Structural diversity in charge transfer salts based on Mo3S7 and Mo3S4Se3 clusters complexes and bis(ethylenedithio)tetrathiafulvalene (ET)

Antonio Alberola; Rosa Llusar; Sonia Triguero; Cristian Vicent; Maxim N. Sokolov; Carlos Gómez-García

doi:10.1039/B703551A

Structural diversity in charge transfer salts based on Mo₃S₇ and Mo₃S₄Se₃ clusters complexes and bis(ethylenedithio)tetrathiafulvalene (ET)†

Antonio Alberola,^a Rosa Llusar,*^a Sonia Triguero,^a Cristian Vicent,*^a Maxim N. Sokolov^b and Carlos Gómez-García^c

* Corresponding authors

^a Departament de Química Física i Analítica, Universitat Jaume I, Campus de Riu Sec, 12071, Castellón, Spain
E-mail: llusar@qfa.uji.es, barrera@sg.uji.es

^b Institute of Inorganic Chemistry, SB RAS, pr. Lavrentyeva 3, Novosibirsk 630090, Russia

^c Instituto de Ciencia Molecular, Universitat de Valencia, Instituto de Ciencia Molecular, Poligono la Coma S/N, E-46980, Paterna, Spain

Abstract

Chemical modification of the trinuclear [Mo₃(μ₃-S)(μ₂-S₂)₃Br₆]²⁻ cluster, at either the outer bromine or the disulfide ligands, allows the facile preparation of the dianions [Mo₃(μ₃-S)(μ₂-S₂)₃(tdas)₃]²⁻ ([1]²⁻) (tdas = 1,2,5-thiadiazole-3,4-dithiol), [Mo₃(μ₃-S)(μ₂-SSe)₃Br₆]²⁻ ([2]²⁻) and [Mo₃(μ₃-S)(μ₂-S₂)₃Cl₆]²⁻ ([3]²⁻). Electrocrystallization of bis(ethylenedithio)tetrathiafulvalene (ET) in the presence of these dianions affords a series of charge transfer salts, namely (ET_A)(ET_B)[1], (ET_A)(n-Bu₄N)[2], (ET_A)(ET_B)[3]₂·CH₃CN, and ((ET_A)(ET_B)(ET_C)(ET_D))₂{[3]₂Cl}·CH₃CN, where the ET subscripts denote crystallographically independent molecules. In all cases, the various cluster–cluster, cluster–donor and donor–donor interactions give rise to rich structural diversity in the inorganic and organic sublattices. Raman spectroscopy has been used to account for the degree of charge transfer in the organic donor ET. The ET molecules are oxidized to the integral 1+ oxidation state in compounds (ET_A)(ET_B)[1] and (ET)(n-Bu₄N)[2] and to the integral value of 2+ in compound (ET_A)(ET_B)[3]₂·CH₃CN. Their transport properties reveal semiconducting behaviour with a room temperature conductivity of 4 × 10⁻⁵ S· cm⁻¹ and an activation energy of 280 meV for compound (ET_A)(ET_B)[1] while the other two compounds are insulators. Non-integer values less than 1+ are observed for ((ET_A)(ET_B)(ET_C)(ET_D))₂{[3]₂Cl}·CH₃CN which shows metallic behavior at high temperatures with an irreversible transition to an activated conductivity at ca. 270 K.

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Article information

DOI: https://doi.org/10.1039/B703551A
Article type: Paper
Submitted: 08 Mar 2007
Accepted: 29 May 2007
First published: 13 Jun 2007

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J. Mater. Chem., 2007,17, 3440-3450

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Structural diversity in charge transfer salts based on Mo₃S₇ and Mo₃S₄Se₃ clusters complexes and bis(ethylenedithio)tetrathiafulvalene (ET)

A. Alberola, R. Llusar, S. Triguero, C. Vicent, M. N. Sokolov and C. Gómez-García, J. Mater. Chem., 2007, 17, 3440 DOI: 10.1039/B703551A

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Journal of Materials Chemistry