Net-Coded Organic Building Blocks for the Reticular Assembly of High-Connectivity Metal–Organic Frameworks

High-connectivity metal-organic frameworks (MOFs) are of great importance in reticular chemistry because of the designed synthesis by judicious selection of organic and inorganic building blocks. However, it remains a challenge to synthesize well-defined polytopic organic linkers with a connectivity ≥ 12. Here we report the synthesis of (4,12)-connected shp- and (6,12)-connected alb-MOFs─denoted as Cu-HDTB-shp, In-HDTB-shp, Fe-HDTB-alb, and Zr-HDTB-alb─by assembly of a 12-connected dodecacarboxylate ligand and preselected inorganic nodes. This dodecacarboxylate ligand, a feasible net-coded organic building block encoding geometric information on the targeted high-connectivity net, allows the rational synthesis of MOFs based on the shp- and alb-derived nets, including rare node-morphing ceh and key nets. Fe-HDTB-alb and Zr-HDTB-alb, on account of the right pore structures, can potentially be applied to natural gas upgrading. This net-coded strategy presents a significant step toward the rational synthesis of high-connectivity framework structures with molecular-level precision.