“Cage Walking” Synthetic Strategy for Unusual Unsymmetrical Supramolecular Cages

Developing novel assembly methods for supramolecular compounds has long been a research challenge. Herein, we describe how to integrate the B–C coupling reaction and “cage walking” process into coordination self-assembly to construct supramolecular cages. In this strategy, dipyridine linkers containing alkynes react with the metallized carborane backbone through B–C coupling and then “cage walking” resulting in metallacages. However, dipyridine linkers without alkynyl groups can form only metallacycles. We can regulate the size of metallacages based on the length of the alkynyl bipyridine linkers. When tridentate-pyridine linkers participate in this reaction, a new type of ravel is formed. The metallization of carboranes, the B–C coupling reaction, and especially the “cage walking” process of carborane cages play a vital role in this reaction. This work provides a promising principle for the synthesis of metallacages and opens up a novel opportunity in the supramolecular field.