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Abstract Although metal–organic frameworks are coordination‐driven assemblies, the structural prediction and design using metal‐ligand interactions can be unreliable due to other competing interactions. Leveraging non‐coordination interactions to develop porous assemblies could enable new materials and applications. Here, we use a multi‐module MOF system to explore important and pervasive impact of ligand‐ligand interactions on metal‐ligand as well as ligand‐ligand co‐assembly process. It is found that ligand‐ligand interactions play critical roles on the scope or breakdown of isoreticular chemistry. With cooperative di‐ and tri‐topic ligands, a family of Ni‐MOFs has been synthesized in various structure types including partitioned MIL‐88‐acs (pacs), interruptedpacs(i‐pacs), and UMCM‐1‐muo. A new type of isoreticular chemistry on the muo platform is established between two drastically different chemical systems. The gas sorption and electrocatalytic studies were performed that reveal excellent performance such as high C₂H₂/CO₂selectivity of 21.8 and high C₂H₂uptake capacity of 114.5 cm³/g at 298 K and 1 bar. 

Abstract Trigonal planar M₃(O/OH) trimers are among the most important clusters in inorganic chemistry and are the foundational features of multiple high‐impact MOF platforms. Here we introduce a concept called isoreticular cluster series and demonstrate that M₃(O/OH), as the first member of a supertrimer series, can be combined with a higher hierarchical member (double‐deck trimer here) to advance isoreticular chemistry. We report here an isoreticular series of pore‐space‐partitioned MOFs called M₃M₆pacsmade from co‐assembly between M₃single‐deck trimer and M_3x2double‐deck trimer. Important factors were identified on this multi‐modular MOF platform to guide optimization of each module, which enables the phase selection of M₃M₆pacsby overcoming the formation of previously‐always‐observed same‐cluster phases. The newpacsmaterials exhibit high surface area and high uptake capacity for CO₂and small hydrocarbons, as well as selective adsorption properties relevant to separation of industrially important mixtures such as C₂H₂/CO₂and C₂H₂/C₂H₄. Furthermore, new M₃M₆pacsmaterials show electrocatalytic properties with high activity.