Molecular Design of Photocatalysts Based on 'Peptide Origami' toward Nitrite Reductase Mimics

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The 'Peptide Origami' is a synthetic strategy of functional metal-peptide complexes. In this strategy, the peptides containing unnatural amino acids capable of coordinating to metal ions fold by coordination to produce functional molecules. This study aims at synthesis of photocatalysts, in which the photo-sensitizing part attaches to the catalytic one, by using the 'Peptide Origami strategy. This reports (1) reevaluation of the emission quantum yield of[Ru(bpy)_3]^<2+>(bpy=2, 2'-bipyridine), (2) the chain reaction for isomerization from trans to cis(Cl)-Ru(bpy)(CO)_2Cl_2, (3) synthesis of the photo-induced charge separation system which consists of a ruthenium-peptide complex, (4) stereoselective formation of chiral metallopeptides, and (5) synthesis of the peptide containing histidine and the unnatural bipyridyl-type amino acid.