The conversion of
closo-o-carborane–containing compounds to the
nido-o-species
via deboronation causes photophysical changes that could be used for sensing applications. 9-Methyl-9
H-carbazole–based
closo- (
closo-Cz) and
nido-o-carboranyl (
nido-Cz) compounds were prepared and fully characterised by multinuclear NMR spectroscopy and elemental analysis, and the solid-state molecular structure of
closo-Cz was analysed by X-ray crystallography. Although the
closo-compound exhibited an emissive pattern centred at
λem =
ca. 530 nm in the rigid state only (in THF at 77 K and as a film),
nido-Cz demonstrated intense emission in the near-UV region (
λem =
ca. 380 nm) in both solution and film states at 298 K. The positive solvatochromic effect of
nido-Cz and the results of theoretical calculations for both the
o-carboranyl compounds supported that these emissive features originate from intramolecular charge transfer (ICT) corresponding to the
o-carborane. Furthermore, the calculations verified that the electronic role of the
o-carboranyl unit changed from acceptor to donor upon deboronation from
closo-Cz to
nido-Cz. Investigations of the radiative decay mechanisms of
closo-Cz and
nido-Cz according to their quantum efficiencies (
Φem) and decay lifetimes (
τobs) suggested that the ICT-based radiative decays of
closo-Cz and
nido-Cz readily occur in the film (solid) and solution state, respectively. These observations implied that the emission of
closo-Cz in the solution state could be drastically enhanced by deboronation to
nido-Cz upon exposure to an increasing concentration of fluoride anions. Indeed, turn-on emissive features in an aqueous solution were observed upon deboronation, strongly suggesting the potential of
closo-Cz as a turn-on and visually detectable chemodosimeter for fluoride ion sensing.Deboronation of a 9-methyl-9
H-carbazole–based
closo-o-carboranyl compound to the
nido-o-carborane in an aqueous solution results in a ratiometric turn-on response in the deep-blue emission region with moderate reactivity.
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