From Metal-Organic Helices to Zeolite-like Supramolecular Assemblies

Zeolite-like metal-organic frameworks (ZMOFs) bridge the structural order of zeolites and the rational design of reticular chemistry, yet achieving their predictable construction remains challenging. Here, we present a generalizable construction strategy that employs metal-organic helices (MOHs) as versatile blueprints for assembling zeolite-like supramolecular assemblies (ZSAs), a unique subclass of ZMOFs or metal-hydrogen bonded organic frameworks (M-HOFs). In the initial stage, a subset of networks exhibiting typical MOH features was analyzed, identifying 29 feasible frameworks potentially derivable from MOHs. Building on these insights, we established the structural prerequisites for MOH-based assembly and experimentally realized several representative frameworks: ZSA-14, constructed from 41- and 43-type MOHs with a gis-type zeolitic topology; ZSA-15 and ZSA-16, built from 31- and 32-type MOHs with sod-type zeolitic topology; and Compound 1, assembled from 21-type MOH with a pts topology. These results demonstrate the generality of the MOH concept in encoding diverse zeolite-like topologies and its compatibility with isoreticular design principles. This work introduces helical blueprints as a new paradigm for the systematic design of ZMOFs and opens a pathway toward programmable framework architectures derived from one-dimensional building units.