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The reduction in esters, nitriles, and imines requires harsh conditions (highly reactive reagents, high temperatures, and pressures) or complex metal-ligand catalytic systems. Catalysts comprising earth-abundant and less toxic elements are desirable from the perspective of green chemistry. In this study, we developed a green hydroboration protocol for the reduction in esters, nitriles, and imines at room temperature (25 °C) using pinacolborane as the reducing agent and a commercially available Grignard reagent as the catalyst. Screening of various alkyl magnesium halides revealed MeMgCl as the optimal catalyst for the reduction. The hydroboration and subsequent hydrolysis of various esters yielded corresponding alcohols over a short reaction time (~0.5 h). The hydroboration of nitriles and imines produced various primary and secondary amines in excellent yields. Chemoselective reduction and density functional theory calculations are also performed. The proposed green hydroboration protocol eliminates the requirements for complex ligand systems and elevated temperatures, providing an effective method for the reduction in esters, nitriles, and imines at room temperature.

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.

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.

9,9′-Spirobifluorene-based o-carboranyl compounds C1 and C2 were prepared and fully characterized by multinuclear nuclear magnetic resonance (NMR) spectroscopy and elemental analysis. The solid-state structure of C1 was also determined by single-crystal X-ray diffractometry. The two carboranyl compounds display major absorption bands that are assigned to π−π* transitions involving their spirobifluorene groups, as well as weak intramolecular charge-transfer (ICT) transitions between the o-carboranes and their spirobifluorene groups. While C1 only exhibited high-energy emissions (λem = ca. 350 nm) in THF at 298 K due to locally excited (LE) states assignable to π−π* transitions involving the spirobifluorene group alone, a remarkable emission in the low-energy region was observed in the rigid state, such as in THF at 77 K or the film state. Furthermore, C2 displays intense dual emissive patterns in both high- and low-energy regions in all states. Electronic transitions that were calculated by time-dependent-DFT (TD-DFT) for each compound based on ground (S0) and first-excited (S1) state optimized structures clearly verify that the low-energy emissions are due to ICT-based radiative decays. Calculated energy barriers that are based on the relative energies associated with changes in the dihedral angle around the o-carborane cages in C1 and C2 clearly reveal that the o-carborane cage in C1 rotates more freely than that in C2. All of the molecular features indicate that ICT-based radiative decay is only available to the rigid state in the absence of structural fluctuations, in particular the free-rotation of the o-carborane cage.

Herein, we investigated the effect of ring planarity by fully characterizing four pyridine-based o-carboranyl compounds. o-Carborane was introduced to the C4 position of the pyridine rings of 2-phenylpyridine and 2-(benzo[b]thiophen-2-yl)pyridine (CB1 and CB2, respectively), and the compounds were subsequently borylated to obtain the corresponding CN-chelated compounds CB1B and CB2B. Single-crystal X-ray diffraction analysis of the molecular structures of CB2 and CB2B confirmed that o-carborane is appended to the aryl moiety. In photoluminescence experiments, CB2, but not CB1, showed an intense emission, assignable to intramolecular charge transfer (ICT) transition between the aryl and o-carborane moieties, in both solution and film states. On the other hand, in both solution and film states, CB1B and CB2B demonstrated a strong emission, originating from π-π * transition in the aryl groups, that tailed off to 650 nm owing to the ICT transition. All intramolecular electronic transitions in these o-carboranyl compounds were verified by theoretical calculations. These results distinctly suggest that the planarity of the aryl groups have a decisive effect on the efficiency of the radiative decay due to the ICT transition.