B- and N-Embedded π-Conjugation Units Tuning Intermolecular Interactions and Optical Properties of Platinum(II) Complexes.

A new series of neutral and cationic platinum(II) complexes containing a B- or N-embedded π-conjugation unit has been prepared. Notably, significantly different intermolecular interactions (Pt-Pt, π-π, head to tail, and head to head) and interesting optical properties exist in these complexes, which can be attributed to the difference in spatial structures and π-electron properties between B- and N-embedded π-conjugation units. Unexpectedly, under a hypoxic atmosphere, N-embedded neutral complex PtNacac can display a distinct dual-emission with both fluorescence and phosphorescence, whereas only a single fluorescence emission was observed in the air, which is different from the B-embedded neutral complex PtBacac with only a single phosphorescence emission at any atmosphere, as well confirmed by lifetime measurement and oxygen sensing experiments. DFT calculations reveal that unusual ligand-to-metal charge transfer (LMCT) excited state character and low spin orbit coupling (SOC) elements can be found in N-embedded complexes due to the strong electron-donating ability of the N-embedded unit. Based on this, as a novel ratiometric oxygen probe with a simple structure, PtNacac can be successfully used to examine intracellular oxygen levels by monitoring both fluorescence and phosphorescence signals via ratiometric photoluminescence imaging and time-resolved luminescence imaging (TRLI) technology. This work provides a completely new idea for designing fluorescence/phosphorescence dual-emissive complexes.