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<p>Serious hypoxia in solid tumor as well as
vicious aggregation-caused fluorescence quenching (ACQ) of conventional photosensitizers
(PSs) limit the
progress of the fluorescence imaging-guided photodynamic (PDT) although it has obvious
advantages in precise spatial-temporal control and
noninvasive treatment. The photosensitizers featuring Type I reactive
oxygen species (ROS) based on free radical and novel aggregation-induced emission (AIE) characteristic (AIE-PSs)
could offer precious opportunity
to resolve above problems, but there was rare feasible molecular engineering in
previous reports. Herein, we proposed that the strategy of fabricating stronger
intermolecular charge transfer (ICT) effect in electron-rich anion-π<sup>+ </sup>AIE-active
luminogens (AIEgens) aimed to help suppressing
nonradiative internal conversion (IC) as well as promote radiative and
intersystem crossing (ISC) processes for boosting more free radical generation. Systematic and detailed
experimental and theoretical calculations proved our ideas when the
electron-donating abilities enhanced in collaborative
donors, and the AIE-PSs exhibited higher performance in near-infrared
red (NIR) fluorescence image-guided cancer PDT <i>in vitro/vivo</i>. This work would become an
important reference to the design of AIE-active free radical generators for overcoming ACQ
effect and tumor hypoxia
in future PDT.</p>
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