Preparation of new inorganic superlattices by two-dimensional ordering of metal orbitals

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The present study aimed at precise structural control of various inorganic clusters by using cast films of bilayr membranes of synthetic amphiphiles. Major accomplishments are as follows.1) A new bilayr with dicationic viologen head group was synthesized to enhance the density of inorganic guest molecules incorporated into the interlayr.2) Ni (CN)_4, Au (CN)_4, Pt (CN)_4, MoS_4, were introduced into the layr by ion exchange, and then Cu (II) ion was introduced by immersion. Infrared spectroscopy indicated the formation of cyano-bridged clusters in the case of Ni-Cu and Pt-Cu films. ESR spectroscopy of these two films display remarkable anisotropies which suggest that a Cu (II) d orbital is placed parallel to the film layr with regular spin ordering similar to that of crystals.3) The MoS_4/Cu (II) complex that was prepared by sequential synthesis on the cast film template does not give ESR signals of Cu (II) itself in consistence with the presumed structure. Therefore, cluster formation that accompany redox reaction of the precursor ion is achieved.4) Photo-induced growth of a Fe (II) -Fe (III) mixed valence complex was found by using the monolayr template at the air-water interface.