Formation of Hetero-binuclear Pt(II)-M(II) Complexes Based on (2-(1H-Tetrazol-5-yl)phenyl)diphenylphosphine Oxide for Superior Phosphorescence of Monomers

Novel hetero-binuclear platinum complexes (HBC-Pt(II)-M(II), M = Ca(II), Mg(II), Zn(II), and Cd(II)) have been synthesized by the reaction of the corresponding precursors [Pt(ppy)(μ-Cl)]2with (2-(1H-tetrazol-5-yl)phenyl)diphenylphosphine oxide (TTPPO). The X-ray structures of the complexes show that two ancillary ligands TTPPO in the square-planar Pt(II) moiety act as a quadridentate chelating agent for the other metal center, eventually forming a distorted octahedral configuration. There are no significant π–π interactions and Pt–M metallophilic interactions in the crystal lattice, due to the steric hindrances associated with the rigid octahedral structure together with the bulky TTPPO. Consequently, HBC-Pt-M complexes show monomer emission characteristics with quantum yields up to 59% in powder, suggesting their great potential for practical applications. DFT and TD-DFT calculations on HBC-Pt-Zn reveal that the phosphorescence can be ascribed to intraligand charge transfer (3ILCT) combined with some metal-to-ligand charge transfer (3MLCT) in the Pt(ppy) moiety, which is consistent with the observations from the photophysical investigations.