10.1021/ic302045m.s001
Qi Li
Qi
Li
Jinzhen Lu
Jinzhen
Lu
John F. Boas
John F.
Boas
Daouda
A. K. Traore
Daouda
A. K.
Traore
Matthew C. J. Wilce
Matthew
C. J. Wilce
Fuzhi Huang
Fuzhi
Huang
Lisandra L. Martin
Lisandra L.
Martin
Tadaharu Ueda
Tadaharu
Ueda
Alan M. Bond
Alan M.
Bond
Spontaneous Redox Synthesis
of the Charge Transfer
Material TTF<sub>4</sub>[SVMo<sub>11</sub>O<sub>40</sub>]
American Chemical Society
2012
EPR spectra
material
Spontaneous Redox Synthesis
Scanning electron microscopy images
2.6 K
TTF
V atom positionally
state reactions
bond lengths
Mo atoms
TCNQ
voltammetric analysis
redox reaction
state phases
Spectral evidence
semiconducting range
SVMo 11O Raman spectra support
4N
room temperature
2012-12-03 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Spontaneous_Redox_Synthesis_of_the_Charge_Transfer_Material_TTF_sub_4_sub_SVMo_sub_11_sub_O_sub_40_sub_/2464630
The charge-transfer material TTF-SV<sup>IV</sup>Mo<sub>11</sub>O<sub>40</sub> (TTF = tetrathiafulvalene) was prepared by
a spontaneous
redox reaction between TTF and the vanadium-substituted polyoxometalate
(n-Bu<sub>4</sub>N)<sub>3</sub>[SV<sup>V</sup>Mo<sub>11</sub>O<sub>40</sub>] in both solution and solid state phases. Single crystal
X-ray diffraction gave the stoichiometry TTF<sub>4</sub>[SVMo<sub>11</sub>O<sub>40</sub>]·2H<sub>2</sub>O·2CH<sub>2</sub>Cl<sub>2</sub>, with the single V atom positionally disordered with
eight Mo atoms over the whole α-Keggin polyanion [SVMo<sub>11</sub>O<sub>40</sub>]<sup>4‑</sup>. 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-Bu<sub>4</sub>N)<sub>3</sub>[SV<sup>V</sup>Mo<sub>11</sub>O<sub>40</sub>] 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-SV<sup>IV</sup>Mo<sub>11</sub>O<sub>40</sub> materials prepared from either solution or solid state reactions
are equivalent. The newly isolated TTF-SV<sup>IV</sup>Mo<sub>11</sub>O<sub>40</sub> material represents a new class of TTF-polyoxometalate
compound having dual electrical and magnetic functionality derived
from both the cationic and anionic components.