A Trimming‐π Strategy for Constructing Functional Conductive Metal–Organic Frameworks Using Metalloporphyrazine Units

Abstract Developing functional metal–organic frameworks (MOFs) with high electrical conductivity is crucial for their applications as advanced electronic materials. In this work, we for the first time construct a new family of functional and highly conductive MOFs using metalloporphyrazine (MPz) ligands based on a trimming‐π concept via cutting the benzene ring from molecular metallopthalocynine (MPc). The deprotonation‐after‐coordination synthetic method affords crystalline MPz−Cu−NH MOFs with square lattices. Four‐point probe conductivity measurements reveal the high room temperature electrical conductivity of MPz‐based MOFs ranging from 3.5×10 −2 to 1.3×10 −1 S cm −1 , two orders of magnitude higher than the MPc‐based MOF counterparts. Temperature‐dependent conductivity measurements and electronic band structure analysis demonstrate ultra‐small activation energies with potential metallic conducting behavior for the MPz−Cu−NH MOFs. Encapsulation of the aromatic guest molecules with different electron‐donating and ‐withdrawing features allows the conductivity modulation of the CuPz−Cu−NH in a wide range spanning two orders of magnitude. These conductive MPz−Cu−NH MOFs with built‐in MPz functional units exhibit MPz identity‐dependent sensing performance, and realize highly sensitive detection of NH 3 and NO 2 using a low driving voltage of 0.1 V.