Fulvenyl-Functionalized Polyisocyanides: Redox-active (Cross-) Conjugated Polymers as Materials for Organic Polymer Batteries and Electrochromic Diodes

富烯基官能化多异氰化物：氧化还原活性（交叉）共轭聚合物作为有机聚合物电池和电致变色二极管的材料

• 批准号: 282201761
• 负责人: Privatdozent Dr. Frank Pammer
• 金额: --
• 依托单位: Helmholtz-Institut Ulm für Elektrochemische Energiespeicherung (HIU)
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2015
• 资助国家: 德国
• 起止时间: 2014-12-31 至 2019-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/282201761?language=en
• 关键词: Fulvenyl; Functionalized; Polyisocyanides; Redox; active

The research project is aimed at combining the properties of fulvenes and polyisocyanides (PICs), in order to access a new type of reversibly redox-active conjugated polymer that may serve as charge storage material in organic polymer batteries, or as redox-active dye in electrochromic diodes. Polyisocyanides are formally conjugated polymers that consist of a backbone of sp2-hybridized carbon atoms. However, the electronic structure of the polymer is such that the carbon atoms within the main-chain are linked by single bonds and are therefore cross-conjugated. As a consequence, electronic effects typically associated with extended conjugation are not observed. However, introduction of redox-active fulvenyl-groups into conjugated side-chains furnishes a polymer in which electrochemical reduction or oxidation may facilitate to a redistribution of the pi-electrons along polymer-backbone, transforming it into a fully conjugated polyacetylene-like pi-system. Ideally, this redox-response will allow to reversibly switch the color of the polymer electro-chemically, e.g. from virtually colorless to black. Furthermore, the introduction of specific redox-active sites allows the polymer to store up to one (1) full charge per repeat unit. For the simplest conceivable systems this corresponds to energy densities of up to 200-300 Ah/kg, which compares favorably e.g. with the classic lead/sulfuric acid battery (177 Ah/kg). Funding will be invested primarily in the preparation of new tria-, penta-, and hepta-fulvenyl functionalized PICs, and their physical, optical, and electrochemical characterization. Preparation of organic electronic devices will be pursued in close collaboration with independently funded cooperation partners.

该研究项目旨在结合富烯和聚异氰（PIC）的性质，以获得一种新型的可逆氧化还原活性共轭聚合物，可用作有机聚合物电池中的电荷存储材料，或作为电致变色二极管中的氧化还原活性染料。聚异腈是由sp2杂化碳原子的主链组成的形式上共轭的聚合物。然而，聚合物的电子结构使得主链内的碳原子通过单键连接，因此是交叉共轭的。因此，没有观察到通常与扩展共轭相关的电子效应。然而，将氧化还原活性富烯基引入共轭侧链中会破坏聚合物，其中电化学还原或氧化可促进π电子沿着聚合物主链的重新分布，将其转化为完全共轭的聚乙炔样π体系。理想地，这种氧化还原响应将允许可逆地电化学地转换聚合物的颜色，例如从几乎无色到黑色。此外，特定氧化还原活性位点的引入允许聚合物每个重复单元存储多达一（1）个完全电荷。对于最简单的可想到的系统，这对应于高达200-300 Ah/kg的能量密度，这与例如传统的铅/硫酸电池（177 Ah/kg）相比是有利的。资金将主要用于制备新的三-，五-和七-富烯基官能化的PIC，及其物理，光学和电化学表征。有机电子器件的制备将与独立资助的合作伙伴密切合作。

项目成果

Gold(I) Complexes of Fulvenyl-Functionalized Arylisocyanides

富烯基官能化芳基异氰化物的金(I)配合物

• DOI: 10.1002/ejic.201801031
• 发表时间: 2019
• 期刊: European Journal of Inorganic Chemistry
• 影响因子: 2.3
• 作者: S. Schraff;Y. Sun;A. Orthaber;F. Pammer
• 通讯作者: F. Pammer

Fulvenyl-Functionalized Polyisocyanides: Cross-Conjugated Electrochromic Polymers with Variable Optical and Electrochemical Properties

• DOI: 10.1021/acs.macromol.8b00977
• 发表时间: 2018-07-24
• 期刊: MACROMOLECULES
• 影响因子: 5.5
• 作者: Schraff, Sandra;Sun, Yu;Pammer, Frank
• 通讯作者: Pammer, Frank

All-conjugated donor–acceptor block copolymers featuring a pentafulvenyl-polyisocyanide-acceptor

• DOI: 10.1039/c9py01879d
• 发表时间: 2020-03
• 期刊: Polymer Chemistry
• 影响因子: 4.6
• 作者: Sandra Schraff;Sudeshna Maity;Laura Schleeper;Yifan Dong;Sebastian Lucas;A. Bakulin;E. von Hauff