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A covalent attraction between two molecular cation TTF·+

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Abstract

The optimized structure of the tetrathiafulvalence radical-cation dimer (TTF·+-TTF·+) with all-real frequencies is obtained at MP2/6-311G level, which exhibits the attraction between two molecular cation TTF·+. The new attraction interaction is a 20-center-2-electron intermolecular covalent π/π bonding with a telescope shape. The covalent π/π bonding has the bonding energy of about −21 kcal·mol−1 and is concealed by the Coulombic repulsion between two TTF·+ cations. This intermolecular covalent attraction also influences the structure of the TTF·+ subunit, i.e., its molecular plane is bent by an angle θ = 5.6°. This work provides new knowledge on intermolecular interaction.

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Authors and Affiliations

  1. State Key Laboratory of Theoretical and Computational Chemistry, Institute of Theoretical Chemistry, Jilin University, Changchun, 130023, China

    FangFang Wang, BingQiang Wang, YinFeng Wang, Fang Ma & ZhiRu Li

  2. Basic Course of Public Security Department, China Criminal Police University, Shenyang, 110035, China

    Yi Wang

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  1. FangFang Wang
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Correspondence to ZhiRu Li.

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Supported by the National Natural Science Foundation of China (Grant No. 20773046)

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Wang, F., Wang, Y., Wang, B. et al. A covalent attraction between two molecular cation TTF·+ . Sci. China Ser. B-Chem. 52, 1980–1986 (2009). https://doi.org/10.1007/s11426-009-0262-1

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