Optically Distinguishable Electronic Spin-isomers of a Stable Organic Diradical

Herein, we introduce a model of electronic spin isomers, the electronic counterpart of nuclear spin isomers, by using a stable organic diradical. The diradical, composed of two benzotriazinyl radicals connected by a rigid triptycene skeleton, exhibits a small singlet–triplet energy gap of −3.0 kJ/mol, indicating ca. 1:1 coexistence of the two spin states at room temperature. The diradical shows characteristic near-IR absorption bands, which are absent in the corresponding monoradical subunit. Variable temperature measurements revealed that the absorbance of the NIR band depends on the abundance of the singlet state, allowing us to identify the NIR band as the singlet-specific absorption band. It enables photoexcitation of one of the two spin states coexisting in thermal equilibrium. Transient absorption spectroscopy disclosed that the two spin states independently follow qualitatively different excited-state dynamics. These results demonstrate a novel approach to the design and study of electronic spin isomers based on organic diradicals.

We demonstrate that an organic diradical can be regarded as its electronic counterpart of nuclear spin isomers (e.g., ortho/para-hydrogens) with spin bistability and spin-dependent properties.