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.