Isoreticular Linker Substitution in Conductive Metal–Organic Frameworks with Through‐Space Transport Pathways

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 repl...

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Bibliographic Details
Main Authors: Xie, Lilia S., Park, Sarah Sunah, Chmielewski, Michał J., Liu, Hanyu, Kharod, Ruby A., Yang, Luming, Campbell, Michael Glenn, Dinca, Mircea
Other Authors: Massachusetts Institute of Technology. Department of Chemistry
Format: Article
Language:English
Published: Wiley 2020
Online Access:https://hdl.handle.net/1721.1/128209
Description
Summary: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 Mn2+, Zn2+, and Cd2+. 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.