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Issue 37, 2018
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High electrical conductivity and high porosity in a Guest@MOF material: evidence of TCNQ ordering within Cu3BTC2 micropores

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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

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Publication details

The article was received on 05 Jun 2018, accepted on 07 Aug 2018 and first published on 08 Aug 2018


Article type: Edge Article
DOI: 10.1039/C8SC02471E
Chem. Sci., 2018,9, 7405-7412
  • Open access: Creative Commons BY-NC license
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    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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