Direct Excitation of Triplet State of Molecule by Enhanced Magnetic Field of Dielectric Metasurfaces

Abstract Efficient excitation of a triplet (T 1 ) state of a molecule has far‐reaching effects on photochemical reaction and energy conversion systems. Because the optical transition from a ground singlet (S 0 ) to a T 1 state is spin‐forbidden, a T 1 state is generated via intersystem crossing (ISC) from an excited singlet (S 1 ) state. Although the excitation efficiency of a T 1 state can be increased by enhancing ISC utilizing a heavy atom effect, energy loss during S 1 →T 1 relaxation is inevitable. Here, a general approach to directly excite a T 1 state from a ground S 0 state via magnetic dipole transition, which is boosted by enhanced magnetic field induced by a dielectric metasurface, is proposed. As a dielectric metasurface, a hexagonal array of silicon (Si) nanodisks is employed; the nanodisk array induces a strongly enhanced magnetic field on the surface due to the toroidal dipole (TD) resonance. A proof‐of‐concept experiment is performed using ruthenium (Ru) complexes placed on a metasurface and demonstrates that the phosphorescence is 35‐fold enhanced on a metasurface when the TD resonance is tuned to the wavelength of the direct S 0 →T 1 transition. These results indicate that photon energy necessary to excite the T 1 state can be reduced by more than 400 meV compared to the process involving the ISC. By combining optical measurements with numerical simulations, the mechanism of the phosphorescence enhancement is quantitatively discussed.