Controlled Orthogonal Self-Assembly of Heterometal-Decorated Coordination Cages

Multiple orthogonal coordinative interactions were utilized to construct heterometal-decorated tetrahedral cages from in situ formed trinuclear ZrIV clusters through the combination with other metal ions such as CuII or PdII. Through effective use of the hard/soft acid/base principle, the orthogonal self-assembly process of Zr-bpydc-CuCl2 (H2bpydc=2,2-bipyridine-5,5-dicarboxylic acid) can be finely controlled using three strategies: post-synthetic metallization, a stepwise metalloligand approach, or a one-pot reaction.