Preparation and Assemblization of Highly Functionalized Organic Magnetic Molecules

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Development of organic magnetic metals is one of the most interest investigation for molecular magnetism. In such spin system, it is required a spin correlation between conduction electrons and local spins. We designed a series of open-shell donors which are candidate molecules as components of such spin system. The open shell donors are constructed with a donor and a radical unit and they are connected so as to become a cross-conjugate pi-system when one-electron oxidation takes place. We prepared two open-shell donor isomers (2,7- and 2,8-isomer) composed of two nitronyl nitroxides as radical unit and a thianthrene as a donor unit. SQUID measurements showed that these isomers are ground state triplet and singlet in neutral state, respectively. The ESR study showed that they changes the ground state multiplicity from triplet and singlet to both quartet through one-electron oxidation. Three TTF-based open-shell donors were also prepared. Cyclic voltammetry and ESR measurement indicate that these donors have a similar donor ability to the mother donors and the electronic character as the open-shell donor. These results indicate that these open-shell donors satisfy one of required conditions for the components of organic magnetic metals. Preparations of mixed valent radical ion salts composed of these radicals are in progress.