A Carbazole-Bridged Biscyclometalated Diplatinum Complex: Synthesis, Characterization, and Dual-Mode...

A cationic carbazole-bridged biscyclometalated diplatinum complex 4 has been synthesized and characterized. Single-crystal X-ray analysis demonstrates that complex 4 displays a dimeric structure with noncovalent π-π stacking and unique double Pt-Pt interactions. In aerated dilute CH₃CN, complex 4 is characterized by a very weak monomeric yellow emission (λ_emi = 547 nm; Φ = 0.51%), which is attributed to the triplet intraligand (³LC) excited state mixing with some charge transfer characters. In contrast, under aerated conditions, the dispersion of 4 in a mixed solvent of CH₃CN/Et₂O (1/9, v/v) or CH₃CN/H₂O (1/9, v/v) displays intense yellow (λ_emi = 550 nm; Φ = 35.5%; τ = 11.10 μs) and red emission (λ_emi = 635 nm; Φ = 14.1%; τ = 7.00 μs), respectively. These aggregation-induced phosphorescent emission enhancements are considered being caused by the oxygen-shielding effect and the molecular rigidification-induced decrease of nonradiative decays in the aggregate state. The morphology and size of the aggregates under these two conditions are examined by scanning electron microscope and dynamic light scattering analysis. The absorption and emission properties of 4 are further rationalized by time-dependent density functional theory calculations on a model compound.