酢酸銅をモチーフとした集積型金属錯体

抄録

In this review, a new method for the preparation of metal-assembled complexes based on copper(II) acetate type dinuclear systems has been reported. A variety of coordination modes of carboxylato group were classified into ten types of groups including bis-, tris-, and tetrakis-bridging based on our complexes and discussed in relation to mononuclear, dinuclear, oligonuclear, and polynuclear systems. An interdimer interaction could not be observed in temperature dependence of magnetic susceptibilities at 4.5—300 K region in case of one-dimensional chain systems of copper(II) pivalate with N,N'-bidentate ligands such as pyrazine, 4,4'-bipyridine, 1,4-diazabicyclo[2.2.2]octane. Adsorption property for nitrogen gas was found in a chain system of copper(II) benzoate with pyrazine. Mesomorphic properties were also found for chain systems of copper(II) carboxylates with long alkyl chains. By using copper(II) trichloroacetate, a chain molecule consisting of alternated arrangement of tetranuclear cubane and pyrazine was isolated. Two-dimensional and three-dimensional assembled complexes were obtained by reactions of copper(II) trifluoroacetate and copper(II) propionate, respectively, with pyrazine. Bis-adducts of copper(II) propionate with pyridyl nitronyl nitroxides, copper(II) acetate with a stable adamantanyloxyamino radical, and dinuclear copper(II) complexes with 4-carboxy-2,2,6,6-tetramethylpiperidinyloxy and 3-carboxy-2,2,5,5-tetramethyl-1-pyrrolidinyloxy were prepared as radical-containing copper(II) acetate systems.