Arrangements, Reactivities and Functions of Organic and Organometallic Molecules in Inorganic Layred Spaces

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We have intercalated organic, organometallic molecules and metal complexes into the interlayr spaces of inorganic compounds and studied molecular arrangements and electronic states of guest molecules in the interlayr spaces and found unique physical properties and reactivities of them characteristic of those in the interlayr spaces.1) Intercalation of ferrocenyl derivatives into the interlayr spaces of mixed vanadyl-niobyl phosphates and behaviors of the guest molecules in the spaces have clarified the fundamental characteristics of them in arrangements and electronic states in the interlayr space of the VOPO_4-intercalation compounds formed by redox reactions.2) 3-Methyl-and 3.5-dimethylpyrrole have been intercalated into the VOPO_4 interlayr space, accompanied with polymerization, to afford intercalation compounds. 4-Anilinoaniline has been also polymerized in the VOPO_4 and V_2O_5 interlayr spaces and the polymerization process has been clarified.3) Substituted quinolinium and isoqu … More inolinium cations and the acridinium cation have been intercalated into the interlayr space alpha-zirconium phoshate. Fluorescence spectra and fluorescence lifetimes of them have been measured. The lifetimes are somewhat shortened in the interlayr space compared with in solution, and components having short lifetimes of 4-5 ns are present in the interlayr space.4) Several substituted pyridine derivatives and dipyridyl compounds have been intercalated into the V_2O_5 interlayr space, where pyridyl nitrogen atoms have been partially protonated. The abundances of the protonated nitrogen atoms do not depend on strengths of basicity of a guest molecule. Protonation is affected by the charge separation due to dissociation of water molecules in the interlayr space. The interlayr distances have been clarified to be lengthened with the increase of the abundances of protonated nitrogen atoms per vanadium of the host layr.5) NaTMS clay-intercalation compounds containing spin-crossover iron (II or II) complexes have been prepared. ESR spectra and temperature-dependence of magnetic susceptibilities of them have clarified that these metal complexes have two or three surroundings in the clay interlayr space, the changes between high spin and low spin states occurring in the wide temperature range. Thermodynamic parameters of the equilibria in the spin states have been estimated. Less