Influence of Electronic Environment on the Radiative Efficiency of 9-Phenyl-9-carbazole-Based -Carboranyl Luminophores.

The photophysical properties of carboranyl-based donor-acceptor dyads are known to be affected by the electronic environment of the carborane cage but the influence of the electronic environment of the donor moiety remains unclear. Herein, four 9-phenyl-9-carbazole-based --carboranyl compounds (, , , and ), in which an -carborane cage was appended at the C3-position of a 9-phenyl-9-carbazole moiety bearing various functional groups, were synthesized and fully characterized using multinuclear nuclear magnetic resonance spectroscopy and elemental analysis. Furthermore, the solid-state molecular structures of and were determined by X-ray diffraction crystallography. For all the compounds, the lowest-energy absorption band exhibited a tail extending to 350 nm, attributable to the spin-allowed π-π* transition of the 9-phenyl-9-carbazole moiety and weak intramolecular charge transfer (ICT) between the -carborane and the carbazole group. These compounds showed intense yellowish emission (λ = ~540 nm) in rigid states (in tetrahydrofuran (THF) at 77 K and in films), whereas considerably weak emission was observed in THF at 298 K. Theoretical calculations on the first excited states (S) of the compounds suggested that the strong emission bands can be assigned to the ICT transition involving the -carborane. Furthermore, photoluminescence experiments in THF‒water mixtures demonstrated that aggregation-induced emission was responsible for the emission in rigid states. Intriguingly, the quantum yields and radiative decay constants in the film state were gradually enhanced with the increasing electron-donating ability of the substituent on the 9-phenyl group (‒F for < ‒H for < ‒CH for < ‒C(CH) for ). These features indicate that the ICT-based radiative decay process in rigid states is affected by the electronic environment of the 9-phenyl-9-carbazole group. Consequently, the efficient ICT-based radiative decay of -carboranyl compounds can be achieved by appending the -carborane cage with electron-rich aromatic systems.