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

The photophysical properties of closo-ortho-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-9H-carbazole-based closo-ortho-carboranyl compounds (1F, 2P, 3M, and 4T), in which an o-carborane cage was appended at the C3-position of a 9-phenyl-9H-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 1F and 4T 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-9H-carbazole moiety and weak intramolecular charge transfer (ICT) between the o-carborane and the carbazole group. These compounds showed intense yellowish emission (λem = ~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 (S1) of the compounds suggested that the strong emission bands can be assigned to the ICT transition involving the o-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 1F < ‒H for 2P < ‒CH3 for 3M < ‒C(CH3)3 for 4T). These features indicate that the ICT-based radiative decay process in rigid states is affected by the electronic environment of the 9-phenyl-9H-carbazole group. Consequently, the efficient ICT-based radiative decay of o-carboranyl compounds can be achieved by appending the o-carborane cage with electron-rich aromatic systems.

Deboronation-Induced Ratiometric Emission Variations of Terphenyl-Based Closo-o-Carboranyl Compounds: Applications to Fluoride-Sensing.

Closo-o-carboranyl compounds bearing the ortho-type perfectly distorted or planar terphenyl rings (closo-DT and closo-PT, respectively) and their nido-derivatives (nido-DT and nido-PT, respectively) were synthesized and fully characterized using multinuclear NMR spectroscopy and elemental analysis. Although the emission spectra of both closo-compounds exhibited intriguing emission patterns in solution at 298 and 77 K, in the film state, closo-DT mainly exhibited a π-π* local excitation (LE)-based emission in the high-energy region, whereas closo-PT produced an intense emission in the low-energy region corresponding to an intramolecular charge transfer (ICT) transition. In particular, the positive solvatochromic effect of closo-PT and theoretical calculation results at the first excited (S1) optimized structure of both closo-compounds strongly suggest that these dual-emissive bands at the high- and low-energy can be assigned to each π-π* LE and ICT transition. Interestingly, both the nido-compounds, nido-DT and nido-PT, exhibited the only LE-based emission in solution at 298 K due to the anionic character of the nido-o-carborane cages, which cannot cause the ICT transitions. The specific emissive features of nido-compounds indicate that the emissive color of closo-PT in solution at 298 K is completely different from that of nido-PT. As a result, the deboronation of closo-PT upon exposure to increasing concentrations of fluoride anion exhibits a dramatic ratiometric color change from orange to deep blue via turn-off of the ICT-based emission. Consequently, the color change response of the luminescence by the alternation of the intrinsic electronic transitions via deboronation as well as the structural feature of terphenyl rings indicates the potential of the developed closo-o-carboranyl compounds that exhibit the intense ICT-based emission, as naked-eye-detectable chemodosimeters for fluoride ion sensing.

Alteration of intramolecular electronic transition via deboronation of carbazole-based o-carboranyl compound and intriguing 'turn-on' emissive variation.

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-9H-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 λ em = 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 (λ em = 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 (Φ em) and decay lifetimes (τ obs) 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.