Synthesis and Adduct Formation of Metal Complexes with a Repetitive Structure

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Metal complexes containing a polypyridine ligand and an amino acid or a peptide were synthesized, and their structures were determined by X-ray diffraction method. Adduct formations between platinum(II) complexes and biological molecules such as nucleotides and cofactors by noncovalent interactions were established. Self-assembly of the complexes of copper(II) etc.led to formation of supramolecular structures.(1)Pt(II) complexes as functional units, [Pt(A)(DA)] where A refers to an amino acid and DA to an aromatic diimine such as 1,10-phenanthroline (phen), were synthesized. New Pt(II)-peptide complexes having methionyiglycine or arginyiglycine in place of A and a pyrazine-bridged dinuclear Pt-glycylglycine complex were also synthesized but were found to be less soluble in water and other solvents than the amino acid complexes.(2)The stability constants for the [Pt(A)(DA)]-nucleotide adducts (DA=phen ; nucleotide=AMP or GMP) were determined by spectroscopic methods and calorimetry. X-r … More ay analysis of [Pt(arg)(phen)]-GMP (arg=arginine) revealed that GMP is bound to the complex by both stacking and hydrogen bonding. The redox potential of FMN (=flavin mononucleotide) was found to be controlled by stacking with the Pt(II) complexes.(3)The structures and stability constants of the ternary Cu(II) complexes containing a synthetic aromatic ligand and glycyltyrosine revealed the existence of the intramolecular CH-π interaction as a structure-determining factor.(4)Various Os(II)-polypyridine complexes were established to be effective mediators of the GOx-glucose redox reaction (GOx = glucose oxidase) and thus may be used for determining the blood glucose level. Ru(II)-polypyridine complexes containing an amino acid were found to undergo light-induced cleavage of DNA in the presence of H_2O_2.(5)An aqueous solution containing Cu(II), M(=Fe(II), Co(II), or Ru(II)), an EDTA derivative L with a longer methylene chain, and phen gave [M(phen)_3]_2[Cu_2L_2], which is considered to be constructed by self-assembly of complex molecules by π-π and CH-π interactions. Less