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Here, we report the rational design and synthesis of a fluorophore (XSOTA) by linking a dibenzothiophene\u2010\n                    <jats:italic>S<\/jats:italic>\n                    ,\n                    <jats:italic>S<\/jats:italic>\n                    \u2010dioxide acceptor to triphenylamine donor via a vinyl bridge. Detailed experimental studies and theoretical calculations reveal that XSOTA exhibits a hybridized local and charge transfer (HLCT) excited\u2010state character. This HLCT feature endows XSOTA with dual photophysical functionality: the locally excited (LE) state facilitates rapid radiative decay for high fluorescence quantum yield, while the charge\u2010transfer (CT) state promotes efficient intersystem crossing and ROS generation. Consequently, XSOTA achieves an outstanding fluorescence quantum yield of 89.2% in toluene, a large two\u2010photon absorption cross\u2010section of 7000 GM, and a high ROS yield of 56.3%. When encapsulated into biocompatible nanoparticles, XSOTA enables deep\u2010tissue two\u2010photon fluorescence imaging of mouse vasculature, achieving imaging depths of 320\u00a0\u00b5m in bladder vessels and 350\u00a0\u00b5m in liver tissue. Moreover, XSOTA\u2010based nanoparticles demonstrate effective imaging\u2010guided photodynamic therapy, significantly suppressing tumor growth without observable toxicity to major organs. These findings establish HLCT\u2010based fluorophores as promising dual\u2010function agents for image\u2010guided photodynamic cancer therapy.\n                  <\/jats:p>","DOI":"10.1002\/smll.202509586","type":"journal-article","created":{"date-parts":[[2026,1,23]],"date-time":"2026-01-23T12:10:45Z","timestamp":1769170245000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":2,"title":["Multifunctional Hybridized Local and Charge\u2010Transfer Small Molecular Fluorophore for Imaging\u2010Guided Photodynamic Anticancer Therapy"],"prefix":"10.1002","volume":"22","author":[{"given":"Liwen","family":"Hu","sequence":"first","affiliation":[{"name":"School of Optoelectronic Engineering Guangdong Polytechnic Normal University  Guangzhou China"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Qiuru","family":"Deng","sequence":"additional","affiliation":[{"name":"School of Optoelectronic Engineering Guangdong 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