Development of Multi-functional Ligands for Application of Metal Complexes

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1. The acylation of a Co(III)-DHPTA mononuclear complex have been examined in order to obtain oligomers or polymers in which an octahedral complex are as the side chain, where DHPTA represents 1,3-diamino-2-hydroxypropane-N,N,N',N'-tetraacetic acid. The non-coordinated hydroxyl group in the complex was successfully methacrylated by the reaction of the corresponding acid anhydride with the complex in aprotic solvent, only in the presence of a cryptand. In the presence of a polymerization inhibitor, one methacryl group which can be polymerized, was introduced. On the other hand, the products, which may be formed by sequential polymerization after the acylation, from the methacrylation of the complex without polymerization inhibitor, gave a hydro-gel. This result indicates that the multi-ligand oligomer or polymer is obtained in the chemical modification. We are now examininig the possibility to obtain films of ceramics by the use of hydro-gel obtained here, as an application.2. Removal of Nitrogen oxides in atmosphere is an important subject, not only for chemistry. In this project, we have investigated the coordination behaviors of nitrite ion toward iron(III) in the presence of the above multi-functional ligand, DHPTA. We found the formation of mu -oxo tetranuclear Fe(III) complex ion involving two bridging nitrite ions, from the X-ray crystal structure determination of an isolated green compound Significantly, the multinuclear complex was discovered from an acidic aqueous solution, pH below 2.5. This result suggests that the reaction system consisted of iron(III) and DHPTA may afford an opportunity for capture of nitrogen oxides from serious acid rain and their removal. Moreover, the novel tetranuclear complex are interested in both fields of biochemistry and magnetochemistry.