Construction of Covalent Organic Cages with Aggregation‐Induced Emission Characteristics from Metallacages for Mimicking Light‐Harvesting Antenna

Abstract A series of covalent organic cages built from fluorophores capable of aggregation‐induced emission (AIE) were elegantly prepared through the reduction of preorganized M 2 (L A ) 3 (L B ) 2 ‐type metallacages, simultaneously taking advantage of the synthetic accessibility and well‐defined shapes and sizes of metallacages, the good chemical stability of the covalent cages as well as the bright emission of AIE fluorophores. Moreover, the covalent cages could be further post‐synthetically modified into an amide‐functionalized cage with a higher quantum yield. Furthermore, these presented covalent cages proved to be good energy donors and were used to construct light‐harvesting systems employing Nile Red as an energy acceptor. These light‐harvesting systems displayed efficient energy transfer and relatively high antenna effect, which enabled their use as efficient photocatalysts for a dehalogenation reaction. This research provides a new avenue for the development of luminescent covalent cages for light‐harvesting and photocatalysis.