Length and conjugation-controlled memristive functions of metallopolymer monolayers  

长度和共轭可控的金属聚合物单层的忆阻功能

作　　者：Chang Wei Ziming Zhou Shumu Li Yuan Li Wenjing Hong Xuan Pang Mao Li 魏畅;周子明;李书沐;李远;洪文晶;庞烜;李茂

机构地区：[1]State Key Laboratory of Polymer Physics and Chemistry,Changchun Institute of Applied Chemistry,Chinese Academy of Sciences,Changchun,130022,China [2]University of Science and Technology of China,Hefei,230026,China [3]Key Laboratory of Analytical Chemistry for Living Biosystems,Institute of Chemistry,Chinese Academy of Sciences,Beijing Mass Spectrum Center,Beijing,100190,China [4]Key Laboratory of Organic Optoelectronics and Molecular Engineering,Department of Chemistry,Tsinghua University,Beijing,100084,China [5]State Key Laboratory of Physical Chemistry of Solid Surfaces,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen,361005,China [6]State Key Laboratory of Supramolecular Structure and Materials,College of Chemistry,Jilin University,Changchun,130012,China

出　　处：《Science China Materials》2025年第4期998-1003,共6页中国科学(材料科学)(英文版)

基　　金：supported by the National Natural Science Foundation of China(91963125,52473176,22273045);Beijing National Laboratory for Molecular Sciences BNLMS202005;National Key Research and Development Program of China(2017YFA0204902);Tsinghua University Independent Scientific Research Plan for Young Investigator;Tsinghua University Initiative Scientific Research Program。

摘　　要：Solid-phase synthesis as a bottom-up strategy may be a superior way to integrate sophisticated functions into an ultrathin film for miniaturized devices.However,the sluggish reaction dynamics at the solid-liquid interface have been a great challenge.Herein,we present four electrochemical reactions for rapidly synthesizing length and conjugation-controlled metallopolymer monolayers.This electrosynthesis requires self-assembled monolayers as templates as a prerequisite to predefine the growth and orientation of the metallopolymers.Electrosynthesis involves a pair of redox reactions:the oxidation self-coupling of pyrene or carbazole,and the reduction self-coupling of the alkyne or vinyl,respectively.They can form conjugation-controlled connections of monomers and provide different lengths of metallopolymers.The resulting metallopolymer monolayers show similar values in thickness and theoretical molecular length,indicating that these metallopolymers stand almost vertically and uniaxially on electrodes with minimum polymer disorder.These crystalline monolayers exhibit both high modulus and conductance while presenting the memristive functions with optical and electrical binary responses as a function of the length and conjugation-controlled metallopolymer monolayers.It is highly anticipated that critical factors including reproducibility,speed,and operational simplicity with the robust design of various molecular junctions will enable rapid automated synthesis of two-dimensional semiconductors for integrated and miniaturized optoelectric devices.固相合成作为一种自下而上分子合成策略,有利于复杂结构与功能分子单层薄膜制备.但是,固液界面缓慢反应动力学难以满足类单分散分子单层制备.本研究利用四种电化学反应加速界面反应效率,通过固相有机电合成制备了分子长度和共轭结构可控的金属聚合物单层.聚合物单层厚度和理论分子长度相当,表明这些金属聚合物近垂直直立在电极表面.结果表明,具有结晶性的分子单层具有高模量和低电荷传输衰减系数,同时呈现出分子长度和共轭结构可控的光学和电学响应的忆阻功能.这种程序化电化学制备方法不仅易于自动化合成,同时有利于表面忆阻器集成.

关 键 词：solid-phase synthesis solid-phase electrosynthesis polymer monolayer polymer brush MEMRISTOR 

分 类 号：O63[理学—高分子化学]