Design and Synthesis of Al 7 Ni 2 Heterometallic Clusters Based on Metal Substitution and Ligands Protection Strategies †

Comprehensive Summary The synthesis of heterometallic aluminum‐based materials is challenging yet attractive, due to their potential applications in optics, catalysis, magnetism and semiconductor device. We have now successfully synthesized two Al 7 Ni 2 heterometallic clusters bearing different peripheral alkoxide ligands through a heterometal substitution strategy. Single crystal structure analysis shows that they are isostructural, only with slight differences in the number of OH and guests. We found that benzyl alkoxides protected Al 7 Ni 2 cluster compound is more stable in H 2 O and various organic solvents when compared with ethoxides coordinated one. Moreover, it can be used as a reliable catalyst in aldol condensation reactions with higher activity. This work provides a new method for the design of stable crystalline heterometallic aluminum oxo compounds and reveals their excellent catalysis performance.