Stepwise and Controllable Synthesis of Mesoporous Heterotrimetallic Catalysts Based on Predesigned Al4Ln4 Metallocycles

The motivation for making heterometallic compounds stemmed from their emergent synergistic properties and enhanced capabilities for applications. However, the atomically precisely controlled synthesis of heterometallic compounds remains a daunting challenge of the complications that arise when applying several metals and linkers. Herein, a stepwise and controlled method is reported for the accurate addition of second and third metals to homometallic aluminum macrocycles based on the synergistic coordination and hard-soft acid-base theory. These heterometallic compounds showed a good Lewis acid catalytic effect, and the addition of hetero-metals significantly improved the catalytic effect and rate, among that the conversion rate of compound AlOC-133 reached 99.9% within half an hour. This method combines both the independent controllability of stepwise assembly with the universality of one-step methods. Based on the large family of clusters, the establishment of this method paves the way for the controllable and customized molecular-level synthesis of heterometallic materials and creates materials customized for preferential application.