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

Schneider, Christian; Ukaj, Dardan; Koerver, Raimund; Talin, A. Alec; Kieslich, Gregor; Pujari, Sidharam P.; Zuilhof, Han; Janek, Jürgen; Allendorf, Mark D.; Fischer, Roland A.

doi:10.1039/C8SC02471E

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

Journal Article · Wed Aug 08 00:00:00 EDT 2018 · Chemical Science

DOI:https://doi.org/10.1039/C8SC02471E· OSTI ID:1464563

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Department of Chemistry, Technical University Munich, 85748 Garching, Germany
Institute of Physical Chemistry, Center for Materials Research (ZFM), Justus-Liebig-University Giessen, 35392 Giessen, Germany
Sandia National Laboratories, Livermore, USA
Laboratory of Organic Chemistry, Wageningen University & Research, 6708 WE Wageningen, The Netherlands
Laboratory of Organic Chemistry, Wageningen University & Research, 6708 WE Wageningen, The Netherlands, School of Pharmaceutical Sciences and Technology

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.

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Research Organization:: Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE National Nuclear Security Administration (NNSA); USDOE Laboratory Directed Research and Development (LDRD) Program; German Academic Scholarship Foundation; German Chemical Industry Fund (FCI); German Academic Exchange Service (DAAD)

Grant/Contract Number:: NA0003525

OSTI ID:: 1464563

Alternate ID(s):: OSTI ID: 1624964

Journal Information:: Chemical Science, Journal Name: Chemical Science Vol. 9 Journal Issue: 37; ISSN 2041-6520

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United Kingdom

Language:: English

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Cited by: 63 works

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

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