Ligand‐Insertion Strategy for Constructing 2D Conjugated Metal‐Organic Framework with Large Pore Size for Electrochemical Analytics

Abstract Two‐dimensional conjugated metal–organic frameworks (2D c ‐MOFs) have shown great promise in various electrochemical applications due to their intrinsic electrical conductivity. A large pore aperture is a favorable feature of this type of material because it facilitates the mass transport of chemical species and electrolytes. In this work, we propose a ligand insertion strategy in which a linear ligand is inserted into the linkage between multitopic ligands, extending the metal ion into a linear unit of ‐M‐ligand‐M‐, for the construction of 2D c ‐MOFs with large pore apertures, utilizing only small ligands. As a proof‐of‐concept trial of this strategy, a 2D c ‐MOF with mesopores of 3.2 nm was synthesized using commercially available ligands hexahydrotriphenylene and 2,5‐dihydroxybenzoquinone. The facilitation of the diffusion of redox species by the large pore size of this MOF was demonstrated through a series of probes. With this feature, it showed superior performance in the electrochemical analysis of a variety of biological species.