L-Alanine-derived optically active trans-platinum complexes bearing azobenzene moieties, L-trans-Pt[P(Ph) 2 -1,4-C 6 H 4 -CONH-C*H(CH 3 )-CONH-1,4- (L-2a-5c) were synthesized by the ligand exchange reaction of trans-Pt(PPh 3 ) 2 (CCPh) 2 and cis-Pt(cod)(CCPh) 2 , respectively, with L-P(Ph) 2 -1,4-C 6 H 4 -CONH-C*H(CH 2 Ph)-CONH-1,4-C 6 H 4 -NN-Ph. The trans-azobenzene moieties of the complexes isomerized to the cis form upon UV-light irradiation and returned to the trans form upon visible-light irradiation. L-2a-5t displayed weak circular dichroism (CD) signals irrespective of the trans and cis forms of the azobenzene moieties. On the other hand, L-2a-5c with trans-azobenzene moieties displayed strong CD signals, whose intensity decreased upon UV-light irradiation, accompanied by an increase in CD signals based on cis-azobenzene moieties. DFT calculations of the complexes indicated that intramolecular hydrogen bonds form between the amide moieties of two ligands in the cis-platinum complexes, resulting in retention of conformation. A noncovalent interaction plot analysis also indicated that the π−π interaction between the benzene rings of the ligands also contributes to conformational maintenance. The D-alanine-derived counterparts, D-2a-5t and D-2a-5c, exhibited mirror-image CD spectroscopic patterns in comparison to those of L-2a-5t and L-2a-5c. Solution-state IR absorption spectroscopic peaks of CO stretching and N−H bending vibrations of L-2a-5c were observed broadly at ca. 10 cm −1 lower and higher than those of P(Ph) 2 -1,4-C 6 H 4 -CONH-C*H(CH 3 )-CONH-1,4-C 6 H 4 -NN-Ph (L-2a), respectively, thus supporting the formation of intramolecular hydrogen bonding at the amide groups.
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