Component‐Programmed Self‐Assembly for Topological Transformation: From a 2D Network to a Discrete Star of David

Abstract

ABSTRACT Controllable modifications on dimensionalities and topologies of supramolecules are crucial for tuning their properties. Here, we report a robust component‐controlled topological transformation, initiating with a two‐dimensional (2D) layered coordination network S2 formed by the self‐assembly of a metallo‐organic ligand (MOL) LA with Zn(II). The strategic introduction of a V‐shaped modulator LB with peripheral arms into the S2 system triggered a remarkable topological transformation, thus affording a discrete zero‐dimensional (0D) hexagon‐framed Star of David S1 . This unprecedented 2D to 0D control facilitates direct comparison of their intrinsic properties, with structures unequivocally confirmed by nuclear magnetic resonance (NMR) spectroscopy, high‐resolution electrospray ionization mass spectrometry (ESI‐MS), traveling‐wave ion mobility mass spectrometry (TWIM‐MS), and microscopy. In the aerobic sulfide oxidation, the extended 2D network S2 exhibited significantly improved photocatalytic performance over S1 . This enhanced efficiency was attributed to S2 ’s pseudo‐heterogeneous nature, which maximizes active site exposure and overcomes typical limitations of heterogeneous catalysts. This work not only establishes a novel strategy for controlling supramolecular architecture but also compellingly demonstrates that for catalytic applications, ensuring active site accessibility through judicious structural design can be a more potent strategy than pursuing isolated structural complexity.