A Self‐Assembly‐Induced Exciton Delocalization Strategy for Converting a Perylene Diimide Derivative from a Type‐II to Type‐I Photosensitizer

Abstract Type‐I photosensitizers have shown advantages in addressing the shortcomings of traditional oxygen‐dependent type‐II photosensitizers for the photodynamic therapy (PDT) of hypoxic tumors. However, developing type‐I photosensitizers is yet a huge challenge because the type‐II energy transfer process is much faster than the type‐I electron transfer process. Herein, from the fundamental point of view, an effective approach is proposed to improve the electron transfer efficiency of the photosensitizer by lowering the internal reorganization energy and exciton binding energy via self‐assembly‐induced exciton delocalization. An example proof is presented by the design of a perylene diimide (PDI)‐based photosensitizer (PDIMp) that can generate singlet oxygen ( 1 O 2 ) via a type‐II energy transfer process in the monomeric state, but induce the generation of superoxide anion (O 2 ˙ˉ) via a type‐I electron transfer process in the aggregated state. Significantly, with the addition ofcucurbit[6]uril (CB[6]), the self‐assembled PDIMp can convert back to the monomeric state via host–guest complexation and consequently recover the generation of 1 O 2 . The biological evaluations reveal that supramolecular nanoparticles (PDIMp‐NPs) derived from PDIMp show superior phototherapeutic performance via synergistic type‐I PDT and mild photothermal therapy (PTT) against cancer under either normoxia or hypoxia conditions.