Excited State Dynamics of Geometrical Evolution of α-Substituted Dibenzoylmethanatoboron Difluoride Complex with...

Organic molecules with an aggregation-induced emission (AIE) property have been attracting much attention from the viewpoint of application to solid state emissive materials. For the AIE mechanism, quantum mechanical studies proposed the restriction of the intramolecular motion (RIM) model with the contribution of the conical intersection (CI) and deduced the importance of the restricted access to a conical intersection (RACI) in the potential energy surface (PES). Although these theoretical studies have contributed to the elucidation of AIE phenomena, direct detection of the reaction dynamics is indispensable to clarify the actual PES and the deactivation mechanism. Along this line, we investigated excited state dynamics of the AIE molecule with dibenzoylmethanatoboron difluoride complexes using time-resolved absorption spectroscopies in both visible and infrared (IR) regions. While the reference system of 1,3-bis(4-methoxyphenyl)methanatoboron difluoride (2aBF₂) showed strong emission in solution, the methyl-substituted derivative at the α-position of the dioxaborine ring (2amBF₂) led to the very weak fluorescence in solution but strong emission in the solid state. Time-resolved visible absorption measurements revealed a peak shift and broadening of the stimulated emission in the solution of 2amBF₂, owing to the rapid change of the molecular geometry. With the temporal evolution of time-resolved IR absorption signals and density functional theory (DFT) calculation of these systems, it was deduced that 2amBF₂ has two stable geometries, namely, planar and bending, in the S₁ state and the bending geometry in the S₁ state led to rapid conversion to the S₀ state. These results support the RACI model in the aggregated states, leading to the AIE properties.