Molecular Design and Synthesis of Ferro-and Ferri-Magnetic Inorganic Polymers and Complexes with Tetrathiolate Ligands

Abstract
The orbital-symmetry rules for superexchange couplings of unpaired electrons via ligands were applied to one-dimensional (ID) polymers composed of heteropoly transition-metal tetrathiolates (poly(M1TM2), T: tetrathiolate). The polymers composed of the Cu(II)-Fe(I?)(LS) and Ni(II)(HS)-Fe(III)(LS) units are predicted to be ferromagnetic within ID chains, whereas several polymers such as the Co(II)(HS)-Cu(II) alternating one are considered to be ferrimagnetic. Ferromagnetic metals, dense Kondo and spin-mediated superconductors composed of trinuclear M2TM1TM2 complexes (M1═Ni) are also designed on the basis of the theoretical results. According to these guiding principles, we have performed the synthesis of ferro-and ferrimagnetic polymers composed of heteropoly transition-metal tetrathiolates (poly(M1TM2), T: tetrathiolate). The magnetic measurements of the solids were also carried out and the observed intrachain effective exchange integrals are summarized.

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