Impact of deboronation on the electronic characteristics of closo-o-carborane: intriguing photophysical changes in triazole-appended carboranyl luminophores

5-Phenyl-1,2,4-triazole-appended closo- (CB1 and CB2) and nido-o-carboranyl (nido-CB1 and nido-CB2) compounds were prepared and fully characterized using multinuclear NMR spectroscopy and elemental analysis. The solid-state molecular structures of both closo-compounds were analyzed by X-ray crystallography. Although the closo-compounds exhibited dual emissive patterns in the rigid state (in THF at 77 K), which were assignable to a pi-pi* local excitation (LE)-based emission (lambda(em) = ca. 380 nm) on the triazole moieties and to an intramolecular charge transfer (ICT)-based emission (ca. 460 nm) in which the o-carborane units acted as the acceptor (A), at 298 K in THF, the LE-based emission dominated. In contrast, the nido-compounds exhibited an intensive emission originating from ICT transitions in which the o-carborane units reversibly acted as the donor (D). In particular, the positive solvatochromic effects of both nido-compounds and the results of theoretical calculations for the o-carboranyl compounds supported the electronic role of the o-carboranyl unit in each compound. Investigation of the radiative decay mechanism of the closo- and nido-compounds using their quantum efficiency (phi(em)) and decay lifetime (tau(obs)) suggested that the ICT-based radiative decay of nido-compounds occurred more efficiently than the LE-based decay of closo-compounds. These results implied that emission from the closo-compounds was drastically enhanced by the deboronation reaction upon exposure to an increasing concentration of fluoride anions, and finally became similar to the emission color (sky-blue) of the nido-compounds.

Automated summary

The research examined the luminescent properties of closo- and nido-carboranyl compounds with different structural effects, revealing their radiative decay mechanisms. The findings indicate distinct differences in the luminescent properties of the different compounds in THF, with significant effects of fluoride ions on the luminescence of closo compounds.