Spontaneous redox synthesis of the charge transfer material TTF4[SVMo11O40]

Qi Li, Jinzhen Lu, John Frank Boas, Daouda A K Traore, Matthew Charles James Wilce, Fuzhi Huang, Lisandra Lorraine Martin, Tadaharu Ueda, Alan Maxwell Bond

Research output: Contribution to journalArticleResearchpeer-review

Abstract

The charge-transfer material TTF-(SVMo11O40)-Mo-IV (TTF = tetrathiafulvalene) was prepared by a spontaneous redox reaction between TTF and the vanadium-substituted polyoxometalate (n-Bu4N)(3)[(SVMo11O40)-Mo-V] in both solution and solid state phases. Single crystal X-ray diffraction gave the stoichiometry TTF4[SVMo11O40]center dot 2H(2)O center dot 2CH(2)Cl(2), with single V atom positionally disordered with eight Mo atoms over the whole alpha-Reggin polyanion [SVMo11O40](4-). Raman spectra support the 1+ charge assigned to the oxidized TTF deduced from bond lengths, and elemental and voltammetric analysis also are consistent with this formulation. Scanning electron microscopy images showed a rod-type morphology for the new charge-transfer material. The conductivity of the solid at room temperature is in the semiconducting range. The TTF and (n-Bu4N)(3)[(SVMo11O40)-Mo-V] solids also undergo a rapid interfacial reaction, as is the case with TTF and TCNQ (TCNQ = tetracyanoquinodimethane) solids. EPR spectra at temperatures down to 2.6 K confirm the presence of two paramagnetic species, V(IV) and the oxidized TTF radical. Spectral evidence shows that the TTF-(SVMo11O40)-Mo-IV materials prepared from either solution or solid state reactions are equivalent. The newly isolated TTF-(SVMo11O40)-Mo-IV material represents a new class of TTF-polyoxometalate compound having dual electrical and magnetic functionality derived from both the cationic and anionic components.
Original languageEnglish
Pages (from-to)12929 - 12937
Number of pages9
JournalInorganic Chemistry
Volume51
Issue number23
DOIs
Publication statusPublished - 2012

Cite this

@article{43550c80363244deb5da9ed207e7527f,
title = "Spontaneous redox synthesis of the charge transfer material TTF4[SVMo11O40]",
abstract = "The charge-transfer material TTF-(SVMo11O40)-Mo-IV (TTF = tetrathiafulvalene) was prepared by a spontaneous redox reaction between TTF and the vanadium-substituted polyoxometalate (n-Bu4N)(3)[(SVMo11O40)-Mo-V] in both solution and solid state phases. Single crystal X-ray diffraction gave the stoichiometry TTF4[SVMo11O40]center dot 2H(2)O center dot 2CH(2)Cl(2), with single V atom positionally disordered with eight Mo atoms over the whole alpha-Reggin polyanion [SVMo11O40](4-). Raman spectra support the 1+ charge assigned to the oxidized TTF deduced from bond lengths, and elemental and voltammetric analysis also are consistent with this formulation. Scanning electron microscopy images showed a rod-type morphology for the new charge-transfer material. The conductivity of the solid at room temperature is in the semiconducting range. The TTF and (n-Bu4N)(3)[(SVMo11O40)-Mo-V] solids also undergo a rapid interfacial reaction, as is the case with TTF and TCNQ (TCNQ = tetracyanoquinodimethane) solids. EPR spectra at temperatures down to 2.6 K confirm the presence of two paramagnetic species, V(IV) and the oxidized TTF radical. Spectral evidence shows that the TTF-(SVMo11O40)-Mo-IV materials prepared from either solution or solid state reactions are equivalent. The newly isolated TTF-(SVMo11O40)-Mo-IV material represents a new class of TTF-polyoxometalate compound having dual electrical and magnetic functionality derived from both the cationic and anionic components.",
author = "Qi Li and Jinzhen Lu and Boas, {John Frank} and Traore, {Daouda A K} and Wilce, {Matthew Charles James} and Fuzhi Huang and Martin, {Lisandra Lorraine} and Tadaharu Ueda and Bond, {Alan Maxwell}",
year = "2012",
doi = "10.1021/ic302045m",
language = "English",
volume = "51",
pages = "12929 -- 12937",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "23",

}

Spontaneous redox synthesis of the charge transfer material TTF4[SVMo11O40]. / Li, Qi; Lu, Jinzhen; Boas, John Frank; Traore, Daouda A K; Wilce, Matthew Charles James; Huang, Fuzhi; Martin, Lisandra Lorraine; Ueda, Tadaharu; Bond, Alan Maxwell.

In: Inorganic Chemistry, Vol. 51, No. 23, 2012, p. 12929 - 12937.

Research output: Contribution to journalArticleResearchpeer-review

TY - JOUR

T1 - Spontaneous redox synthesis of the charge transfer material TTF4[SVMo11O40]

AU - Li, Qi

AU - Lu, Jinzhen

AU - Boas, John Frank

AU - Traore, Daouda A K

AU - Wilce, Matthew Charles James

AU - Huang, Fuzhi

AU - Martin, Lisandra Lorraine

AU - Ueda, Tadaharu

AU - Bond, Alan Maxwell

PY - 2012

Y1 - 2012

N2 - The charge-transfer material TTF-(SVMo11O40)-Mo-IV (TTF = tetrathiafulvalene) was prepared by a spontaneous redox reaction between TTF and the vanadium-substituted polyoxometalate (n-Bu4N)(3)[(SVMo11O40)-Mo-V] in both solution and solid state phases. Single crystal X-ray diffraction gave the stoichiometry TTF4[SVMo11O40]center dot 2H(2)O center dot 2CH(2)Cl(2), with single V atom positionally disordered with eight Mo atoms over the whole alpha-Reggin polyanion [SVMo11O40](4-). Raman spectra support the 1+ charge assigned to the oxidized TTF deduced from bond lengths, and elemental and voltammetric analysis also are consistent with this formulation. Scanning electron microscopy images showed a rod-type morphology for the new charge-transfer material. The conductivity of the solid at room temperature is in the semiconducting range. The TTF and (n-Bu4N)(3)[(SVMo11O40)-Mo-V] solids also undergo a rapid interfacial reaction, as is the case with TTF and TCNQ (TCNQ = tetracyanoquinodimethane) solids. EPR spectra at temperatures down to 2.6 K confirm the presence of two paramagnetic species, V(IV) and the oxidized TTF radical. Spectral evidence shows that the TTF-(SVMo11O40)-Mo-IV materials prepared from either solution or solid state reactions are equivalent. The newly isolated TTF-(SVMo11O40)-Mo-IV material represents a new class of TTF-polyoxometalate compound having dual electrical and magnetic functionality derived from both the cationic and anionic components.

AB - The charge-transfer material TTF-(SVMo11O40)-Mo-IV (TTF = tetrathiafulvalene) was prepared by a spontaneous redox reaction between TTF and the vanadium-substituted polyoxometalate (n-Bu4N)(3)[(SVMo11O40)-Mo-V] in both solution and solid state phases. Single crystal X-ray diffraction gave the stoichiometry TTF4[SVMo11O40]center dot 2H(2)O center dot 2CH(2)Cl(2), with single V atom positionally disordered with eight Mo atoms over the whole alpha-Reggin polyanion [SVMo11O40](4-). Raman spectra support the 1+ charge assigned to the oxidized TTF deduced from bond lengths, and elemental and voltammetric analysis also are consistent with this formulation. Scanning electron microscopy images showed a rod-type morphology for the new charge-transfer material. The conductivity of the solid at room temperature is in the semiconducting range. The TTF and (n-Bu4N)(3)[(SVMo11O40)-Mo-V] solids also undergo a rapid interfacial reaction, as is the case with TTF and TCNQ (TCNQ = tetracyanoquinodimethane) solids. EPR spectra at temperatures down to 2.6 K confirm the presence of two paramagnetic species, V(IV) and the oxidized TTF radical. Spectral evidence shows that the TTF-(SVMo11O40)-Mo-IV materials prepared from either solution or solid state reactions are equivalent. The newly isolated TTF-(SVMo11O40)-Mo-IV material represents a new class of TTF-polyoxometalate compound having dual electrical and magnetic functionality derived from both the cationic and anionic components.

U2 - 10.1021/ic302045m

DO - 10.1021/ic302045m

M3 - Article

VL - 51

SP - 12929

EP - 12937

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 23

ER -