Computational Study of Photochemical Relaxation Pathways of Platinum(II) Complexes

A series of functional platinum(II) complexes (Pt1-Pt3), which present high activity in four-photon absorption, in vivo imaging, and precise cancer therapy, as previously reported by the experimental work of Zhang et al. (Inorg. Chem. 2021, 60, 2362-2371), are computationally investigated in the article. We find that after the complex goes through four-photon absorption to the S₁ state, it undergoes intersystem crossing to the T₂ state and eventually reaches the T₁ state through internal conversion. On the T₁ state, both radiative and nonradiative decay to S₀ exit. The radiative decay forms the basis for the phosphorescence imaging in tissues as reported in the original paper. In addition, the nonradiative decay can simultaneously generate cytotoxic singlet oxygen by the excited energy transfer process, also known as triplet oxygen's quenching of triplet states. We conclude that the phosphorescence property as well as the photosensitizer character jointly bring high activity of in vivo imaging and photodynamic therapy to these complexes.