Influences of Conjugation Extent on the Aggregation-Induced Emission Quantum Efficiency in Silole Derivatives: A Computational Study.

The photophysical properties of a series of silole derivatives, with hydrogen (TPS), bromine (BrTPS), and conjugated phenyl (HPS), triphenylsilyethynyl (BTPES), and dimethylfluorene (BFTPS) substituents at 2,5-positions in both gas and aggregate phases have been investigated computationally by employing the correlation function rate formalism coupled with a hybrid quantum/molecular mechanics (QM/MM) approach. It is found that the solid-state fluorescence quantum efficiency first increases sharply with the degree of π-conjugation of the 2,5-substituents, then levels off, and finally starts to decrease slightly. This is because the side-group conjugation tends to enhance the radiative decay rate in both gas and solid phases. However, a further increase in conjugation leads to saturation in the radiative decay rate but increases the non-raditiave decay rate due to the decreased energy gap.