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Snap-Fit Assembly of Multicomponent Pt(II) Metallacages Enabling Through-Space Electron Transfer and Enhanced Photocatalysis

2026/06/10 by Jikun Li, Shijin Jian, Zilin Zhou +5 · 1 voice
Chemistry · Materials Science · #Magnetism in coordination complexes #Supramolecular Chemistry and Complexes #Synthesis and Properties of Aromatic Compounds

paper · doi:10.1021/jacs.6c00051

openalex publication_date 2026/06/10 · openalex created_date 2026/06/11 · openalex updated_date 2026/06/25

Abstract

The rational design of heteroleptic metallacages from multiple ligands remains a significant challenge in supramolecular chemistry due to the tendency for thermodynamic mixtures and poorly defined assemblies. Herein, we demonstrate a snap-fit-inspired self-assembly strategy for the construction of heteroleptic platinum(II) cages containing three types of organic ligands. An asymmetric tetracarboxylate ligand acts as a multifaceted connector, guiding the two distinct tetrapyridyl panels to snap into place around the Pt(II) vertices, yielding a type of box-shaped metallacage with reduced constitutional symmetry. Spatial combination of electron-rich anthracene or dimethoxybenzene donors with electron-deficient perylene diimide acceptors within a single metallacage facilitates efficient through-space photoinduced electron transfer and charge separation. As a result, the metallacages promote the generation of superoxide radical anions and enable photocatalytic benzimidazole formation from o -phenylenediamine and aromatic aldehydes via a condensation–oxidative cyclization sequence. This snap-fit assembly concept provides a modular and programmable approach to multicomponent metallacages and enables deliberate control over intramolecular electronic communication for supramolecular photocatalysis.

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