Functional supramolecular tetrathiafulvalene-based films with mixed valences states

•A supramolecular polymeric charge-tunable film based on TTF molecules is presented.•Mixed valence state of TTF molecules in the film was achieved.•The charge transport of the film was showed using Electrostatic Force Microscopy.

Tetrathiafulvalene molecules substituted with a carboxylic acid group (TTFCOOH) were bound as redox-active moieties into a poly(4-vinyl pyridine) (P4VP) skeleton through non-covalent interactions (hydrogen bonds). The aspect of the resulting P4VP-TTFCOOH films showed a uniform and smooth morphology. Moreover, the redox function of TTFCOOH in P4VP-TTFCOOH was demonstrated using tetrachloroauric acid, iron(III) perchlorate and iodine vapors as doping agents. The oxidized states of TTFCOOH as well as the mixed valance state TTFCOOH0-TTFCOOH+• were generated in a controlled manner in solid state, resulting in an organic film capable of charge transport. The charge transport along the organic donor molecules hydrogen bonded to the polymer matrix was demonstrated employing Electrostatic Force Microscopy (EFM).

Graphical abstractCharge-tunable films based on a complex of poly(4-vinyl pyridine) and tetrathiafulvalene for electrostatic responsive functional materials.Download high-res image (220KB)Download full-size image