Polarity‐Evolution Control and Luminescence Regulation in Multiple‐Site Hydrogen‐Bonded Organic Frameworks

Hydrogen-bonded organic frameworks (HOFs) have shown great potential in separation, sensing and host-guest chemistry, however, the pre-design of HOFs remains challenging due to the uncertainty of solvents' participation in framework formation. Herein, the polarity-evolution-controlled framework/luminescence regulation is demonstrated based on multiple-site hydrogen-bonded organic frameworks. Several distinct HOFs were prepared by changing bonding modes of building units via the evolution of electrostatic forces induced by various solvent polarities. High-polar solvents with strong electrostatic attraction to surrounding units showed the tendency to form cage structures, while low-polar solvents with weak electrostatic attraction only occupy hydrogen-bond sites, conducive to the channel formation. Furthermore, the conformation of optical building unit can be adjusted by affecting the solvent polarity, generating different luminescence outputs. These results pave the way for the rational design of ideal HOFs with on-demand framework regulation and luminescence properties.