Synthesis of Discrete Polynuclear Complexes and Units for Metal-Assembled Compounds

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1) Heterodinuclear metal complexes of various combinations of metal ions were prepared using compartmental ligands and their physicochemical properties and functions were examined. Extensive magnetic studies were made for the complexes to reveal the significance of the electronic structures in determining the nature of magnetic interaction.2) Cyanide-bridged bimetallic compounds of various network structures were prepared and their magnetic nature was studied. Spontaneous magnetization occurs for 2-D and 3-D network compounds but not for 1-D compounds. [Mn(glya)]_3[Cr(CN)_6]_3 (glya=glycine amide) has a 3-D network based on a defective cubane structure and shows ferromagnetic ordering with Tc=71 K, that is the highest among molecular magnets so far structurally characterized.3) A new class of cluster compounds, comprising of 。ニorgano-metallic。ヌ unit and metal oxide unit, were prepared and their properties were studied. They include 。ニdouble bookshelf。ヌ type, 。ニwindmill。ヌ type, 。ニtriple cubane。ヌ type etc. and unique reactivities were found for some of them.4) Porous coordination polymers of various networks were designed by the combination of metal ions and an organic building ligand such as 4,4'-bipyridine. They function as a host for including quest molecules such as CH_4, CO_2, O_2 and N_2.5) Construction of covalently-linked linear metal clusters was studied and linear M-Mo-Mo-M (M=Rh, Ir) clusters were obtained by the reaction of Mo_2(pyphos)_4 (pyphos=6-dipenylphosphino-pyridonate) with M(I) complexes. The terminal metal is reactive due to coordinative unsaturation and some unique reactions were developed.6) Tetranuclear Fe(III) compounds of a cubane structure were prepared using tridentate alcoholic ligands and their magnetic properties were examined. The complex [Fe_4(sae)_4(MeOH)_4] (sae=salicylideneaminoethanolate) was found to be a single-molecule magnet based on various magnetic studies.