Circularly Polarized Luminescence of Cyclometalated Platinum(II) Complex Excimers: Large Difference between Isomers

A series of platinum(II) complexes bearing a chiral beta- diketonato ligand and a cyclometalated ligand have been prepared. The platinum(II) complexes, (SP-4-3)-[Pt(ppy)(D-tac)] (ppy = 2-phenyl-pyridine, D-tac = 3-trifluoroacetyl-(D)-camphor), (SP-4-4)-[Pt(ppy)(D-tac)], (SP-4-3)-[Pt(ppy)(D-pbc)] (D-pbc = 3-perfluorobutyryl-(D)-camphor), and (SP-4-4)-[Pt(ppy)(D-pbc)], and their enantiomers were isolated and characterized by elemental analysis, NMR, and X-ray structural analysis. Photoisomerization between SP-4-3 (trans) and SP-4-4 (cis) isomers was observed. Green emission due to the monomer was observed in diluted solutions for all complexes. Higher quantum yields and longer lifetimes of green emission were observed in nonpolar solvents compared to polar solvents. The two geometrical isomers had surprisingly different excimer formation efficiencies. For the trans isomers, orange emission due to the excimers was observed in nonpolar solvents at high concentrations, whereas negligible intensities of the excimer emission were observed for the cis isomers. The formation of the excimers was evaluated by emission decay and time-resolved emission spectra. For the trans isomers, the green emission due to the monomer showed negligible CPL signals, but the orange emission gave pronounced CPL signals. The dissymmetry factors, g-values, of the excimer CPL (glum = 0.002) were enhanced over those of the circular dichroism (gabs = 0.0002, glum/gabs = 10). The intensities of the emission and the CPL of the excimer under oxygen were very small, although those under an argon atmosphere were very strong. Therefore, the emission color of the trans-isomers was changed from green to orange by deoxygenation.