Although there are some proposed explanations for aggregation-induced emission, a phenomenon with applications that range from biosensors to organic light-emitting diodes, current understanding of the quantum-mechanical origin of this photophysical behaviour is limited. To address this issue, we assessed the emission properties of a series of BF-hydrazone-based dyes as a function of solvent viscosity. These molecules turned out to be highly efficient fluorescent molecular rotors. This property, in addition to them being aggregation-induced emission luminogens, enabled us to probe deeper into their emission mechanism. Time-dependent density functional theory calculations and experimental results showed that the emission is not from the S state, as predicted from Kasha's rule, but from a higher energy (>S) state. Furthermore, we found that suppression of internal conversion to the dark S state by restricting the rotor rotation enhances fluorescence, which leads to the proposal that suppression of Kasha's rule is the photophysical mechanism responsible for emission in both viscous solution and the solid state.

No abstract

Over the past decade, fluorophores that exhibit "mega" Stokes shifts, defined to be Stokes shifts of greater than 100 nm, have gained considerable attention due to their potential technological applications. A subset of these fluorophores have Stokes shifts of at least 10,000 cm −1 , for whom we suggest the moniker "giga" Stokes shift. The majority of "giga" Stokes shifts reported in the literature arise from the twisted intramolecular charge transfer mechanism, but this mechanism does not fit empirical characterization of triazolopyridinium (TOP). This observation inspired a density functional theory (DFT) and time-dependent DFT study of TOP, and several related fluorophores, to elucidate the novel photophysical origin for the "giga" Stokes shift of TOP. The resulting computational models revealed that photoexcitation of TOP yields a zwitterionic excited state that undergoes significant structural relaxation prior to emission. Most notably, TOP has two orthogonal moieties in the ground state that adopt a coplanar geometry in the excited state. According to Huckel's rule, both the heterocycle and phenyl moieties of TOP should be aromatic in an orthogonal ground state. However, according to Baird's rule, these individual moieties should be anti-aromatic in the excited state. By relaxing to a coplanar conformation in the excited state, TOP likely forms a single aromatic system consisting of both the heterocycle and phenyl moieties.

Zirconium-catalyzed alkene hydrophosphination and dehydrocoupling with an air-stable, fluorescent primary phosphine 8-[(4-phosphino)phenyl]-4,4-dimethyl-1,3,5,7-tetramethyl-2,6-diethyl-4-bora-3a,4a-diaza-s-indacene furnishes fluorescent phosphine products. Hydrophosphination of the fluorescent phosphine produces products with a complete selectivity for the secondary product. A key intermediate in catalysis, a zirconium phosphido compound, was isolated.

No abstract