Expanding the Ligand Scope of Pore-Space-Partitioned MOFs with a Chiral Camphorate Linker

Expanding the scope of isoreticular chemistry to include chiral ligands remains a fundamental challenge, particularly for high-symmetry framework topologies that generally favor symmetry matching between building blocks and the crystallographic sites they occupy. Here, we demonstrate that the partitioned acs (pacs) platform can accommodate a chiral dicarboxylate ligand, (1 R,3 S )-(+)-camphoric acid ( d -cam), representing the first pacs MOF constructed from a chiral L1 ligand. The successful assembly of the framework is enabled by the cooperative structure-directing effects of a tripyridyl pore-partitioning ligand and heterometallic Co/In trinuclear clusters, which collectively enforce alignment of ligand coordination vectors while permitting subtle charge and size tunability through variable Co 2+ /In 3+ ratios within the trimers. Structural analysis reveals that the framework preserves the characteristic pacs architecture despite geometric distortion arising from the stereochemical features and low symmetry of the ligand. These results suggest that geometric mismatch is redistributed throughout the framework through cooperative distortion of ligand orientation, cage geometry, and trimer coordination environment. Gas sorption studies reveal preferential adsorption of C 2 H 2 over CO 2, while breakthrough experiments demonstrate stable C 2 H 2 /CO 2 separation over multiple cycles. More broadly, this work suggests that cooperative multimodule assembly can relax classical symmetry-matching constraints in isoreticular chemistry.