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Issue 11, 2012
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Hydrogen-bonded maleate counter anions in tetrathiafulvalene crystals

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Intramolecular and/or intermolecular hydrogen-bonded maleate (HMA) monoanions were introduced into cation radical salts of tetrathiafulvalene (TTF), forming three kinds of crystals: (TTF+)(H2MA)(HMA) (1), (TTF+)3(HMA)3(CH3OH)(H2O)0.5 (2), and (TTF+)3(TTF0)5(HMA)3 (3). In crystals 1 and 2, the monovalent TTF+ cation formed a strong π-dimer of (TTF+)2 and a π-trimer of (TTF+)3, respectively. In crystal 3, a non-uniform π-stack of TTF0 and TTF+ was formed, which was further surrounded by neutral TTF through S⋯S and S⋯π interactions, forming a cylindrical TTF0 array around the π-stack. A charge-separated electronic state of (TTF+)3(TTF0)5(HMA)3 in crystal 3 was observed in the Raman spectra. Crystal 3 showed a semiconducting temperature dependent behavior with a room temperature conductivity of 3 × 10−3 S cm−1, which was six orders of magnitude higher than those of crystals 1 and 2. The protonated state of the (H2MA)(HMA) anion in crystal 1 was representative of an (HMA⋯H+⋯HMA) dimer, where the bridging proton between the two HMA anions was located at the midpoint between the two oxygen sites. A very strong intramolecular symmetrical O–H⋯O hydrogen-bonding interaction was observed in crystals 1–3 according to potential energy calculations of proton coordination in the O–H⋯O hydrogen bonding.

Graphical abstract: Hydrogen-bonded maleate counter anions in tetrathiafulvalene crystals

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Supplementary files

Article information

11 Jan 2012
15 Mar 2012
First published
16 Mar 2012

CrystEngComm, 2012,14, 3875-3881
Article type

Hydrogen-bonded maleate counter anions in tetrathiafulvalene crystals

S. Jayanty, T. Akutagawa and T. Nakamura, CrystEngComm, 2012, 14, 3875
DOI: 10.1039/C2CE25050K

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