Carborane Dyads for Photoinduced Electron Transfer: Photophysical Studies on Carbazole and Phenyl‐o‐carborane Molecular Assemblies

o-Carborane-based donor-acceptor dyads comprising an o-carboranyl phenyl unit combined with N-carbazole (1) or 4-phenyl-N-carbazole (2) were prepared, and their dyad characters were confirmed by steady-state photochemistry and photodynamic experiments as well as electrochemical studies. The absorption and electrochemical properties of the dyads were essentially the sum of those of the carbazole and o-carboranyl phenyl units; this indicates negligible interaction between the carbazole and o-carborane units in the ground state. However, the emission spectra of 1 and 2 indicated that carbazole fluorescence was effectively quenched and a new charge-transfer (CT) emission was observed in solvents, varying from hexane to acetonitrile, which exhibited large Stoke shifts. The CT emission properties of o-carborane-based dyads were further analyzed by using Lippert-Mataga plots to show that unit charge separation occurred to form a charge-separated species in the excited state, namely, 1⋅2. This excited-state species was confirmed by nanosecond transient absorption spectra and spectroelectrochemical measurements; the photoexcitation of carbazole generated the CT state in which a radical cation and anion were formed at the carbazole and o-carborane units, respectively, within a few nanoseconds. DFT calculations corroborated the presence of this CT species and showed localized populations of the highest singly occupied molecular orbital on 2 in the reduced anionic state. As a result, molecular assemblies formed by linking the carbazole group with the o-carborane cage through a phenylene or multi-phenylene spacer revealed that the photoinduced electron-transfer process occurred intramolecularly.