Designable assembly of atomically precise Al 4 O 4 cubane supported mesoporous heterometallic architectures.

Heterometallic cluster-based framework materials are of interest in terms of both their porous structures and multi-metallic reactivity. However, such materials have not yet been extensively investigated because of difficulties in their synthesis and structural characterization. Herein, we reported the designable synthesis of atomically precise heterometallic cluster-based framework compounds and their application as catalysts in aldol reactions. By using the synergistic coordination protocol, we successfully isolated a broad range of compounds with the general formula, [Al 4 M 4 O 4 (L) 12 (DABCO) 2 ] (L = carboxylates; DABCO = 1,4-diazabicyclo[2.2.2]-octane; M 2+ = Co 2+ , Mn 2+ , Zn 2+ , Fe 2+ , Cd 2+ ). The basic heterometallic building blocks contain unprecedented main-group γ-alumina moieties and surrounding unsaturated transition metal centers. Interestingly, the porosity and interpenetration of these frameworks can be rationally regulated through the unprecedented strategy of increment of the metal radius in addition to general introduction of sterically bulky groups on the ligand. Furthermore, these porous materials are effective catalysts for aldol reactions. This work provides a catalytic molecular model platform with accurate molecular bonding between the supporters and catalytically active metal ions.