Spin-Correlated Luminescence of a Carbazole-Containing Diradical Emitter: Single-Molecule Magnetoluminescence and Thermally Activated Emission.

Luminescent radicals have been intensively studied as a new class of materials exhibiting novel photofunctions unique to open-shell systems. When luminescent radicals are assembled, intriguing spin-correlated luminescence phenomena emerge, including excimer-like emission and magnetic-field effects on luminescence (i.e., magnetoluminescence, MagLum). However, the underlying mechanisms of these phenomena arising from spin multiplicity and spin-dependent excited-state dynamics are poorly understood due to the limited number of luminescent polyradical systems available for study. In particular, the correlation between stronger intramolecular exchange interactions (|2 J / k _B | > ∼10 K, where J and k _B are the intramolecular exchange coupling constant and the Boltzmann constant, respectively) and luminescence properties has not been fully explained. In this study, a novel carbazole-containing diradical emitter ( 1 ) and the corresponding monoradical ( 2 ) were prepared for the in-depth study of spin-correlated luminescence properties, with luminescence measurements under magnetic fields of up to 18 T. Diradical 1 has a negative 2 J / k _B value of several tens of kelvin and exhibits a single-molecule MagLum and thermally activated luminescence, whereas 2 does not. Detailed quantitative analyses revealed that both the spin-correlated luminescence properties of 1 are strongly dominated by ground-state spin statistics based on the Boltzmann distribution (i.e., 2 J / k _B values). Furthermore, diradical 1 exhibits external heavy-atom effects in heavy-atom-containing solvents such as iodobenzene, whereas monoradical 2 does not. This is the first experimental verification of external heavy-atom effects in polyradical emitters. This work demonstrates that polyradical emitters can be designed based on spin degrees of freedom in both ground and excited states.