4.15 g (5.25 mmol) of dibromopyridine-substituted triphenylamine, 3.13 g (26.25 mmol) of benzotriazole, 0.20 g (1.05 mmol) of cuprous iodide, 0.19 g (2.10 mmol) of N,N'-dimethylethylenediamine, and 1.45 g (10.5 mmol) of potassium carbonate were placed in a Schlenk flask, and three vacuum-nitrogen cycles were applied. 53 mL of dimethyl sulfoxide was added as a solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 100 °C for 48 h under a nitrogen atmosphere. After the reaction was complete, 20 mL of deionized water was slowly added to the reaction mixture, and extraction was performed with ethyl acetate (3 × 20 mL). The organic phase was collected and dried over anhydrous sodium sulfate, filtered, and the organic solvent in the filtrate was removed by vacuum distillation. Ethyl acetate / petroleum ether was used as the eluent (V... 乙酸乙酯 V 石油醚 The crude product was purified by column chromatography at a ratio of 15:1 to obtain 2.03 g of the target product (multidentate organic ligand) containing the structure "triphenylamine-pyridine-benzotriazole", with a yield of 41%.

[0132] Example 7

[0133] The structure of the multidentate organic ligand is shown below:

[0134]

[0135] (1) In a Schlenk flask, add 16.35 g (50.0 mmol) bis(4-bromophenyl)amine, 22.90 g (100.0 mmol) 4-iodocyanobenzene, 0.48 g (2.5 mmol) cuprous iodide, 0.45 g (2.5 mmol) o-phenanthroline, and 22.45 g (0.4 mol) potassium hydroxide, and apply three vacuum-nitrogen cycles. Finally, add 250 mL of anhydrous toluene as solvent, and perform three more vacuum-nitrogen cycles. Heat to 120 °C under a nitrogen atmosphere and react for 25 h. After the reaction is complete, filter, wash the catalyst with dichloromethane (3 × 10 mL), collect the filtrate, and wash with dichloromethane (3 × 10 mL) and deionized water (3 × 7.5 mL). Combine the organic phases and dry with anhydrous sodium sulfate. Filter under vacuum, and remove the organic solvent from the filtrate by vacuum distillation. Use dichloromethane / petroleum ether as the eluent (V 二氯甲烷 V 石油醚 =10:1), the crude product was purified by silica gel chromatography to obtain 7.92 g of dibromo-containing diphenylamine-substituted compound (dibromo compound), with a yield of 37%.

[0136] (2) 7.92 g (18.5 mmol) of dibromo compound, 14.09 g (55.5 mmol) of bis(pinacolyl)diboron, 10.89 g (111 mmol) of potassium acetate and 0.68 g (0.925 mmol) of [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride were placed in a Schlenk flask and three vacuum-nitrogen cycles were applied. Then, 185 ml of 1,4-dioxane was added as a solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 100 °C for 25 h under a nitrogen atmosphere. After the reaction was completed, the mixture was extracted with dichloromethane (3 × 10 ml) and deionized water (3 × 7.5 ml). The organic phases were combined and dried over anhydrous sodium sulfate. After evaporating the organic solvent, 4.05 g of borate ester was obtained, with a yield of 42%.

[0137] 4.05 g (7.77 mmol) of the borate ester prepared above, 8.46 g (23.31 mmol) of 2,6-dibromo-4-iodopyridine, 6.44 g (46.62 mmol) of potassium carbonate, and 0.45 g (0.39 mmol) of tetrakis(triphenylphosphine)palladium were placed in a Schlenk flask, and three vacuum-nitrogen cycles were applied. 78 mL of 1,4-dioxane and 26 mL of water were added as solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 100 °C for 25 h under a nitrogen atmosphere. After the reaction was complete, the product was discharged into deionized water, filtered, dried, and washed with methanol. 2.53 g of dibromopyridine-substituted triphenylamine compounds were obtained, with a yield of 44%.

[0138] (3) 2.53 g (3.42 mmol) of dibromopyridine-substituted triphenylamine, 2.04 g (17.10 mmol) of benzotriazole, 0.13 g (0.68 mmol) of cuprous iodide, 0.12 g (1.36 mmol) of N,N'-dimethylethylenediamine, and 0.95 g (6.84 mmol) of potassium carbonate were placed in a Schlenk flask, and three vacuum-nitrogen cycles were applied. 34 ml of dimethyl sulfoxide was added as a solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 100 °C for 48 h under a nitrogen atmosphere. After the reaction was complete, 20 ml of deionized water was slowly added to the reaction mixture, and extraction was performed with ethyl acetate (3 × 20 ml). The organic phase was collected and dried over anhydrous sodium sulfate, filtered, and the organic solvent in the filtrate was removed by vacuum distillation. Ethyl acetate / petroleum ether was used as the eluent (V... 乙酸乙酯 V 石油醚 The crude product was purified by column chromatography at a ratio of 12:1 to obtain 1.19 g of the target product (multidentate organic ligand) containing the structure "triphenylamine-pyridine-benzotriazole", with a yield of 39%.

[0139] Example 8

[0140] The structure of the multidentate organic ligand is shown below:

[0141]

[0142] (1) In a Schlenk flask, add 16.35 g (50.0 mmol) bis(4-bromophenyl)amine, 39.00 g (150.0 mmol) 1-iodo-4-(1-methylpropyl)benzene, 0.57 g (3 mmol) cuprous iodide, 0.54 g (3 mmol) o-phenanthroline, and 28.06 g (0.5 mol) potassium hydroxide, and apply three vacuum-nitrogen cycles. Finally, add 250 mL of anhydrous toluene as solvent, and perform three more vacuum-nitrogen cycles. Heat to 130 °C under a nitrogen atmosphere and react for 40 h. After the reaction is complete, filter, wash the catalyst with dichloromethane (3 × 10 mL), collect the filtrate, and wash with dichloromethane (3 × 10 mL) and deionized water (3 × 5 mL). Combine the organic phases and dry with anhydrous sodium sulfate. Filter under vacuum, and remove the organic solvent from the filtrate by vacuum distillation. Use dichloromethane / petroleum ether as the eluent (V 二氯甲烷 V 石油醚 =8:1), the crude product was purified by silica gel chromatography to obtain 7.08 g of dibromo-containing diphenylamine-substituted compound (dibromo compound), with a yield of 31%.

[0143] (2) 7.08 g (15.5 mmol) of dibromo compound, 15.74 g (62 mmol) of bis(pinacolyl)diboron, 12.17 g (124 mmol) of potassium acetate and 0.68 g (0.93 mmol) of [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride were placed in a Schlenk flask and three vacuum-nitrogen cycles were applied. Then, 155 mL of 1,4-dioxane was added as a solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 110 °C for 40 h under a nitrogen atmosphere. After the reaction was complete, the mixture was extracted with dichloromethane (3 × 10 mL) and deionized water (3 × 5 mL). The organic phases were combined and dried over anhydrous sodium sulfate. After evaporating the organic solvent, 3.25 g of borate ester was obtained, with a yield of 38%.

[0144] 3.25 g (5.9 mmol) of the borate ester prepared above, 8.56 g (23.6 mmol) of 2,6-dibromo-4-iodopyridine, 6.52 g (47.2 mmol) of potassium carbonate, and 0.40 g (0.35 mmol) of tetrakis(triphenylphosphine)palladium were placed in a Schlenk flask, and three vacuum-nitrogen cycles were applied. 59 mL of 1,4-dioxane and 20 mL of water were added as solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 110 °C for 40 h under a nitrogen atmosphere. After the reaction was complete, the product was discharged into deionized water, filtered, dried, and washed with methanol. 1.80 g of dibromopyridine-substituted triphenylamine compounds were obtained, with a yield of 40%.

[0145] (3) 1.80 g (2.36 mmol) of dibromopyridine-substituted triphenylamine, 1.97 g (16.52 mmol) of benzotriazole, 0.14 g (0.71 mmol) of cuprous iodide, 0.13 g (1.42 mmol) of N,N'-dimethylethylenediamine, and 0.98 g (7.08 mmol) of potassium carbonate were placed in a Schlenk flask, and three vacuum-nitrogen cycles were applied. 24 mL of dimethyl sulfoxide was added as a solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 120 °C for 72 h under a nitrogen atmosphere. After the reaction was complete, 20 mL of deionized water was slowly added to the reaction mixture, and extraction was performed with ethyl acetate (3 × 20 mL). The organic phase was collected and dried over anhydrous sodium sulfate, filtered, and the organic solvent in the filtrate was removed by vacuum distillation. Ethyl acetate / petroleum ether was used as the eluent (V... 乙酸乙酯 V 石油醚 The crude product was purified by column chromatography at a ratio of 15:1 to obtain 0.59 g of the target product (multidentate organic ligand) containing the structure "triphenylamine-pyridine-benzotriazole", with a yield of 27%.

[0146] Example 9

[0147] The structure of the multidentate organic ligand is shown below:

[0148]

[0149] (1) In a Schlenk flask, add 16.35 g (50.0 mmol) bis(4-bromophenyl)amine, 38.09 g (150.0 mmol) 1-iodonaphthalene, 0.57 g (3 mmol) cuprous iodide, 0.54 g (3 mmol) o-phenanthroline, and 28.06 g (0.5 mol) potassium hydroxide, and apply three vacuum-nitrogen cycles. Finally, add 250 mL of anhydrous toluene as solvent, and perform three more vacuum-nitrogen cycles. Heat to 130 °C under a nitrogen atmosphere and react for 40 h. After the reaction is complete, filter, wash the catalyst with dichloromethane (3 × 10 mL), collect the filtrate, and wash with dichloromethane (3 × 10 mL) and deionized water (3 × 5 mL). Combine the organic phases and dry with anhydrous sodium sulfate. Filter under vacuum, and remove the organic solvent from the filtrate by vacuum distillation. Use dichloromethane / petroleum ether as eluent (V 二氯甲烷 V 石油醚 =10:1), the crude product was purified by silica gel chromatography to obtain 7.89 g of dibromo-containing diphenylamine-substituted compound (dibromo compound), with a yield of 35%.

[0150] (2) 7.89 g (17.5 mmol) of dibromo compound, 17.78 g (75 mmol) of bis(pinacolyl)diboron, 13.74 g (140 mmol) of potassium acetate and 0.77 g (1.05 mmol) of [1,1'-bis(diphenylphosphino)ferrocene]palladium dichloride were placed in a Schlenk flask and three vacuum-nitrogen cycles were applied. Then, 175 ml of 1,4-dioxane was added as a solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 110 °C for 40 h under a nitrogen atmosphere. After the reaction was completed, the mixture was extracted with dichloromethane (3 × 10 ml) and deionized water (3 × 5 ml). The organic phases were combined and dried over anhydrous sodium sulfate. After evaporating the organic solvent, 3.93 g of borate ester was obtained, with a yield of 41%.

[0151] 3.93 g (7.1 mmol) of the borate ester prepared above, 10.30 g (28.4 mmol) of 2,6-dibromo-4-iodopyridine, 7.85 g (56.8 mmol) of potassium carbonate, and 0.50 g (0.43 mmol) of tetrakis(triphenylphosphine)palladium were placed in a Schlenk flask, and three vacuum-nitrogen cycles were applied. 71 mL of 1,4-dioxane and 24 mL of water were added as solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 110 °C for 40 h under a nitrogen atmosphere. After the reaction was complete, the product was discharged into deionized water, filtered, dried, and washed with methanol. 2.43 g of dibromopyridine-substituted triphenylamine compounds were obtained, with a yield of 45%.

[0152] (3) 2.43 g (3.1 mmol) of dibromopyridine-substituted triphenylamine, 2.58 g (21.7 mmol) of benzotriazole, 0.18 g (0.93 mmol) of cuprous iodide, 0.16 g (1.86 mmol) of N,N'-dimethylethylenediamine, and 1.29 g (9.3 mmol) of potassium carbonate were placed in a Schlenk flask, and three vacuum-nitrogen cycles were applied. 31 ml of dimethyl sulfoxide was added as a solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 120 °C for 72 h under a nitrogen atmosphere. After the reaction was complete, 20 ml of deionized water was slowly added to the reaction mixture, and extraction was performed with ethyl acetate (3 × 20 ml). The organic phase was collected and dried over anhydrous sodium sulfate, filtered, and the organic solvent in the filtrate was removed by vacuum distillation. Ethyl acetate / petroleum ether was used as the eluent (V... 乙酸乙酯 V 石油醚 The crude product was purified by column chromatography at a ratio of 20:1 to obtain 1.05 g of the target product (multidentate organic ligand) containing the structure "triphenylamine-pyridine-benzotriazole", with a yield of 37%.

[0153] Example 10

[0154] The structure of the multidentate organic ligand is shown below:

[0155]

[0156] (1) In a Schlenk flask, add 16.35 g (50.0 mmol) bis(4-bromophenyl)amine, 39.00 g (150.0 mmol) 4-iodo-tert-butylbenzene, 0.57 g (3 mmol) cuprous iodide, 0.54 g (3 mmol) o-phenanthroline, and 28.06 g (0.5 mol) potassium hydroxide, and apply three vacuum-nitrogen cycles. Finally, add 250 mL of anhydrous toluene as solvent, and perform three more vacuum-nitrogen cycles. Heat to 130 °C under a nitrogen atmosphere and react for 40 h. After the reaction is complete, filter, wash the catalyst with dichloromethane (3 × 10 mL), collect the filtrate, and wash with dichloromethane (3 × 10 mL) and deionized water (3 × 5 mL). Combine the organic phases and dry with anhydrous sodium sulfate. Filter under vacuum, and remove the organic solvent from the filtrate by vacuum distillation. Use dichloromethane / petroleum ether as eluent (V 二氯甲烷 V 石油醚 =8:1), the crude product was purified by silica gel chromatography to obtain 7.54 g of dibromo-containing diphenylamine-substituted compound (dibromo compound), with a yield of 33%.

[0157] (2) 7.54 g (16.5 mmol) of dibromo compound, 16.76 g (66 mmol) of bis(pinacolyl)diboron, 12.95 g (132 mmol) of potassium acetate and 0.72 g (0.99 mmol) of [1,1'-bis(diphenylphosphine)ferrocene]palladium dichloride were placed in a Schlenk flask and three vacuum-nitrogen cycles were applied. Then, 155 ml of 1,4-dioxane was added as a solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 110 °C for 40 h under a nitrogen atmosphere. After the reaction was completed, the mixture was extracted with dichloromethane (3 × 10 ml) and deionized water (3 × 5 ml). The organic phases were combined and dried over anhydrous sodium sulfate. After evaporating the organic solvent, 3.56 g of borate ester was obtained, with a yield of 39%.

[0158] 3.56 g (6.4 mmol) of the borate ester prepared above, 9.29 g (25.6 mmol) of 2,6-dibromo-4-iodopyridine, 7.08 g (51.2 mmol) of potassium carbonate, and 0.44 g (0.38 mmol) of tetrakis(triphenylphosphine)palladium were placed in a Schlenk flask, and three vacuum-nitrogen cycles were applied. 64 mL of 1,4-dioxane and 21 mL of water were added as solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 110 °C for 40 h under a nitrogen atmosphere. After the reaction was complete, the product was discharged into deionized water, filtered, dried, and washed with methanol. 2.06 g of dibromopyridine-substituted triphenylamine compounds were obtained, with a yield of 42%.

[0159] (3) 2.06 g (2.7 mmol) of dibromopyridine-substituted triphenylamine, 2.25 g (18.9 mmol) of benzotriazole, 0.15 g (0.81 mmol) of cuprous iodide, 0.14 g (1.62 mmol) of N,N'-dimethylethylenediamine, and 1.12 g (8.1 mmol) of potassium carbonate were placed in a Schlenk flask, and three vacuum-nitrogen cycles were applied. 27 mL of dimethyl sulfoxide was added as a solvent using a syringe, and three more vacuum-nitrogen cycles were applied. The reaction was carried out at 120 °C for 72 h under a nitrogen atmosphere. After the reaction was complete, 20 mL of deionized water was slowly added to the reaction mixture, and extraction was performed with ethyl acetate (3 × 20 mL). The organic phase was collected and dried over anhydrous sodium sulfate, filtered, and the organic solvent in the filtrate was removed by vacuum distillation. Ethyl acetate / petroleum ether was used as the eluent (V... 乙酸乙酯 V 石油醚 The crude product was purified by column chromatography at a ratio of 15:1 to obtain 0.77 g of the target product (multidentate organic ligand) containing the structure "triphenylamine-pyridine-benzotriazole", with a yield of 31%.

[0160] Example 11

[0161] The target ligand was polymerized with Fe(BF4)2·6H2O to obtain a transition metal coordination polymer film 1:

[0162] Weigh 176.3 mg (0.2 mmol) of the multidentate organic ligand and 33.8 mg (0.1 mmol) of Fe(BF4)2·6H2O obtained in Example 1 and dissolve them in 100 ml of ethanol. Reflux at 60 °C for 10 h to allow the ligand to completely complex with the metal ions. Filter the insoluble substances while hot, distill under reduced pressure, wash several times with ethanol, and dry under vacuum to obtain 125 mg of solid transition metal coordination polymer.

[0163] Dissolve 50 mg of the above solid in 100 ml of methanol, filter out the insoluble matter, add 5 ml of the solution to the spray bottle of the pneumatic spray gun, and then spray it onto the surface of ITO conductive glass. Place it in an oven and dry it at 30°C for 10 h. After the methanol evaporates on the ITO glass surface, a uniform transition metal coordination polymer film is obtained, which is labeled as film 1.

[0164] Example 12

[0165] The target ligand was polymerized with CoCl2·6H2O to obtain a transition metal coordination polymer film 2:

[0166] Weigh 190.8 mg (0.22 mmol) of the multidentate organic ligand and 23.8 mg (0.10 mmol) of CoCl2·6H2O obtained in Example 4 and dissolve them in 100 ml of ethanol. Reflux at 70 °C for 13 h to allow the ligand to completely complex with the metal ions. Filter the insoluble substances while hot, distill under reduced pressure, wash several times with ethanol, and dry under vacuum to obtain 154 mg of solid transition metal coordination polymer.

[0167] Take 50 mg of the above solid and dissolve it in 100 ml of methanol. Filter out the insoluble matter, take 7 ml of the solution and add it to the spray bottle of the pneumatic spray gun. Then spray it onto the surface of ITO conductive glass and put it in an oven to dry at 40°C for 13 h. After the methanol evaporates on the ITO glass surface, a uniform transition metal coordination polymer film is obtained, which is labeled as film 1.

[0168] Example 13

[0169] The target ligand was polymerized with ZnSO4·7H2O to obtain a transition metal coordination polymer film 3:

[0170] Weigh 216.8 mg (0.25 mmol) of the multidentate organic ligand and 28.8 mg (0.10 mmol) of ZnSO4·7H2O obtained in Example 4 and dissolve them in 100 ml of ethanol. Reflux at 80 °C for 16 h to allow the ligand to completely complex with the metal ions. Filter the insoluble substances while hot, distill under reduced pressure, wash several times with ethanol, and dry under vacuum to obtain 158 mg of solid transition metal coordination polymer.

[0171] Dissolve 50 mg of the above solid in 100 ml of methanol, filter out the insoluble matter, add 9 ml of the solution to the spray bottle of the pneumatic spray gun, and then spray it onto the surface of ITO conductive glass. Place it in an oven and dry it at 50°C for 16 h. After the methanol evaporates on the ITO glass surface, a uniform transition metal coordination polymer film is obtained, which is labeled as film 3.

[0172] Example 14

[0173] The target ligand was polymerized with Ni(OCOCH3)2·4H2O to obtain a transition metal coordination polymer film 4:

[0174] Weigh 275.2 mg (0.3 mmol) of the multidentate organic ligand and 25.9 mg (0.10 mmol) of Ni(OCOCH3)2·4H2O obtained in Example 9 and dissolve them in 100 ml of ethanol. Reflux at 100 °C for 20 h to allow the ligand to completely complex with the metal ions. Filter the insoluble substances while hot, distill under reduced pressure, wash several times with ethanol, and dry under vacuum to obtain 154 mg of solid transition metal coordination polymer.

[0175] Dissolve 50 mg of the above solid in 100 ml of methanol, filter out the insoluble matter, add 10 ml of the solution to the spray bottle of the pneumatic spray gun, and then spray it onto the surface of ITO conductive glass. Place it in an oven and dry it at 60°C for 20 h. After the methanol evaporates on the ITO glass surface, a uniform transition metal coordination polymer film is obtained, which is labeled as film 4.

[0176] Characterization and performance testing

[0177] 1) Figure 1 The 1H NMR spectrum of the multidentate organic ligand prepared in Example 1 is shown below: 1H NMR (500 MHz, Chloroform) δ 8.07 (s, 2H), 7.97 (d, J = 4.1 Hz, 1H), 7.96 (s, 2H), 7.95 (d, J = 4.0 Hz, 1H), 7.56 (s, 1H), 7.54 (s, 1H), 7.41 (d, J = 4.1 Hz, 1H), 7.40 (s, 2H), 7.37 (s, 2H), 7.36 (s, 1H), 7.16 (s, 1H), 7.13 (s, 1H), 7.12 (s, 1H), 2.32 (s, 1H). The peak positions and integrated peak areas are consistent with the structure, indicating the successful preparation of the target organic ligand.

[0178] 2) Figure 2The 1H NMR spectrum of the multidentate organic ligand prepared in Example 4 is shown below: 1H NMR (500 MHz, Chloroform) δ 8.04 (s, 1H), 7.97 (d, J = 4.1 Hz, 1H), 7.96 (s, 1H), 7.95 (d, J = 4.0 Hz, 1H), 7.56 (s, 1H), 7.54 (s, 1H), 7.42–7.40 (m, 1H), 7.40 (s, 1H), 7.39 (s, 1H), 7.38 (d, J = 4.0 Hz, 1H). The peak positions and integrated peak areas are consistent with the structure, indicating the successful preparation of the target organic ligand. (J = 2.5 Hz, 1H), 7.37 (s, 1H), 7.26 (s, 1H), 7.24 (s, 1H), 7.23 (s, 1H), 7.09 (d, J = 1.4 Hz, 1H), 7.07 (d, J = 1.4 Hz, 1H), 7.01 (t, J = 1.5 Hz, 1H), 7.00 (s, 1H), 6.98 (t, J = 1.4 Hz, 1H).

[0179] 3) Figure 7 The hydrogen nuclear magnetic resonance spectrum of the multidentate organic ligand prepared in Example 8 of this invention; 1 ¹H NMR (500MHz, Chloroform) δ 8.10 (s, 1H), 7.96 (s, 2H), 7.55 (s, 1H), 7.55–7.52 (m, 1H), 7.42 (t, J = 7.5Hz, 1H), 7.38 (d, J = 15.0Hz, 2H), 7.37 (s, 1H), 7.18 (s, 1H), 7.18 (s, 1H), 7.06 (s, 1H), 7.06 (s, 1H), 2.55 (s, 1H), 1.52 (s, 1H), 1.16 (s, 1H), 0.76 (s, 1H). The peak positions and integrated peak areas are consistent with the structure, indicating the successful preparation of the target organic ligand.

[0180] 4) Figure 3 X-ray photoelectron spectroscopy (XPS) of the transition metal coordination polymer prepared in Example 11; as shown Figure 3 As shown, XPS elemental analysis detected C and N in the organic ligands, and Fe, B, and F in the metal salts. This demonstrates the successful synthesis of transition metal coordination polymers.

[0181] 5) Figure 4 The image shows the electrochromatogram of the thin film 1 prepared in Example 11. The testing method was as follows: using an electrochemical workstation in Amperometric it Curve mode, voltages of 0V, 1.2V, and 1.3V were applied to the working electrode, and the changes in absorbance at different wavelengths were monitored using a UV-Vis-NIR spectrophotometer. Figure 4As shown, thin film 1 exhibits absorption in both the visible and near-infrared regions. The maximum absorption wavelength of the thin film changes as the voltage increases from 0V to 1.3V.

[0182] 6) Cyclic voltammetry performance of the thin film 1 prepared in Example 11 was tested as follows: The ITO containing the transition metal coordination polymer film from Example 11 was used as the working electrode, a platinum wire as the counter electrode, and Ag / AgCl as the reference electrode. A 0.1 M tetrabutylammonium perchlorate (TBAP) acetonitrile solution was used as the electrolyte. Based on this three-electrode system, the cyclic voltammetry performance was tested using an electrochemical workstation at a scan rate of 100 mV / s. The results are shown in […]. Figure 5 , Figure 5 The cyclic voltammogram of thin film 1 in Example 11; by Figure 5 It can be seen that thin film 1 has a pair of reversible redox potentials.

[0183] 7) Figure 6 The image shows the electrochromic response time spectrum of thin film 1 prepared in Example 11. The testing method was as follows: a square wave voltage of 1.10–1.40 V was applied to the working electrode in Chronoamperometry mode using an electrochemical workstation, while the change in its absorption spectrum at 600 nm was monitored using a UV-Vis-NIR spectrophotometer. Figure 6 It can be seen that the transition metal coordination polymer labeled as film 1 has a fast response speed and excellent cycle stability.

[0184] 8) The solubility of the transition metal coordination polymers prepared in Examples 11-14 was tested. The concentration of the solutions formed by different transition metal coordination polymers in different solvents was 2 mg / mL. The results are shown in Table 1.

[0185] Table 1. Solubility of the transition metal coordination polymers prepared in Examples 11-14 in six common solvents.

[0186]

[0187] Note: ++: Soluble at room temperature; +: Soluble upon heating; -: Insoluble upon heating.

[0188] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. A multidentate organic ligand, characterized in that, The structural formula is shown in Formula I; Formula I is selected from the following structural formulas:

2. A method for preparing the multidentate organic ligand according to claim 1, characterized in that, Includes the following steps: Bis(4-bromophenyl)amine and iodide undergo the Ullmann reaction to prepare dibromo-substituted diphenylamine compounds; the reaction route is as follows: The dibromo-containing diphenylamine-substituted compound undergoes a Suzuki reaction with bis(pinacolyl)diboron to prepare a 4,4'-diaboronic acid pinacolyl ester triphenylamine compound; the reaction route is as follows: The 4,4'-diaboronic acid pinacol ester triphenylamine compound was reacted with 2,6-dibromo-4-iodopyridine via a Suzuki reaction to prepare 2,6-dibromopyridine-substituted triphenylamine compounds; the reaction route is as follows: The 2,6-dibromopyridine-substituted triphenylamine compound was reacted with benzotriazole via a Ullmann reaction to prepare the multidentate organic ligand; the reaction route is as follows: R in the reaction pathway corresponds to that in claim 1.

3. The method for preparing the multidentate organic ligand according to claim 2, characterized in that, The molar ratio of the bis(4-bromophenyl)amine to the iodide is 1:(1-3); The molar ratio of the dibromo-containing diphenylamine-substituted compound to the bis(pinacol)diboron is 1:(1.5-4); The molar ratio of the 4,4'-diboronic acid pinacol ester triphenylamine compound to the 2,6-dibromo-4-iodopyridine is 1:(1.5-4); The molar ratio of the 2,6-dibromopyridine-substituted triphenylamine compound to the benzotriazole is 1:(3-7).

4. The method for preparing the multidentate organic ligand according to claim 2, characterized in that, The iodide is 4-iodotoluene, 4-iodoanisole, 9-iodophenanthrene, iodobenzene, 4-iodopropylbenzene, 4-iodobiphenyl, 4-iodocyanobenzene, 1-iodo-4-(1-methylpropyl)benzene, 1-iodonaphthalene, or 4-iodo-tert-butylbenzene.

5. The application of the multidentate organic ligand as described in claim 1 in the preparation of transition metal coordination polymers or electrochromic materials.

6. A method for preparing a transition metal coordination polymer, characterized in that, Includes the following steps: The multidentate organic ligand described in claim 1 is subjected to a complexation reaction with a metal salt to obtain the transition metal coordination polymer.

7. The method for preparing the transition metal coordination polymer according to claim 6, characterized in that, The molar ratio of the multidentate organic ligand to the metal salt is (2-3):1; the metal salt is a transition metal salt; the temperature of the complexation reaction is 60-100℃, and the time is 10-20h.

8. A transition metal coordination polymer prepared by the method of claim 6 or 7.

9. The application of the transition metal coordination polymer as described in claim 8 in the preparation of electrochromic materials.

10. An electrochromic material, characterized in that, This includes the multidentate organic ligand as described in claim 1 or the transition metal coordination polymer as described in claim 8.

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