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光电共价有机框架:将开放晶格转化为有序给体-受体异质结。

Photoelectric covalent organic frameworks: converting open lattices into ordered donor-acceptor heterojunctions.

机构信息

College of Materials Science and Engineering, Beijing Institute of Technology , 5 South Zhongguancun Street, Haidian District, Beijing 100081, China.

出版信息

J Am Chem Soc. 2014 Jul 16;136(28):9806-9. doi: 10.1021/ja502692w. Epub 2014 Jul 1.

Abstract

Ordered one-dimensional open channels represent the typical porous structure of two-dimensional covalent organic frameworks (COFs). Here we report a general synthetic strategy for converting these open lattice structures into ordered donor-acceptor heterojunctions. A three-component topological design scheme was explored to prepare electron-donating intermediate COFs, which upon click reaction were transformed to photoelectric COFs with segregated donor-acceptor alignments, whereas electron-accepting buckyballs were spatially confined within the nanochannels via covalent anchoring on the channel walls. The donor-acceptor heterojunctions trigger photoinduced electron transfer and allow charge separation with radical species delocalized in the π-arrays, whereas the charge separation efficiency was dependent on the buckyball content. This new donor-acceptor strategy explores both skeletons and pores of COFs for charge separation and photoenergy conversion.

摘要

有序一维开口通道代表二维共价有机框架(COFs)的典型多孔结构。在这里,我们报告了一种将这些开放晶格结构转化为有序供体-受体异质结的通用合成策略。探索了一种三组分拓扑设计方案来制备电子供体中间 COFs,通过点击反应将其转化为具有分离供体-受体排列的光电 COFs,而电子受体富勒烯通过共价锚定在通道壁上被空间限制在纳米通道内。供体-受体异质结引发光致电子转移,并允许通过在π 体系中离域的自由基物种进行电荷分离,而电荷分离效率取决于富勒烯的含量。这种新的供体-受体策略探索了 COFs 的骨架和孔用于电荷分离和光能量转换。

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