Integrated Monomer Synthesis and Framework Assembly: Achieving Isoreticular Modulation of Hydrogen‐Bonded Organic Frameworks

Systematic construction of isoreticular hydrogen-bonded organic frameworks (HOFs) promises tailored material properties crucial for diverse applications, yet is challenging due to the weak, flexible, and non-directional nature of hydrogen bonds. Herein, we develop an "integrated monomer synthesis-framework assembly" (ISA) methodology for constructing a series of isoreticular HOFs. Unlike traditional methods where monomers are first synthesized and then assembled into HOFs, the ISA system employs dicyandiamide rigid hydrogen-bonded hexameric clusters as connecting nodes to covalently react with planarized C