Hybrid Hydrogen‐Bonded Organic Frameworks: Structures and Functional Applications

As a new class of porous crystalline materials, hydrogen‐bonded organic frameworks (HOFs) assembled from building blocks by hydrogen bonds have gained increasing attention. HOFs benefit from advantages including mild synthesis, easy purification, and good recyclability. However, some HOFs transform into unstable frameworks after desolvation, which hinders their further applications. Nowadays, the main challenges of developing HOFs lie in stability improvement, porosity establishment, and functionalization. Recently, more and more stable and permanently porous HOFs have been reported. Of all these design strategies, stronger charge‐assisted hydrogen bonds and coordination bonds have been proven to be effective for developing stable, porous, and functional solids called hybrid HOFs, including ionic and metallized HOFs. This Review discusses the rational design synthesis principles of hybrid HOFs and their cutting‐edge applications in selective inclusion, proton conduction, gas separation, catalysis and so forth. Simply HOF! This work reviewed the recent development progress of hybrid hydrogen‐bonded organic frameworks (HOFs), including ionic HOFs and metallized HOFs. The rational design synthesis principles of stable, porous, and functional hybrid HOFs by using charged or metallized building blocks are discussed. Their front applications in selective inclusion, proton conduction, gas separation, and catalysis are highlighted.