Abstract
Phototherapy, encompassing photodynamic therapy (PDT) and photothermal therapy (PTT), presents a promising cancer treatment strategy with high spatial specificity and minimal invasiveness. Optimizing these techniques hinges on the design of high‐performance photosensitizers (PSs) and photothermal agents (PTAs). Single‐atom chalcogen substitution, at both endocyclic and exocyclic positions in conventional organic chromophores, has proven to be a novel strategy for enhancing their photophysical and photochemical properties. Ideal PSs/PTAs exhibit high biocompatibility, visible‐to‐near‐infrared (vis–NIR) absorption, efficient triplet state harvesting, and feasible heat and energy transfer efficiency. Moreover, chalcogen‐based PSs/PTAs show promise for synergistic multimodal therapies, integrating imaging and treatment. This review comprehensively examines recent advancements (within the last five years) in utilizing chalcogen substitution to design robust PSs/PTAs for PDT/PTT. It provides a holistic perspective on spectroscopic characterization and computational analyses, singlet‐oxygen/triplet quantum yields, heat generation efficiency, and in vitro/in vivo biological evaluations of chalcogen‐substituted PSs/PTAs. It is anticipated that this review will stimulate further research endeavors in this promising area.

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