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Title: A cobalt(II) spin-crossover compound with partially charged TCNQ radicals and an anomalous conducting behavior

Abstract

The bifunctional salt [Co(terpy) 2](TCNQ) 3·CH 3CN (terpy = 2,2';6',2"-terpyridine, TCNQ = 7,7,8,8-tetracyanoquino-dimethane) exhibits a high room temperature conductivity of 0.13 S cm -1 and an anomaly in conductivity at ~190 K as evidenced by variable temperature structural, magnetic and conductivity studies. The anomaly in the conductivity at 190 K has been correlated with the temperature dependent structural breathing and Jahn–Teller distortion of the low spin state of the SCO units, as well as the charge fluctuations and supramolecular π-stacking interactions of partially charged TCNQ radicals. Finally, the modular synthetic approach leads to an accessible source of partially charged TCNQ radicals for the facile preparation of bifunctional molecular materials with high electrical conductivity.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [1];  [2];  [1]; ORCiD logo [1]
  1. Texas A&M Univ., College Station, TX (United States). Dept. of Chemistry
  2. Shanghai Univ., Shanghai (China). Dept. of Chemistry, Innovative Drug Research Center
Publication Date:
Research Org.:
Texas A&M Univ., College Station, TX (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1467560
Grant/Contract Number:  
SC0012582
Resource Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 7; Journal Issue: 2; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Zhang, Xuan, Wang, Zhao-Xi, Xie, Haomiao, Li, Ming-Xing, Woods, Toby J., and Dunbar, Kim R. A cobalt(II) spin-crossover compound with partially charged TCNQ radicals and an anomalous conducting behavior. United States: N. p., 2015. Web. doi:10.1039/c5sc03547c.
Zhang, Xuan, Wang, Zhao-Xi, Xie, Haomiao, Li, Ming-Xing, Woods, Toby J., & Dunbar, Kim R. A cobalt(II) spin-crossover compound with partially charged TCNQ radicals and an anomalous conducting behavior. United States. doi:10.1039/c5sc03547c.
Zhang, Xuan, Wang, Zhao-Xi, Xie, Haomiao, Li, Ming-Xing, Woods, Toby J., and Dunbar, Kim R. Tue . "A cobalt(II) spin-crossover compound with partially charged TCNQ radicals and an anomalous conducting behavior". United States. doi:10.1039/c5sc03547c. https://www.osti.gov/servlets/purl/1467560.
@article{osti_1467560,
title = {A cobalt(II) spin-crossover compound with partially charged TCNQ radicals and an anomalous conducting behavior},
author = {Zhang, Xuan and Wang, Zhao-Xi and Xie, Haomiao and Li, Ming-Xing and Woods, Toby J. and Dunbar, Kim R.},
abstractNote = {The bifunctional salt [Co(terpy)2](TCNQ)3·CH3CN (terpy = 2,2';6',2"-terpyridine, TCNQ = 7,7,8,8-tetracyanoquino-dimethane) exhibits a high room temperature conductivity of 0.13 S cm-1 and an anomaly in conductivity at ~190 K as evidenced by variable temperature structural, magnetic and conductivity studies. The anomaly in the conductivity at 190 K has been correlated with the temperature dependent structural breathing and Jahn–Teller distortion of the low spin state of the SCO units, as well as the charge fluctuations and supramolecular π-stacking interactions of partially charged TCNQ radicals. Finally, the modular synthetic approach leads to an accessible source of partially charged TCNQ radicals for the facile preparation of bifunctional molecular materials with high electrical conductivity.},
doi = {10.1039/c5sc03547c},
journal = {Chemical Science},
number = 2,
volume = 7,
place = {United States},
year = {2015},
month = {12}
}

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Cited by: 26 works
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    Works referencing / citing this record:

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    • Inorganic Chemistry, Vol. 46, Issue 21
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    journal, May 2013

    • Knowles, Kathryn E.; Malicki, Michał; Parameswaran, Radha
    • Journal of the American Chemical Society, Vol. 135, Issue 19
    • DOI: 10.1021/ja4003074

    Carrier Concentration Dependent Conduction in Insulator-Doped Donor/Acceptor Chain Compounds
    journal, November 2013

    • Nishio, Masaki; Hoshino, Norihisa; Kosaka, Wataru
    • Journal of the American Chemical Society, Vol. 135, Issue 47
    • DOI: 10.1021/ja409785a

    Evidence of the Chemical Uniaxial Strain Effect on Electrical Conductivity in the Spin-Crossover Conducting Molecular System: [Fe III (qnal) 2 ][Pd(dmit) 2 ] 5 ·Acetone
    journal, May 2008

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    • DOI: 10.1021/ja801585r

    Coexistence of ferromagnetism and metallic conductivity in a molecule-based layered compound
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    • Coronado, Eugenio; Galán-Mascarós, José R.; Gómez-García, Carlos J.
    • Nature, Vol. 408, Issue 6811
    • DOI: 10.1038/35044035

    Long-range magnetic order in a purely organic 2D layer adsorbed on epitaxial graphene
    journal, April 2013

    • Garnica, Manuela; Stradi, Daniele; Barja, Sara
    • Nature Physics, Vol. 9, Issue 6
    • DOI: 10.1038/nphys2610

    The first coordination compound containing three different types of spin carriers: 2p–3d–4f (TCNQ˙–, Cu2+ and Gd3+)
    journal, June 2002

    • Madalan, Augustin M.; Roesky, Herbert W.; Andruh, Marius
    • Chemical Communications, Issue 15
    • DOI: 10.1039/b202628g

    [Fe(sal2-trien)][Ni(dmit)2]: towards switchable spin crossover molecular conductors
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    • Dorbes, St�phane; Valade, Lydie; Real, Jos� A.
    • Chemical Communications, Issue 1
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    Magnetically ordered molecule-based materials
    journal, January 2011


    An unusual discontinuity in the thermal spin transition in [Co(terpy)2][BF4]2
    journal, January 2010

    • Kilner, Colin A.; Halcrow, Malcolm A.
    • Dalton Transactions, Vol. 39, Issue 38
    • DOI: 10.1039/c0dt00295j

    A one-dimensional coordination polymer exhibiting simultaneous spin-crossover and semiconductor behaviour
    journal, January 2011

    • Xue, Wei; Wang, Bao-Ying; Zhu, Jie
    • Chemical Communications, Vol. 47, Issue 37
    • DOI: 10.1039/c1cc12852c

    Soft porous crystal meets TCNQ: charge transfer-type porous coordination polymers
    journal, January 2011

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