Luminescent Platinum(II) Complexes with Stimuli-Responsive Flexible Lewis Pair Ligands: Spectroscopic and Computational Studies.

Abstract

A series of new luminescent bimetallic platinum(II) complexes with stimuli-responsive flexible Lewis pair (FlexLP) ligands are described. The FlexLP ligands consist of a dimesitylboron Lewis acid and diphenylphosphine oxide Lewis base which are in equilibrium between the unbound open form and the Lewis adduct, controlled by the hydrogen bond donating strength of the solvent. Spectroscopic techniques and density functional theory (DFT) calculations were used to interpret the photophysics of the platinum(II) complexes. All complexes exhibit tunable absorption in the region of 300-500 nm and green to orange photoluminescence, depending on the ratio of weak (THF) to strong (MeOH) hydrogen bond donating solvent employed. Spectroscopic and computational data shows that phosphine and peripheral acetylide ligands on the platinum(II) centers have limited influence on the emission energy, indicating the emission originates from the FlexLP-dominated fluorescence. Using time-resolved transient absorption spectroscopy it is shown that the complexes undergo intersystem crossing (ISC) to the triplet excited state upon photoexcitation, and the ISC efficiency is affected by the peripheral acetylide ligands. The triplet excited state lifetime can also be manipulated by the state of the FlexLP ligand, with the closed form complexes having longer lifetimes than the open form complexes.