Method for electrochemically synthesizing sequence-controllable coordination metal polymer

A technique of coordinating metals and synthesizing sequences, applied to electrodes, electrolytic processes, electrolytic components, etc., can solve the problems of long time consumption, low efficiency, and prone to side reactions, etc., and achieve the effect of short synthesis cycle and high reaction efficiency

Inactive Publication Date: 2020-04-10
CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

For example, Du Prez et al. adopted the aminolysis / chain growth two-step iterative synthesis method to synthesize sequence-accurate oligomers with functionalized side groups without the need for protection / deprotection steps. However, all reactions in the polymerization process took overnight. Time-consuming, inefficient, and prone to side reactions (Angew Chem Int Ed 2013,52,13261-13264)
In summary, the existing methods for the controlled synthesis of polymer sequences still need to be improved

Method used

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  • Method for electrochemically synthesizing sequence-controllable coordination metal polymer
  • Method for electrochemically synthesizing sequence-controllable coordination metal polymer
  • Method for electrochemically synthesizing sequence-controllable coordination metal polymer

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0026] Example 1: Synthesis of monomers with electroactive units

[0027] Just take the synthesis of the following structural monomer as an example, the active core unit of electrochemical oxidation is carbazole, the active core unit of electrochemical reduction is vinyl substituted by benzene ring, and the central element unit of complex metal core is ruthenium.

[0028] Basic synthetic route:

[0029]

[0030] 1. Synthesis of 4'-vinyl-[2,2'; 6',2"] terpyridine

[0031] 200mg (0.64mM) 4'-bromo-2,2':6',2"-terpyridine, 104mg (0.76mM) potassium vinyl trifluoroborate, 3mg (0.0128mM) palladium acetate, 10mg (0.04mM) three Phenylphosphine and 652mg (2mM) cesium carbonate were reacted in 10mL of tetrahydrofuran / water solvent with a volume ratio of 24 / 1 at 85°C for 48 hours. After the reaction was cooled, it was quenched with water, extracted with dichloromethane, dried over anhydrous magnesium sulfate, and Petroleum ether, dichloromethane, and ammonia water were used as eluents...

Embodiment 2

[0036] Example 2: Synthesis of Self-Assembled Molecules

[0037] Just take the synthesis of self-assembled molecules with the following structure as an example, the end group of the oxidation reaction is carbazole, the end group reacting with the working electrode is a phosphate group, and the central element unit of the complex is ruthenium.

[0038] Basic synthetic route:

[0039]

[0040] 1. Synthesis of [2,2'; 6',2"-terpyridine']-4-diethyl phosphite

[0041] 312mg (1mM) 4'-bromo-2,2':6',2"-terpyridine, 414.3mg (3mM) diethyl phosphite, 57.8mg (0.05mM) tetrakistriphenylphosphine palladium, 0.3mL ( 2mM) triethylamine was reacted in 30mL toluene solvent at 95°C for 12 hours. After the reaction was cooled, add water to quench the reaction, extract with dichloromethane, dry over anhydrous magnesium sulfate, use dichloromethane and methanol as eluent, and perform column chromatography Purification afforded a white solid (86% yield). 1 H NMR (400MHz, CDCl 3 ,25℃): δ(ppm)8.8...

Embodiment 3

[0044] Example 3: Electrochemical synthesis of sequence-controllable coordination metal polymers

[0045] 1. Electrolyte preparation

[0046] The synthesized complex monomer was dissolved in the electrolyte solution, and the concentration of the compound was 0.5 mM. The supporting electrolyte is tetrabutylammonium hexafluorophosphate with a concentration of 0.1mol / L. The solvent is acetonitrile.

[0047] 2. Use of electrodes

[0048] (1) Working electrode:

[0049] Just take the self-assembled monolayer prepared by using indium tin oxide (ITO) electrodes on the assembly substrate as an example:

[0050] The ITO glass was soaked in 0.1mM self-assembled molecules / methanol solution for 12 hours in the dark, ultrasonically cleaned in an ethanol bath, the surface was rinsed with dichloromethane, and dried with nitrogen gas for later use.

[0051] (2) Counter electrode: platinum wire electrode

[0052] (3) Reference electrode: silver-silver chloride electrode

[0053] 3. Poly...

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Abstract

The invention relates to a method for electrochemically synthesizing a sequence-controllable coordination metal polymer, and belongs to the technical field of polymer synthesis. The technical problemsthat an existing polymer sequence controllable synthesis method is long in consumed time, low in efficiency and prone to side reaction are solved. According to the method for electrochemically synthesizing the sequence-controllable coordination metal polymer, a monomer simultaneously with an electrochemical oxidative coupling reaction unit and an electrochemical reductive coupling reaction unit is synthesized, an electroactive self-assembled single layer is introduced as a template, and the selectivity and the reaction degree are controlled through program conversion of positive and negativepotentials; and therefore, the polymer with controllable composition, sequence and chain length is electrochemically synthesized. Compared with the prior art, the method provided by the invention hasthe advantages of high reaction efficiency and short synthesis period, is beneficial to personalized synthesis of coordination polymers with definite structures and complex structures and functions, and has automatic synthesis potential and commercial value. Such polymers are difficult or impossible to prepare with usual chemical methods.

Description

technical field [0001] The invention belongs to the technical field of polymer synthesis, and in particular relates to a method for electrochemically synthesizing sequence-controllable coordination metal polymers. Background technique [0002] Coordination metallopolymers are widely used in sensors, catalysis, and bio-related fields due to their unique properties, and coordination metallopolymers with controllable structure, composition, and sequence have more advantages in the fields of photoelectric information conversion, storage, and processing. Practical application value. The current common synthetic methods are stepwise polymerization, chain polymerization and multi-step growth synthesis. These methods require special monomer design and selection to roughly control the structure of the polymer, and it is difficult to achieve precise sequence-controlled polymerization. For example, the Lutz group took advantage of the alternate copolymerization properties of styrene / m...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C25B3/02C25B3/04C25B3/12C25B11/08C25B3/23C25B3/13C25B3/25
CPCC25B3/13C25B3/23C25B3/25C25B11/073
Inventor 李茂王艳芳张健
Owner CHANGCHUN INST OF APPLIED CHEMISTRY - CHINESE ACAD OF SCI
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