Constructing Isoreticular Metal–Organic Frameworks by Silver–Carbon Bonds

The incorporation of new coordinate bonds and the development of universal methods for new structures have always been of major interest in metal–organic framework (MOF) research. The poor reversibility makes metal–carbon (M–C) bonds a great challenge to adopt as linkages to construct crystalline MOFs. Herein, three isoreticular microcrystalline MOFs connected by silver–carbon (Ag–C) bonds are presented for the first time and named AgC-MOFs. Their structures contain a double coordination mode (σ and π) between Ag­(I) and alkynyl. The three AgC-MOFs all exhibit three-dimensional (3D) frameworks with uniform one-dimensional (1D) hexagonal channels, and the pore width could be tuned from 1.1 to 1.8 nm. The construction of crystalline MOFs using poorly reversible Ag–C coordinate bonds extends the nexuses for the MOF structure and lights up more possibilities for the systematic design of MOFs.