Circularly Polarized Luminescence of Chiral Pt(pppb)Cl (pppbH=1-pyridyl-3-(4,5-pinenopyridyl)benzene) Aggregate in the Excited State

摘要

We prepared enantiomers of chiral Pt-II complexes, Pt(pppb)Cl and Pt(pppb)CN (pppbH=1-pyridyl-3-(4,5-pinenopyridyl)benzene), and measured their CPL (circularly polarized luminescence) spectra for excimer and trimer emission. The contribution of the pinene moiety to CPL was considerably low for the -* emission of the monomer but large for MMLCT (metal-metal-to-ligand charge-transfer) of the excimer and trimer which had a helical structure induced in a face-to-face stacking fashion. The trimer CPL for (+)-Pt(pppb)Cl was larger in intensity than that of excimer CPL; on the other hand, that for (+)-Pt(pppb)CN was opposite in sign compared with that of excimer CPL. We conclude that differences in the excited-state structure of the aggregate between Pt(pppb)Cl and Pt(pppb)CN account for the variation in the CPL spectra. By the aid of TD-DFT calculations it was predicted that the dihedral angle (Cl-Pt-Pt-Cl) was 50-60 degrees or 110-140 degrees for Pt(pppb)Cl aggregates and 160 degrees for Pt(pppb)CN aggregates.