Self-Assembly of Three-Dimensional Supramolecular Polymers through Cooperative Tetrathiafulvalene Radical Cation Dimerization

Authors

  • Jia Tian,

    1. Department of Chemistry, Fudan University, 220 Handan Road, Shanghai 200433 (China), Fax: (+86) 21-65641740
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  • Yu-Di Ding,

    1. Department of Chemistry, Fudan University, 220 Handan Road, Shanghai 200433 (China), Fax: (+86) 21-65641740
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  • Tian-You Zhou,

    1. Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032 (China)
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  • Dr. Kang-Da Zhang,

    1. Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032 (China)
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  • Prof. Xin Zhao,

    1. Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 345 Lingling Lu, Shanghai 200032 (China)
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  • Dr. Hui Wang,

    Corresponding author
    1. Department of Chemistry, Fudan University, 220 Handan Road, Shanghai 200433 (China), Fax: (+86) 21-65641740
    • Hui Wang, Department of Chemistry, Fudan University, 220 Handan Road, Shanghai 200433 (China), Fax: (+86) 21-65641740

      Yi Liu, The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (USA)

      Zhan-Ting Li, Department of Chemistry, Fudan University, 220 Handan Road, Shanghai 200433 (China), Fax: (+86) 21-65641740

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  • Prof. Dan-Wei Zhang,

    1. Department of Chemistry, Fudan University, 220 Handan Road, Shanghai 200433 (China), Fax: (+86) 21-65641740
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  • Prof. Yi Liu,

    Corresponding author
    1. The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (USA)
    • Hui Wang, Department of Chemistry, Fudan University, 220 Handan Road, Shanghai 200433 (China), Fax: (+86) 21-65641740

      Yi Liu, The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (USA)

      Zhan-Ting Li, Department of Chemistry, Fudan University, 220 Handan Road, Shanghai 200433 (China), Fax: (+86) 21-65641740

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  • Prof. Zhan-Ting Li

    Corresponding author
    1. Department of Chemistry, Fudan University, 220 Handan Road, Shanghai 200433 (China), Fax: (+86) 21-65641740
    • Hui Wang, Department of Chemistry, Fudan University, 220 Handan Road, Shanghai 200433 (China), Fax: (+86) 21-65641740

      Yi Liu, The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, CA 94720 (USA)

      Zhan-Ting Li, Department of Chemistry, Fudan University, 220 Handan Road, Shanghai 200433 (China), Fax: (+86) 21-65641740

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Abstract

The self-assembly of a new type of three-dimensional (3D) supramolecular polymers from tetrahedral monomers in both organic and aqueous media is described. We have designed and synthesized two tetraphenylmethane derivatives T1 and T2, both of which bear four tetrathiafulvalene (TTF) units. When the TTF units were oxidized to the radical cation TTF.+, their pre-organized tetrahedral arrangement remarkably enhanced their intermolecular dimerization, leading to the formation of new 3D spherical supramolecular polymers. The structure of the supramolecular polymers has been inferred on the basis of UV/Vis absorption, electron paramagnetic resonance, cyclic voltammetry, and dynamic light scattering (DLS) analysis, as well as by comparing these properties with those of the self-assembled structures of mono-, di-, and tritopic control compounds. DLS experiments revealed that the spherical supramolecular polymers had hydrodynamic diameters of 68 nm for T1 (75 μM) in acetonitrile and 105 nm for T2 (75 μM) in water/acetonitrile (1:1). The 3D spherical structures of the supramolecular polymers formed in different solvents were also supported by SEM and AFM experiments.

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