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Title: 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 electricallymore » conducting MOFs.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2];  [3]; ORCiD logo [1]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [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
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
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)
OSTI Identifier:
1464563
Alternate Identifier(s):
OSTI ID: 1624964
Grant/Contract Number:  
NA0003525
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 9 Journal Issue: 37; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry

Citation Formats

Schneider, Christian, Ukaj, Dardan, Koerver, Raimund, Talin, A. Alec, Kieslich, Gregor, Pujari, Sidharam P., Zuilhof, Han, Janek, Jürgen, Allendorf, Mark D., and Fischer, Roland A. High electrical conductivity and high porosity in a Guest@MOF material: evidence of TCNQ ordering within Cu3BTC2 micropores. United Kingdom: N. p., 2018. Web. doi:10.1039/C8SC02471E.
Schneider, Christian, Ukaj, Dardan, Koerver, Raimund, Talin, A. Alec, Kieslich, Gregor, Pujari, Sidharam P., Zuilhof, Han, Janek, Jürgen, Allendorf, Mark D., & Fischer, Roland A. High electrical conductivity and high porosity in a Guest@MOF material: evidence of TCNQ ordering within Cu3BTC2 micropores. United Kingdom. doi:10.1039/C8SC02471E.
Schneider, Christian, Ukaj, Dardan, Koerver, Raimund, Talin, A. Alec, Kieslich, Gregor, Pujari, Sidharam P., Zuilhof, Han, Janek, Jürgen, Allendorf, Mark D., and Fischer, Roland A. Wed . "High electrical conductivity and high porosity in a Guest@MOF material: evidence of TCNQ ordering within Cu3BTC2 micropores". United Kingdom. doi:10.1039/C8SC02471E.
@article{osti_1464563,
title = {High electrical conductivity and high porosity in a Guest@MOF material: evidence of TCNQ ordering within Cu3BTC2 micropores},
author = {Schneider, Christian and Ukaj, Dardan and Koerver, Raimund and Talin, A. Alec and Kieslich, Gregor and Pujari, Sidharam P. and Zuilhof, Han and Janek, Jürgen and Allendorf, Mark D. and Fischer, Roland A.},
abstractNote = {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.},
doi = {10.1039/C8SC02471E},
journal = {Chemical Science},
number = 37,
volume = 9,
place = {United Kingdom},
year = {2018},
month = {8}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C8SC02471E

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Cited by: 8 works
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