Semiconducting Neutral Microstructures Fabricated by Coordinative Self‐Assembly of Intramolecular Charge‐Transfer Tetrathiafulvalene Derivatives

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Abstract
A new class of tetrathiafulvalene‐based microstructures fabricated by coordinative self‐assembly has been prepared by a solution process. Upon incorporation of Pb2+ and Zn2+ ions, 1D wirelike microstructures and spherical polymer particles were achieved, respectively (see picture). The neutral coordination polymers are conductive and magnetic at room temperature without external manipulation. A new class of tetrathiafulvalene(TTF)‐based microstructures fabricated by coordinative self‐assembly has been successfully prepared by a solution process. The morphology of the TTF coordination polymers is readily tuned by the variation of metal ions. Upon incorporation of Pb2+ and Zn2+ ions, one‐dimensional (1D) wirelike microstructures and spherical polymer particles were achieved, respectively. These results indicate that the coordinative approach pursued in this work, in which the building blocks of 1 are linked in a coordination polymer chain by association with metal ions, is an efficient and versatile approach to produce more mechanically robust micro‐ and nanometer‐sized coordination polymer materials. More interestingly, the neutral coordination polymers are conductive and magnetic at room temperature without external manipulation. Such conductivity is reminiscent of the behavior of the neutral conductive TTF in single crystals.