Issue 37, 2018

High electrical conductivity and high porosity in a Guest@MOF material: evidence of TCNQ ordering within Cu3BTC2 micropores

Abstract

The host–guest system TCNQ@Cu3BTC2 (TCNQ = 7,7,8,8-tetracyanoquinodimethane, BTC = 1,3,5-benzenetricarboxylate) is a striking example of how semiconductivity can be introduced by guest incorporation in an otherwise insulating parent material. Exhibiting both microporosity and semiconducting behavior such materials offer exciting opportunities as next-generation sensor materials. Here, we apply a solvent-free vapor phase loading under rigorous exclusion of moisture, obtaining a series of the general formula xTCNQ@Cu3BTC2 (0 ≤ x ≤ 1.0). By using powder X-ray diffraction, infrared and X-ray absorption spectroscopy together with scanning electron microscopy and porosimetry, we provide the first structural evidence for a systematic preferential arrangement of TCNQ along the (111) lattice plane and the bridging coordination motif to two neighbouring Cu-paddlewheels, as was predicted by theory. For 1.0TCNQ@Cu3BTC2 we find a specific electrical conductivity of up to 1.5 × 10−4 S cm−1 whilst maintaining a high BET surface area of 573.7 m2 g−1. These values are unmatched by MOFs with equally high electrical conductivity, making the material attractive for applications such as super capacitors and chemiresistors. Our results represent the crucial missing link needed to firmly establish the structure–property relationship revealed in TCNQ@Cu3BTC2, thereby creating a sound basis for using this as a design principle for electrically conducting MOFs.

Graphical abstract: High electrical conductivity and high porosity in a Guest@MOF material: evidence of TCNQ ordering within Cu3BTC2 micropores

Supplementary files

Article information

Article type
Edge Article
Submitted
05 Jun 2018
Accepted
07 Aug 2018
First published
08 Aug 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2018,9, 7405-7412

High electrical conductivity and high porosity in a Guest@MOF material: evidence of TCNQ ordering within Cu3BTC2 micropores

C. Schneider, D. Ukaj, R. Koerver, A. A. Talin, G. Kieslich, S. P. Pujari, H. Zuilhof, J. Janek, M. D. Allendorf and R. A. Fischer, Chem. Sci., 2018, 9, 7405 DOI: 10.1039/C8SC02471E

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