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Hybrid Material Based on the Lindquist Polyoxometalate [W6O19]2− and the organosulfur donor o-Me2TTF: A Combined Structural and Spectroscopic Study

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Abstract

The synthesis, crystal structure and spectroscopic properties of the hybrid radical cation salt containing oxidized o-3,4-dimethyltetrathiafulvalene (o-Me2TTF) and the Lindquist polyoxometalate anion [W6O19]2− are reported. The title salt represents the first time a Lindquist polyoxometalate has been utilized as the counter anion with this unsymmetrical member of the TTF family of derivatives. The salt crystallizes in the triclinic space group \( P\bar{1} \)with a = 7.6211(7) Å, b = 9.5231(9) Å, c = 12.2148(11) Å, α = 105.5870(10)°, β = 106.8340(10)° and γ = 95.6950(10)°. Resolution of the solid state structure revealed that the o-Me2TTF radical cations aggregate as isolated face-to-face dimers with intradimer interactions between neighboring sulfur atoms at distances <3.6 Å. Hydrogen bonding was also observed between hydrogen atoms bound to sp 2-hybridized carbon atoms of o-Me2TTF and bridging oxygen atoms of [W6O19]2−. Single crystal IR and Raman spectra were also collected and provide further evidence that the o-Me2TTF donors have been oxidized to their corresponding radical cationic states.

Graphical Abstract

Herein we present the structure and single crystal spectroscopic properties of the hybrid salt (o-Me2TTF)2[W6O19], which combines the unsymmetrical TTF derivative o-Me2TTF with the closed shell Lindquist polyoxometalate [W6O19]2−.

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Acknowledgments

This work was supported by the Polish–French Polonium 2009–2010 Program No. 20083YF, the CNRS-PAN program, and by the French Agence Nationale de la Recherche (Contract No. BLAN08-3 317277) for financial support. MF also thanks the ANR for additional financial support (Contract No. 08-BLAN-0140 3/4-Filled). EWR thanks the French Government for financial support in the form of a Chateaubriand Fellowship (Dossier #634148J). We also thank Thierry Roisnel (CDIFX Rennes) for the X-ray data collection.

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  1. Eric W. Reinheimer

    Present address: Department of Chemistry and Biochemistry and W.M. Keck Foundation Center for Molecular Structure, California State University San Marcos, 333 S. Twin Oaks Valley Road, San Marcos, CA, 92096, USA

Authors and Affiliations

  1. Institut des Sciences Chimiques de Rennes, UMR 6226 CNRS-Université Rennes 1, Campus de Beaulieu, 35042, Rennes, France

    Eric W. Reinheimer & Marc Fourmigué

  2. Institute of Molecular Physics, Polish Academy of Sciences, ul. M. Smoluchowskiego 17, 60-179, Poznań, Poland

    Damian Jankowski & Roman Świetlik

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  1. Eric W. Reinheimer
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Correspondence to Eric W. Reinheimer.

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Reinheimer, E.W., Jankowski, D., Świetlik, R. et al. Hybrid Material Based on the Lindquist Polyoxometalate [W6O19]2− and the organosulfur donor o-Me2TTF: A Combined Structural and Spectroscopic Study. J Chem Crystallogr 43, 178–186 (2013). https://doi.org/10.1007/s10870-013-0403-4

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