A Systematic (Spectro-) Electrochemical Approach to the Synthesis and Characterisation of Co(II) and Ni(II) Compounds Containing Reduced Forms of TCNQF

Research output: Contribution to journalArticleResearchpeer-review

Abstract

The electrochemistry of TCNQF (2-fluoro-7,7,8,8-tetracyanoquinodimethane) in acetonitrile (0.1 M Bu4NPF6) in the presence of either Co2+ or Ni2+ is reported. Cyclic voltammetry over an extensive range of potentials revealed that the reduction of TCNQF to either TCNQF1− or the TCNQF2− species provides a route for electrocrystallisation of the respective M(TCNQF)2(H2O)2 and M(TCNQF) materials on the electrode surface. These materials were independently prepared by addition of the corresponding metal salts to a solution of either TCNQF1− or TCNQF2− prepared by bulk electrolysis. Comprehensive characterisation of these solids by Infrared and Raman spectroscopy indicated that the M(TCNQF)2(H2O)2 complexes were similar to other transition metal complexes in the M(TCNQX)2(S)2 series where S=solvent (H2O or CH3OH) and X = H4 or F4. The M(TCNQF) materials containing the TCNQF2− anion were not stable in air, similar to the highly air-sensitive TCNQ2− derivatives. Scanning Electron Microscopy (SEM) images of electrocrystallised samples of Ni(TCNQF)2(H2O)2 were rod-like, whereas the Co(TCNQF)2(H2O)2 formed needles. Energy-dispersive X-ray spectroscopy (EDX) analysis of these samples together with elemental microanalysis and thermogravimetric analysis (TGA) supported the composition and stoichiometry. The solubility products (Ksp values) of M(TCNQF)2(H2O)2 materials were determined spectrophotometrically and voltammetrically in acetonitrile, where Ksp for Co(TCNQF)2(H2O)2 was 3.37×10−11 M3 (or 1.14×10−10 M3 in the presence of electrolyte, 0.1 M Bu4NPF6) and Ni(TCNQF)2(H2O)2 was 5.54×10−12 M3 (or 2.65×10−10 M3 in the presence of electrolyte, 0.1 M Bu4NPF6).

Original languageEnglish
Pages (from-to)221-228
Number of pages8
JournalChemElectroChem
Volume6
Issue number1
DOIs
Publication statusPublished - 2 Jan 2019

Keywords

  • bulk electrolysis
  • cyclic voltammetry
  • electrocrystallisation
  • morphology
  • vibrational spectroscopy

Cite this

@article{5ceca8fc4db54bb3abf7f434b0fb55a5,
title = "A Systematic (Spectro-) Electrochemical Approach to the Synthesis and Characterisation of Co(II) and Ni(II) Compounds Containing Reduced Forms of TCNQF",
abstract = "The electrochemistry of TCNQF (2-fluoro-7,7,8,8-tetracyanoquinodimethane) in acetonitrile (0.1 M Bu4NPF6) in the presence of either Co2+ or Ni2+ is reported. Cyclic voltammetry over an extensive range of potentials revealed that the reduction of TCNQF to either TCNQF1− or the TCNQF2− species provides a route for electrocrystallisation of the respective M(TCNQF)2(H2O)2 and M(TCNQF) materials on the electrode surface. These materials were independently prepared by addition of the corresponding metal salts to a solution of either TCNQF1− or TCNQF2− prepared by bulk electrolysis. Comprehensive characterisation of these solids by Infrared and Raman spectroscopy indicated that the M(TCNQF)2(H2O)2 complexes were similar to other transition metal complexes in the M(TCNQX)2(S)2 series where S=solvent (H2O or CH3OH) and X = H4 or F4. The M(TCNQF) materials containing the TCNQF2− anion were not stable in air, similar to the highly air-sensitive TCNQ2− derivatives. Scanning Electron Microscopy (SEM) images of electrocrystallised samples of Ni(TCNQF)2(H2O)2 were rod-like, whereas the Co(TCNQF)2(H2O)2 formed needles. Energy-dispersive X-ray spectroscopy (EDX) analysis of these samples together with elemental microanalysis and thermogravimetric analysis (TGA) supported the composition and stoichiometry. The solubility products (Ksp values) of M(TCNQF)2(H2O)2 materials were determined spectrophotometrically and voltammetrically in acetonitrile, where Ksp for Co(TCNQF)2(H2O)2 was 3.37×10−11 M3 (or 1.14×10−10 M3 in the presence of electrolyte, 0.1 M Bu4NPF6) and Ni(TCNQF)2(H2O)2 was 5.54×10−12 M3 (or 2.65×10−10 M3 in the presence of electrolyte, 0.1 M Bu4NPF6).",
keywords = "bulk electrolysis, cyclic voltammetry, electrocrystallisation, morphology, vibrational spectroscopy",
author = "Vo, {Nguyen T.} and Martin, {Lisandra L.} and Bond, {Alan M.}",
year = "2019",
month = "1",
day = "2",
doi = "10.1002/celc.201800678",
language = "English",
volume = "6",
pages = "221--228",
journal = "ChemElectroChem",
issn = "2196-0216",
publisher = "Wiley-Blackwell",
number = "1",

}

A Systematic (Spectro-) Electrochemical Approach to the Synthesis and Characterisation of Co(II) and Ni(II) Compounds Containing Reduced Forms of TCNQF. / Vo, Nguyen T.; Martin, Lisandra L.; Bond, Alan M.

In: ChemElectroChem, Vol. 6, No. 1, 02.01.2019, p. 221-228.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - A Systematic (Spectro-) Electrochemical Approach to the Synthesis and Characterisation of Co(II) and Ni(II) Compounds Containing Reduced Forms of TCNQF

AU - Vo, Nguyen T.

AU - Martin, Lisandra L.

AU - Bond, Alan M.

PY - 2019/1/2

Y1 - 2019/1/2

N2 - The electrochemistry of TCNQF (2-fluoro-7,7,8,8-tetracyanoquinodimethane) in acetonitrile (0.1 M Bu4NPF6) in the presence of either Co2+ or Ni2+ is reported. Cyclic voltammetry over an extensive range of potentials revealed that the reduction of TCNQF to either TCNQF1− or the TCNQF2− species provides a route for electrocrystallisation of the respective M(TCNQF)2(H2O)2 and M(TCNQF) materials on the electrode surface. These materials were independently prepared by addition of the corresponding metal salts to a solution of either TCNQF1− or TCNQF2− prepared by bulk electrolysis. Comprehensive characterisation of these solids by Infrared and Raman spectroscopy indicated that the M(TCNQF)2(H2O)2 complexes were similar to other transition metal complexes in the M(TCNQX)2(S)2 series where S=solvent (H2O or CH3OH) and X = H4 or F4. The M(TCNQF) materials containing the TCNQF2− anion were not stable in air, similar to the highly air-sensitive TCNQ2− derivatives. Scanning Electron Microscopy (SEM) images of electrocrystallised samples of Ni(TCNQF)2(H2O)2 were rod-like, whereas the Co(TCNQF)2(H2O)2 formed needles. Energy-dispersive X-ray spectroscopy (EDX) analysis of these samples together with elemental microanalysis and thermogravimetric analysis (TGA) supported the composition and stoichiometry. The solubility products (Ksp values) of M(TCNQF)2(H2O)2 materials were determined spectrophotometrically and voltammetrically in acetonitrile, where Ksp for Co(TCNQF)2(H2O)2 was 3.37×10−11 M3 (or 1.14×10−10 M3 in the presence of electrolyte, 0.1 M Bu4NPF6) and Ni(TCNQF)2(H2O)2 was 5.54×10−12 M3 (or 2.65×10−10 M3 in the presence of electrolyte, 0.1 M Bu4NPF6).

AB - The electrochemistry of TCNQF (2-fluoro-7,7,8,8-tetracyanoquinodimethane) in acetonitrile (0.1 M Bu4NPF6) in the presence of either Co2+ or Ni2+ is reported. Cyclic voltammetry over an extensive range of potentials revealed that the reduction of TCNQF to either TCNQF1− or the TCNQF2− species provides a route for electrocrystallisation of the respective M(TCNQF)2(H2O)2 and M(TCNQF) materials on the electrode surface. These materials were independently prepared by addition of the corresponding metal salts to a solution of either TCNQF1− or TCNQF2− prepared by bulk electrolysis. Comprehensive characterisation of these solids by Infrared and Raman spectroscopy indicated that the M(TCNQF)2(H2O)2 complexes were similar to other transition metal complexes in the M(TCNQX)2(S)2 series where S=solvent (H2O or CH3OH) and X = H4 or F4. The M(TCNQF) materials containing the TCNQF2− anion were not stable in air, similar to the highly air-sensitive TCNQ2− derivatives. Scanning Electron Microscopy (SEM) images of electrocrystallised samples of Ni(TCNQF)2(H2O)2 were rod-like, whereas the Co(TCNQF)2(H2O)2 formed needles. Energy-dispersive X-ray spectroscopy (EDX) analysis of these samples together with elemental microanalysis and thermogravimetric analysis (TGA) supported the composition and stoichiometry. The solubility products (Ksp values) of M(TCNQF)2(H2O)2 materials were determined spectrophotometrically and voltammetrically in acetonitrile, where Ksp for Co(TCNQF)2(H2O)2 was 3.37×10−11 M3 (or 1.14×10−10 M3 in the presence of electrolyte, 0.1 M Bu4NPF6) and Ni(TCNQF)2(H2O)2 was 5.54×10−12 M3 (or 2.65×10−10 M3 in the presence of electrolyte, 0.1 M Bu4NPF6).

KW - bulk electrolysis

KW - cyclic voltammetry

KW - electrocrystallisation

KW - morphology

KW - vibrational spectroscopy

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U2 - 10.1002/celc.201800678

DO - 10.1002/celc.201800678

M3 - Article

VL - 6

SP - 221

EP - 228

JO - ChemElectroChem

JF - ChemElectroChem

SN - 2196-0216

IS - 1

ER -