Advancing Pore‐Space‐Partitioned Metal–Organic Frameworks with Isoreticular Cluster Concept

Abstract Trigonal planar M 3 (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 M 3 (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 M 3 M 6 pacs made from co‐assembly between M 3 single‐deck trimer and M 3x2 double‐deck trimer. Important factors were identified on this multi‐modular MOF platform to guide optimization of each module, which enables the phase selection of M 3 M 6 pacs by overcoming the formation of previously‐always‐observed same‐cluster phases. The new pacs materials exhibit high surface area and high uptake capacity for CO 2 and small hydrocarbons, as well as selective adsorption properties relevant to separation of industrially important mixtures such as C 2 H 2 /CO 2 and C 2 H 2 /C 2 H 4 . Furthermore, new M 3 M 6 pacs materials show electrocatalytic properties with high activity.