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Issue 19, 1998
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S  · · ·  S Contact-assembled tetrathiafulvalene derivatives of copper(I) and silver(I) co-ordination polymers and organic radical cation salt

Abstract

The reactions of 2-[4,5-bis(methylsulfanyl)-1,3-dithiol-2-ylidene]-4,5-bis(2-cyanoethylsulfanyl)-1,3-dithiole (CM-TTF ) with copper(II) and silver(I) salts resulted in the isolation and structural characterization of S  · · ·  S contact assembled co-ordination polymers, [Cu(CM-TTF )][ClO4]·thf 1 and [Ag(CM-TTF )(CF3SO3)] 2, and radical cation salt, [CM-TTF][CuCl2] 3. Both 1 and 2 are 1∶1 metal–ligand complexes in which the metal ions and CM-TTF molecules are alternately linked forming two-dimensional networks and infinite linear chain structures, respectively, which are further reinforced by close intermolecular S  · · ·  S interactions. The structure of 3 consists of segregated stacks of CM-TTF˙+ donors and CuCl2 acceptors associated via short S  · · ·  Cl contacts leading to an alternate donor–acceptor–donor columnar arrangement. The complexes were additionally characterized by IR, UV/VIS and ESR spectra as well as electrical resistivity measurements. All the complexes and their corresponding air-oxidized species are poor electrical conductors, but they show typical charge-transfer ESR signals and electronic absorptions. Complex 3 was found to exhibit transition from antiferro- to ferro-magnetic coupling upon air oxidation.

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Supplementary files


Article type: Paper
DOI: 10.1039/A804945I
J. Chem. Soc., Dalton Trans., 1998, 3255-3262

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    S  · · ·  S Contact-assembled tetrathiafulvalene derivatives of copper(I) and silver(I) co-ordination polymers and organic radical cation salt

    L. Ping Wu, J. Dai, M. Munakata, -. Maekawa, Y. Suenaga and Y. Ohno, J. Chem. Soc., Dalton Trans., 1998, 3255
    DOI: 10.1039/A804945I

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