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

Thanh Hai Le, Ayman Nafady, Jinzhen Lu, Germanas Peleckis, Alan Maxwell Bond, Lisandra Lorraine Martin

Research output: Contribution to journalArticleResearchpeer-review

Abstract

An electrochemical technique has been used to synthesize Ni(TCNQF4)2(H2O)2 (TCNQF4 = 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane). The method involves the reduction of solid TCNQF4 immobilized on an electrode surface in contact with Ni2+ (aq.)-containing electrolyte. The electrochemically irreversible, but chemically reversiblesolid–solid TCNQF4/Ni(TCNQF4)2(H2O)2 interconversion process is governed by nucleation and growth kinetics and is represented by the overall reaction: 2TCNQF4 (s, electrode) + Ni2+ (aq.) + 2H2O + 2e [rlhar2] Ni(TCNQF4)2(H2O)2 (s, electrode). Thus, the formation of Ni(TCNQF4)2(H2O)2 involves the one-electron reduction of TCNQF4 to [TCNQF4]·– coupled with an ingress of Ni2+ (aq.) from the aqueous electrolyte, while the reverse scan represents the oxidation of [TCNQF4]·– to TCNQF4 coupled with the egress of Ni2+ (aq.). Cyclic voltammograms for the TCNQF4/Ni(TCNQF4)2(H2O)2 solid–solid phase transformation are independent of the electrode material and the identity of the Ni2+ (aq.) counteranion but are strongly dependent on the concentration of Ni2+ (aq.) and the scan rate. UV/Vis, infrared, and Raman spectra confirm the presence of [TCNQF4]·– in the newly synthesized material. The composition of Ni(TCNQF4)2(H2O)2 was deduced from thermogravimetric and elemental analyses. Scanning electron microscopic images of Ni(TCNQF4)2(H2O)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.
Original languageEnglish
Pages (from-to)2889 - 2897
Number of pages9
JournalEuropean Journal of Inorganic Chemistry
Volume2012
Issue number17
DOIs
Publication statusPublished - 2012

Cite this

@article{d74bcdc0990648aeb47bea1632fe085a,
title = "Electrochemical synthesis and characterization of semiconducting Ni(TCNQF4)2(H2O)2 (TCNQF4=2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane)",
abstract = "An electrochemical technique has been used to synthesize Ni(TCNQF4)2(H2O)2 (TCNQF4 = 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane). The method involves the reduction of solid TCNQF4 immobilized on an electrode surface in contact with Ni2+ (aq.)-containing electrolyte. The electrochemically irreversible, but chemically reversiblesolid–solid TCNQF4/Ni(TCNQF4)2(H2O)2 interconversion process is governed by nucleation and growth kinetics and is represented by the overall reaction: 2TCNQF4 (s, electrode) + Ni2+ (aq.) + 2H2O + 2e [rlhar2] Ni(TCNQF4)2(H2O)2 (s, electrode). Thus, the formation of Ni(TCNQF4)2(H2O)2 involves the one-electron reduction of TCNQF4 to [TCNQF4]·– coupled with an ingress of Ni2+ (aq.) from the aqueous electrolyte, while the reverse scan represents the oxidation of [TCNQF4]·– to TCNQF4 coupled with the egress of Ni2+ (aq.). Cyclic voltammograms for the TCNQF4/Ni(TCNQF4)2(H2O)2 solid–solid phase transformation are independent of the electrode material and the identity of the Ni2+ (aq.) counteranion but are strongly dependent on the concentration of Ni2+ (aq.) and the scan rate. UV/Vis, infrared, and Raman spectra confirm the presence of [TCNQF4]·– in the newly synthesized material. The composition of Ni(TCNQF4)2(H2O)2 was deduced from thermogravimetric and elemental analyses. Scanning electron microscopic images of Ni(TCNQF4)2(H2O)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.",
author = "Le, {Thanh Hai} and Ayman Nafady and Jinzhen Lu and Germanas Peleckis and Bond, {Alan Maxwell} and Martin, {Lisandra Lorraine}",
year = "2012",
doi = "10.1002/ejic.201101420",
language = "English",
volume = "2012",
pages = "2889 -- 2897",
journal = "European Journal of Inorganic Chemistry",
issn = "1434-1948",
publisher = "Wiley-VCH Verlag GmbH & Co. KGaA",
number = "17",

}

Electrochemical synthesis and characterization of semiconducting Ni(TCNQF4)2(H2O)2 (TCNQF4=2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane). / Le, Thanh Hai; Nafady, Ayman; Lu, Jinzhen; Peleckis, Germanas; Bond, Alan Maxwell; Martin, Lisandra Lorraine.

In: European Journal of Inorganic Chemistry, Vol. 2012, No. 17, 2012, p. 2889 - 2897.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Electrochemical synthesis and characterization of semiconducting Ni(TCNQF4)2(H2O)2 (TCNQF4=2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane)

AU - Le, Thanh Hai

AU - Nafady, Ayman

AU - Lu, Jinzhen

AU - Peleckis, Germanas

AU - Bond, Alan Maxwell

AU - Martin, Lisandra Lorraine

PY - 2012

Y1 - 2012

N2 - An electrochemical technique has been used to synthesize Ni(TCNQF4)2(H2O)2 (TCNQF4 = 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane). The method involves the reduction of solid TCNQF4 immobilized on an electrode surface in contact with Ni2+ (aq.)-containing electrolyte. The electrochemically irreversible, but chemically reversiblesolid–solid TCNQF4/Ni(TCNQF4)2(H2O)2 interconversion process is governed by nucleation and growth kinetics and is represented by the overall reaction: 2TCNQF4 (s, electrode) + Ni2+ (aq.) + 2H2O + 2e [rlhar2] Ni(TCNQF4)2(H2O)2 (s, electrode). Thus, the formation of Ni(TCNQF4)2(H2O)2 involves the one-electron reduction of TCNQF4 to [TCNQF4]·– coupled with an ingress of Ni2+ (aq.) from the aqueous electrolyte, while the reverse scan represents the oxidation of [TCNQF4]·– to TCNQF4 coupled with the egress of Ni2+ (aq.). Cyclic voltammograms for the TCNQF4/Ni(TCNQF4)2(H2O)2 solid–solid phase transformation are independent of the electrode material and the identity of the Ni2+ (aq.) counteranion but are strongly dependent on the concentration of Ni2+ (aq.) and the scan rate. UV/Vis, infrared, and Raman spectra confirm the presence of [TCNQF4]·– in the newly synthesized material. The composition of Ni(TCNQF4)2(H2O)2 was deduced from thermogravimetric and elemental analyses. Scanning electron microscopic images of Ni(TCNQF4)2(H2O)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.

AB - An electrochemical technique has been used to synthesize Ni(TCNQF4)2(H2O)2 (TCNQF4 = 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane). The method involves the reduction of solid TCNQF4 immobilized on an electrode surface in contact with Ni2+ (aq.)-containing electrolyte. The electrochemically irreversible, but chemically reversiblesolid–solid TCNQF4/Ni(TCNQF4)2(H2O)2 interconversion process is governed by nucleation and growth kinetics and is represented by the overall reaction: 2TCNQF4 (s, electrode) + Ni2+ (aq.) + 2H2O + 2e [rlhar2] Ni(TCNQF4)2(H2O)2 (s, electrode). Thus, the formation of Ni(TCNQF4)2(H2O)2 involves the one-electron reduction of TCNQF4 to [TCNQF4]·– coupled with an ingress of Ni2+ (aq.) from the aqueous electrolyte, while the reverse scan represents the oxidation of [TCNQF4]·– to TCNQF4 coupled with the egress of Ni2+ (aq.). Cyclic voltammograms for the TCNQF4/Ni(TCNQF4)2(H2O)2 solid–solid phase transformation are independent of the electrode material and the identity of the Ni2+ (aq.) counteranion but are strongly dependent on the concentration of Ni2+ (aq.) and the scan rate. UV/Vis, infrared, and Raman spectra confirm the presence of [TCNQF4]·– in the newly synthesized material. The composition of Ni(TCNQF4)2(H2O)2 was deduced from thermogravimetric and elemental analyses. Scanning electron microscopic images of Ni(TCNQF4)2(H2O)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.

U2 - 10.1002/ejic.201101420

DO - 10.1002/ejic.201101420

M3 - Article

VL - 2012

SP - 2889

EP - 2897

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

SN - 1434-1948

IS - 17

ER -