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具有空间传输路径的导电金属有机框架中的等规连接体取代

Isoreticular Linker Substitution in Conductive Metal-Organic Frameworks with Through-Space Transport Pathways.

作者信息

Xie Lilia S, Park Sarah S, Chmielewski Michał J, Liu Hanyu, Kharod Ruby A, Yang Luming, Campbell Michael G, Dincă Mircea

机构信息

Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, MA, 02139, USA.

Faculty of Chemistry, Biological and Chemical Research Centre, University of Warsaw, Żwirki i Wigury 101, 02-089, Warszawa, Poland.

出版信息

Angew Chem Int Ed Engl. 2020 Oct 26;59(44):19623-19626. doi: 10.1002/anie.202004697. Epub 2020 May 25.

Abstract

The extension of reticular chemistry concepts to electrically conductive three-dimensional metal-organic frameworks (MOFs) has been challenging, particularly for cases in which strong interactions between electroactive linkers create the charge transport pathways. Here, we report the successful replacement of tetrathiafulvalene (TTF) with a nickel glyoximate core in a family of isostructural conductive MOFs with Mn , Zn , and Cd . Different coordination environments of the framework metals lead to variations in the linker stacking geometries and optical properties. Single-crystal conductivity data are consistent with charge transport along the linker stacking direction, with conductivity values only slightly lower than those reported for the analogous TTF materials. These results serve as a case study demonstrating how reticular chemistry design principles can be extended to conductive frameworks with significant intermolecular contacts.

摘要

将网状化学概念扩展到导电三维金属有机框架(MOF)一直具有挑战性,特别是对于电活性连接体之间的强相互作用形成电荷传输途径的情况。在这里,我们报告了在一系列具有Mn、Zn和Cd的同构导电MOF中,用乙二肟镍核成功取代四硫富瓦烯(TTF)。框架金属的不同配位环境导致连接体堆积几何形状和光学性质的变化。单晶电导率数据与沿连接体堆积方向的电荷传输一致,电导率值仅略低于类似TTF材料报道的值。这些结果作为一个案例研究,展示了如何将网状化学设计原则扩展到具有显著分子间接触的导电框架。

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