Controlled potential electrodeposition of a microcrystalline thin film of the charge transfer material tetrathiafulvalene-polyoxometalate of approximate composition (TTF)(5.3)(Bu4N)(0.7)[P2W18O62]center dot 3H(2)O

Qi Li, Chuan Zhao, Alan Bond, John Boas, Anthony Wedd, Boujemaa Moubaraki, Keith Murray

Research output: Contribution to journalArticleResearchpeer-review

Abstract

Electrocrystallisation provides a systematic approach to the preparation of tetrathiafulvalene (TTF)-polyoxometalate materials in the form of films having significant conductivity. In this study, a highly uniform microcrystalline thin film derived from TTF+ and the Dawson-Wells anion [alpha-P2W18O62](6-) has been deposited onto glassy carbon, gold and indium tin oxide surfaces by controlled potential oxidative electrolysis of TTF in the presence of K-6[P2W18O62] in acetonitrile (0.1 M [Bu4N][PF6]). Elemental analytical data are consistent with the formation of this conducting charge transfer salt having the approximate composition (TTF)(5.3)(Bu4N)(0.7)[P2W18O62]center dot 3H(2)O. Spectroscopic data support this conclusion. Mechanistic aspects of the electrocrystallisation process have been monitored by cyclic voltammetry, electrochemical quartz crystal microbalance and chronoamperometric methods. A less crystalline form of this material with a slightly different composition also can be produced by bulk electrolysis of TTF to TTF+ followed by addition of K-6[P2W18O62]. The conductivity of the film at room temperature is in the semiconducting range. The EPR spectra, together with the field strength and temperature dependence of the magnetic susceptibility, suggest that regions of film behave as a quasi one-dimensional system, with antiferromagnetic and spin-flop behaviour at low temperatures. The Raman spectra are consistent with an average TTF charge state of +1, while voltammetry confirms the presence of [P2W18O62](6-). The morphology and crystallinity of the electrocrystallised and chemically prepared materials were investigated by scanning electron microscopy and X-ray diffraction, respectively.
Original languageEnglish
Pages (from-to)5398 - 5407
Number of pages10
JournalJournal of Materials Chemistry
Volume21
Issue number14
DOIs
Publication statusPublished - 2011

Cite this

@article{f3ef4875fac145eab47450ddb2849f21,
title = "Controlled potential electrodeposition of a microcrystalline thin film of the charge transfer material tetrathiafulvalene-polyoxometalate of approximate composition (TTF)(5.3)(Bu4N)(0.7)[P2W18O62]center dot 3H(2)O",
abstract = "Electrocrystallisation provides a systematic approach to the preparation of tetrathiafulvalene (TTF)-polyoxometalate materials in the form of films having significant conductivity. In this study, a highly uniform microcrystalline thin film derived from TTF+ and the Dawson-Wells anion [alpha-P2W18O62](6-) has been deposited onto glassy carbon, gold and indium tin oxide surfaces by controlled potential oxidative electrolysis of TTF in the presence of K-6[P2W18O62] in acetonitrile (0.1 M [Bu4N][PF6]). Elemental analytical data are consistent with the formation of this conducting charge transfer salt having the approximate composition (TTF)(5.3)(Bu4N)(0.7)[P2W18O62]center dot 3H(2)O. Spectroscopic data support this conclusion. Mechanistic aspects of the electrocrystallisation process have been monitored by cyclic voltammetry, electrochemical quartz crystal microbalance and chronoamperometric methods. A less crystalline form of this material with a slightly different composition also can be produced by bulk electrolysis of TTF to TTF+ followed by addition of K-6[P2W18O62]. The conductivity of the film at room temperature is in the semiconducting range. The EPR spectra, together with the field strength and temperature dependence of the magnetic susceptibility, suggest that regions of film behave as a quasi one-dimensional system, with antiferromagnetic and spin-flop behaviour at low temperatures. The Raman spectra are consistent with an average TTF charge state of +1, while voltammetry confirms the presence of [P2W18O62](6-). The morphology and crystallinity of the electrocrystallised and chemically prepared materials were investigated by scanning electron microscopy and X-ray diffraction, respectively.",
author = "Qi Li and Chuan Zhao and Alan Bond and John Boas and Anthony Wedd and Boujemaa Moubaraki and Keith Murray",
year = "2011",
doi = "10.1039/c0jm03011b",
language = "English",
volume = "21",
pages = "5398 -- 5407",
journal = "Journal of Materials Chemistry",
issn = "0959-9428",
publisher = "The Royal Society of Chemistry",
number = "14",

}

Controlled potential electrodeposition of a microcrystalline thin film of the charge transfer material tetrathiafulvalene-polyoxometalate of approximate composition (TTF)(5.3)(Bu4N)(0.7)[P2W18O62]center dot 3H(2)O. / Li, Qi; Zhao, Chuan; Bond, Alan; Boas, John; Wedd, Anthony; Moubaraki, Boujemaa; Murray, Keith.

In: Journal of Materials Chemistry, Vol. 21, No. 14, 2011, p. 5398 - 5407.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Controlled potential electrodeposition of a microcrystalline thin film of the charge transfer material tetrathiafulvalene-polyoxometalate of approximate composition (TTF)(5.3)(Bu4N)(0.7)[P2W18O62]center dot 3H(2)O

AU - Li, Qi

AU - Zhao, Chuan

AU - Bond, Alan

AU - Boas, John

AU - Wedd, Anthony

AU - Moubaraki, Boujemaa

AU - Murray, Keith

PY - 2011

Y1 - 2011

N2 - Electrocrystallisation provides a systematic approach to the preparation of tetrathiafulvalene (TTF)-polyoxometalate materials in the form of films having significant conductivity. In this study, a highly uniform microcrystalline thin film derived from TTF+ and the Dawson-Wells anion [alpha-P2W18O62](6-) has been deposited onto glassy carbon, gold and indium tin oxide surfaces by controlled potential oxidative electrolysis of TTF in the presence of K-6[P2W18O62] in acetonitrile (0.1 M [Bu4N][PF6]). Elemental analytical data are consistent with the formation of this conducting charge transfer salt having the approximate composition (TTF)(5.3)(Bu4N)(0.7)[P2W18O62]center dot 3H(2)O. Spectroscopic data support this conclusion. Mechanistic aspects of the electrocrystallisation process have been monitored by cyclic voltammetry, electrochemical quartz crystal microbalance and chronoamperometric methods. A less crystalline form of this material with a slightly different composition also can be produced by bulk electrolysis of TTF to TTF+ followed by addition of K-6[P2W18O62]. The conductivity of the film at room temperature is in the semiconducting range. The EPR spectra, together with the field strength and temperature dependence of the magnetic susceptibility, suggest that regions of film behave as a quasi one-dimensional system, with antiferromagnetic and spin-flop behaviour at low temperatures. The Raman spectra are consistent with an average TTF charge state of +1, while voltammetry confirms the presence of [P2W18O62](6-). The morphology and crystallinity of the electrocrystallised and chemically prepared materials were investigated by scanning electron microscopy and X-ray diffraction, respectively.

AB - Electrocrystallisation provides a systematic approach to the preparation of tetrathiafulvalene (TTF)-polyoxometalate materials in the form of films having significant conductivity. In this study, a highly uniform microcrystalline thin film derived from TTF+ and the Dawson-Wells anion [alpha-P2W18O62](6-) has been deposited onto glassy carbon, gold and indium tin oxide surfaces by controlled potential oxidative electrolysis of TTF in the presence of K-6[P2W18O62] in acetonitrile (0.1 M [Bu4N][PF6]). Elemental analytical data are consistent with the formation of this conducting charge transfer salt having the approximate composition (TTF)(5.3)(Bu4N)(0.7)[P2W18O62]center dot 3H(2)O. Spectroscopic data support this conclusion. Mechanistic aspects of the electrocrystallisation process have been monitored by cyclic voltammetry, electrochemical quartz crystal microbalance and chronoamperometric methods. A less crystalline form of this material with a slightly different composition also can be produced by bulk electrolysis of TTF to TTF+ followed by addition of K-6[P2W18O62]. The conductivity of the film at room temperature is in the semiconducting range. The EPR spectra, together with the field strength and temperature dependence of the magnetic susceptibility, suggest that regions of film behave as a quasi one-dimensional system, with antiferromagnetic and spin-flop behaviour at low temperatures. The Raman spectra are consistent with an average TTF charge state of +1, while voltammetry confirms the presence of [P2W18O62](6-). The morphology and crystallinity of the electrocrystallised and chemically prepared materials were investigated by scanning electron microscopy and X-ray diffraction, respectively.

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U2 - 10.1039/c0jm03011b

DO - 10.1039/c0jm03011b

M3 - Article

VL - 21

SP - 5398

EP - 5407

JO - Journal of Materials Chemistry

JF - Journal of Materials Chemistry

SN - 0959-9428

IS - 14

ER -