The property of organic light-responsive materials is determined by their electronic excited states to a large extent, for instance, the radiative decay rate constants, redox potentials, and lifetimes. Tuning the excited state properties with external stimuli will lead to versatile functional materials; a representative example is the fluorescence molecular probes, in which the singlet excited states are controlled by the external stimuli, i.e., by interaction with the analytes. In comparison, controlling the triplet excited state with external stimuli has been rarely reported, although it is also crucial for the development of novel materials for targeted photodynamic therapy (PDT) reagents and phosphorescent molecular probes. The reported results show that the principles used in singlet excited state tuning are unable to be simply applied to the triplet excited state. In this review article, we summarized the recent results on controlling the triplet excited states by the external stimuli (chemical or light), and the application of the triplet state tuning in the chemical/light controllable triplet–triplet-annihilation upconversion (TTA UC). We discussed the methods for the control of the triplet states, as well as singlet excited state, for the purpose of controlling the TTA UC. Both successful and unsuccessful methods are discussed. This information is helpful for understanding the photophysical processes in which the triplet excited state is involved, and the development of novel external stimuli-responsive triplet photosensitizers.

Recently varieties of Bodipy derivatives showing intersystem crossing (ISC) have been reported as triplet photosensitizers, and the application of these compounds in photocatalysis, photodynamic therapy (PDT), and photon upconversion are promising. In this review we summarized the recent development in the area of Bodipy-derived triplet photosensitizers and discussed the molecular structural factors that enhance the ISC ability. The compounds are introduced based on their ISC mechanisms, which include the heavy atom effect, exciton coupling, charge recombination (CR)-induced ISC, using a spin converter and radical enhanced ISC. Some transition metal complexes containing Bodipy chromophores are also discussed. The applications of these new triplet photosensitizers in photodynamic therapy, photocatalysis, and photon upconversion are briefly commented on. We believe the study of new triplet photosensitizers and the application of these novel materials in the abovementioned areas will be blooming.

Photodynamic therapy (PDT) is an attractive method for cancer treatment. Triplet photosensitizers (PSs) are critical for this method; upon photoexcitation, efficient intersystem crossing (ISC) occurs for triplet PSs, the triplet-excited state of the triplet PSs is populated, then via intermolecular triplet energy transfer, the O₂, in triplet-spin multiplicity at ground state, is sensitized to the singlet-excited state, i.e., singlet oxygen (¹O₂) is produced. This strong reactive oxygen species (ROS) will oxidize the biomolecules in the tumor tissue. Thus, the design of novel triplet PSs as efficient PDT agents is vital. In this review article, we will introduce the recent development of the heavy atom-free triplet PSs used for PDT, including those based on spin-orbit charge transfer ISC (SOCT-ISC), twisting of the π-conjugation framework-induced ISC, radical enhanced ISC, and thionated carbonyl-induced ISC. The ISC mechanisms and molecular structure design rationales are discussed. The less studied electron spin selectivity of the ISC of the triplet PSs is also introduced. This information is helpful for the future design of new efficient triplet PSs for PDT.