Theoretical investigation of multi-spin excited states of anthracene radical-linked π-conjugated spin systems by computational chemistry.

Multi-spin excited states of chromophore radical-linked π-conjugated spin systems are investigated by molecular orbital calculations based on density functional theory (DFT). The investigated systems consist of an anthracene photosensitive unit leading to a triplet-excited-state ( S = 1), π-conjugated linker to propagate spin exchange-coupling, and stable organic radical with a doublet-ground-state ( S = 1/2). The intramolecular exchange coupling ( J DQ ), g value, and fine-structure interaction of their excited states depended on the π-conjugation network (π-topology), type of radical, and molecular structure of the π-linker (length and dihedral angle). The exchange interaction was dependent on the π-topology and the type of radical species. A decrease in the dihedral angle between the anthracene moiety and phenyl linker in the photo-excited state led to larger exchange coupling. With an increase in the π-linker length ( r ), the magnitude of the exchange coupling gradually decreased in the photoexcited states according to J DQ = J Ex0 exp(- βr ), similar to the ground-state exchange. The g values of the quartet (Q) state depended only on the radical type (independent of the linker). Conversely, the fine-structure interaction of the Q state was independent of the radical type and depended on both the linker length and the dihedral angle.