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Electrochemical synthesis and characterization of semiconducting Ni(TCNQF4)2(H2O)2(TCNQF4=2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane)

Journal Article


Abstract


  • An electrochemical technique has been used to synthesize Ni(TCNQF 4) 2(H 2O) 2 (TCNQF 4 = 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane). The method involves the reduction of solid TCNQF 4 immobilized on an electrode surface in contact with Ni 2+ (aq.)-containing electrolyte. The electrochemically irreversible, but chemically reversiblesolid-solid TCNQF 4/ Ni(TCNQF 4) 2(H 2O) 2 interconversion process is governed by nucleation and growth kinetics and is represented by the overall reaction: 2TCNQF 4 (s, electrode) + Ni 2+ (aq.) + 2H 2O + 2e [rlhar2] Ni(TCNQF 4) 2(H 2O) 2 (s, electrode). Thus, the formation of Ni(TCNQF 4) 2(H 2O) 2 involves the one-electron reduction of TCNQF 4 to [TCNQF 4] ·- coupled with an ingress of Ni 2+ (aq.) from the aqueous electrolyte, while the reverse scan represents the oxidation of [TCNQF 4] ·- to TCNQF 4 coupled with the egress of Ni 2+ (aq.). Cyclic voltammograms for the TCNQF 4/ Ni(TCNQF 4) 2(H 2O) 2 solid-solid phase transformation are independent of the electrode material and the identity of the Ni 2+ (aq.) counteranion but are strongly dependent on the concentration of Ni 2+ (aq.) and the scan rate. UV/Vis, infrared, and Raman spectra confirm the presence of [TCNQF 4] ·- in the newly synthesized material. The composition of Ni(TCNQF 4) 2(H 2O) 2 was deduced from thermogravimetric and elemental analyses. Scanning electron microscopic images of Ni(TCNQF 4) 2(H 2O) 2 electrocrystallized onto the surface of an indium tin oxide electrode show a thin film morphology. Magnetic and conductivity data demonstrate that the complex behaves as a classical paramagnet and is a typical semiconductor with a band gap close to that of an insulator. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Authors


  •   Le, Tri Hai (external author)
  •   Nafady, A (external author)
  •   Lu, Jinzhen (external author)
  •   Peleckis, Germanas
  •   Bond, Alan M. (external author)
  •   Martin, Lisandra L. (external author)

Publication Date


  • 2012

Citation


  • Le, T. Hai., Nafady, A., Lu, J., Peleckis, G., Bond, A. M. & Martin, L. L. (2012). Electrochemical synthesis and characterization of semiconducting Ni(TCNQF4)2(H2O)2(TCNQF4=2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane). European Journal of Inorganic Chemistry, (17), 2889-2897.

Scopus Eid


  • 2-s2.0-84861823798

Ro Metadata Url


  • http://ro.uow.edu.au/engpapers/4876

Has Global Citation Frequency


Number Of Pages


  • 8

Start Page


  • 2889

End Page


  • 2897

Issue


  • 17

Place Of Publication


  • Germany

Abstract


  • An electrochemical technique has been used to synthesize Ni(TCNQF 4) 2(H 2O) 2 (TCNQF 4 = 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane). The method involves the reduction of solid TCNQF 4 immobilized on an electrode surface in contact with Ni 2+ (aq.)-containing electrolyte. The electrochemically irreversible, but chemically reversiblesolid-solid TCNQF 4/ Ni(TCNQF 4) 2(H 2O) 2 interconversion process is governed by nucleation and growth kinetics and is represented by the overall reaction: 2TCNQF 4 (s, electrode) + Ni 2+ (aq.) + 2H 2O + 2e [rlhar2] Ni(TCNQF 4) 2(H 2O) 2 (s, electrode). Thus, the formation of Ni(TCNQF 4) 2(H 2O) 2 involves the one-electron reduction of TCNQF 4 to [TCNQF 4] ·- coupled with an ingress of Ni 2+ (aq.) from the aqueous electrolyte, while the reverse scan represents the oxidation of [TCNQF 4] ·- to TCNQF 4 coupled with the egress of Ni 2+ (aq.). Cyclic voltammograms for the TCNQF 4/ Ni(TCNQF 4) 2(H 2O) 2 solid-solid phase transformation are independent of the electrode material and the identity of the Ni 2+ (aq.) counteranion but are strongly dependent on the concentration of Ni 2+ (aq.) and the scan rate. UV/Vis, infrared, and Raman spectra confirm the presence of [TCNQF 4] ·- in the newly synthesized material. The composition of Ni(TCNQF 4) 2(H 2O) 2 was deduced from thermogravimetric and elemental analyses. Scanning electron microscopic images of Ni(TCNQF 4) 2(H 2O) 2 electrocrystallized onto the surface of an indium tin oxide electrode show a thin film morphology. Magnetic and conductivity data demonstrate that the complex behaves as a classical paramagnet and is a typical semiconductor with a band gap close to that of an insulator. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Authors


  •   Le, Tri Hai (external author)
  •   Nafady, A (external author)
  •   Lu, Jinzhen (external author)
  •   Peleckis, Germanas
  •   Bond, Alan M. (external author)
  •   Martin, Lisandra L. (external author)

Publication Date


  • 2012

Citation


  • Le, T. Hai., Nafady, A., Lu, J., Peleckis, G., Bond, A. M. & Martin, L. L. (2012). Electrochemical synthesis and characterization of semiconducting Ni(TCNQF4)2(H2O)2(TCNQF4=2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane). European Journal of Inorganic Chemistry, (17), 2889-2897.

Scopus Eid


  • 2-s2.0-84861823798

Ro Metadata Url


  • http://ro.uow.edu.au/engpapers/4876

Has Global Citation Frequency


Number Of Pages


  • 8

Start Page


  • 2889

End Page


  • 2897

Issue


  • 17

Place Of Publication


  • Germany