Boosting Singlet Oxygen Generation in Donor–Acceptor Binary Hydrogen‐Bonded Organic Frameworks for Photodynamic Antibacterium

Incorporating donor–acceptor (D–A) architectures into hydrogen‐bonded organic frameworks (HOFs) offers a promising route to boost exciton utilization for photodynamic therapy (PDT). However, conventional strategies that fuse donor and acceptor moieties into a single building block pose severe synthetic challenges. Herein, we address this limitation via a modular binary assembly approach, constructing D–A HOFs in which spatially separated donor and acceptor units are precisely integrated through hydrogen‐bonding networks instead of covalent conjugation. This modular design greatly simplifies synthesis by allowing independent optimization of D and A components, reduces the bandgap to 1.98 eV (from 2.63 eV for the single building block), and enhances singlet oxygen generation by 4–8 times, leading to markedly improved PDT antibacterial efficacy. This work not only provides fundamental insights into exciton manipulation in hydrogen‐bonded systems but also establishes a generalizable paradigm for developing high‐performance PDT materials through supramolecular D–A engineering.