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

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.