Self-assembly of three-dimensional supramolecular polymers through cooperative tetrathiafulvalene radical cation dimerization

Jia Tian, Yu Di Ding, Tian You Zhou, Kang Da Zhang, Xin Zhao, Hui Wang*, Dan Wei Zhang, Zhan Ting Li

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

51 Citations (Scopus)


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 TTFC+, 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 mm) in acetonitrile and 105 nm for T2 (75 mm) 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.

Original languageEnglish
Pages (from-to)575-584
Number of pages10
JournalChemistry - A European Journal
Issue number2
Publication statusPublished - 7 Jan 2014


  • Dimerization
  • Radical cations
  • Stacking interactions
  • Supramolecular polymers
  • Tetrathiafulvalene


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