Forbidden Electronic Transitions between the Singlet Ground State and the Triplet Excited State of Pt(II) Complexes

Direct access to the triplet emitting state from the ground state is observed for Pt(II) complexes containing heterocyclic (CwedgeC', CwedgeN, NwedgeN') and bis(diphenylphosphino)alkane (PwedgeP') ligands. Extinction coefficients for such transitions are in the range 4-25 M(-)(1) cm(-)(1). Emission quantum yields resulting from singlet-to-triplet excitation are as high as 61-77 times the emission quantum yields resulting from singlet-to-singlet excitation at 296 K. The intersystem crossing quantum yield from the singlet excited state to triplet emitting state is lower than 2% at 296 K but is greatly enhanced at 77 K. The forbidden electronic transition observed for Pt(II) complexes is attributed to result from spin-orbit coupling due to the presence of Pt(II) in the skeleton structure. The importance of excitation spectra on the computation of emission quantum yields is discussed.