Function-Switchable Supramolecular System with Channel Structure

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The results obtained during the research period (1999-2000) is summarized as follows.(1) A sulfur-linked cross-cyclophane donor was found to afford a semiconductive and paramagnetic ion radical salt which exhibits a structure phase transition at 160 K.In the low-temperature phase the conductivity of the salt was increased by one-order and the number of paramagnetic spins was decreased by one-half compared with those of the high temperature phase. The phase transition turns out to be reversible and it takes place triggered by the dynamics of counter-ions and solvent molecules inside of the channel constructed in the ion radical salts. A full paper to be submitted to J.Am Chem Soc. is in preparation.(2) A selen-linked cross-cyclophane donor also afforded a semiconductive ion radical salt with a channel structure in a more organized manner. The self-assembled structure of the singly oxidized donor of the cross cyclophane shape is an excellent example which demonstrates the characteristics of a self-assembly composed of a polyhedral building block. A short communication was submitted to Chem. Communication.(3) A layer-structured ion radical salt composed of BEDT-TTF_3 Cl_2 5H_2O was discovered to exhibit a rectifying effect on the conducting property. The origin of the rectifying effect was ascribe to the current-induced translocation of counter ions assisted by the change of the hydrogen-bonding scheme in the hydrated counter ion layer. A full paper is now in preparation.