Radical enhanced intersystem crossing mechanism, electron spin dynamics of high spin states and their applications in the design of heavy atom-free triplet photosensitizers

Heavy atom-free triplet photosensitizers (PSs) can overcome the high cost and biological toxicity of traditional molecular systems containing heavy atoms (such as Pt(II), Ir(III), Ru(II), Pd(II), Lu(III), I, or Br atoms) and, therefore, are developing rapidly. Connecting a stable free radical to the chromophore can promote the intersystem crossing (ISC) process through electron spin exchange interaction to produce the triplet state of the chromophore or the doublet (D) and quartet (Q) states when taking the whole spin system into account. These molecular systems based on the radical enhanced ISC (REISC) mechanism are important in the field of heavy atom-free triplet PSs. The REISC system has a simple molecular structure and good biocompatibility, and it is especially helpful for building high-spin quantum states (D and Q states) that have the potential to be developed as qubits in quantum information science. This review introduces the molecular structure design for the purpose of high-spin states. Time-resolved electron paramagnetic resonance (TREPR) is the most important characterization method to reveal the properties of these molecular systems, generation mechanism and electron spin polarization (ESP) of the high spin states. The spin polarization manipulation of high spin states and potential application in the field of quantum information engineering are also summarized. Moreover, molecular design principles of the REISC system to obtain long absorption wavelength, high triplet state quantum yield and long triplet state lifetime are introduced, as well as applications of the compounds in triplet-triplet annihilation upconversion, photodynamic therapy and bioimaging. This review is useful for the design of heavy atom-free triplet PSs based on the radical-chromophore molecular structure motif and the study of the photophysics of the compounds, as well as the electron spin dynamics of the multi electron system upon photoexcitation.