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

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/C8SC02471E· OSTI ID:1464563
 [1];  [1];  [2];  [3];  [1];  [4];  [5];  [2];  [3];  [1]
  1. Department of Chemistry, Technical University Munich, 85748 Garching, Germany
  2. Institute of Physical Chemistry, Center for Materials Research (ZFM), Justus-Liebig-University Giessen, 35392 Giessen, Germany
  3. Sandia National Laboratories, Livermore, USA
  4. Laboratory of Organic Chemistry, Wageningen University & Research, 6708 WE Wageningen, The Netherlands
  5. Laboratory of Organic Chemistry, Wageningen University & Research, 6708 WE Wageningen, The Netherlands, School of Pharmaceutical Sciences and Technology
+ Show Author Affiliations
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.
Research Organization:
Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
German Academic Exchange Service (DAAD); German Academic Scholarship Foundation; German Chemical Industry Fund (FCI); USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE National Nuclear Security Administration (NNSA)
Grant/Contract Number:
NA0003525
OSTI ID:
1464563
Alternate ID(s):
OSTI ID: 1624964
Journal Information:
Chemical Science, Journal Name: Chemical Science Journal Issue: 37 Vol. 9; ISSN 2041-6520; ISSN CSHCBM
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United Kingdom
Language:
English

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Chemistry