The stepwise substitution in the hierarchical building of {Co₁₁Cd₆} cluster-based MOFs from {Co₁₄} precursor

Abstract

A heterometallic aggregation of {Co11Cd6} can be hierarchical built from a {Co14} precursor directly. HRESI-MS technique was used to track the stepwise Cd2+-capture: {Co14} → {Co8} → {Co8Cd2} → {Co8Cd3} → {Co8Cd4} → {Co8Cd5} → {Co8Cd6} → {Co11Cd6}.

Hierarchical Construction and Magnetic Difference of {Co12M12} (M = Co2+/Cd2+) Aggregates from {Co14} Cluster-Based Precursors in the Presence of Homo/Heterometal Salts

“…Coordination clusters with potential active sites (e.g., metal-ligand complexes exhibiting coordinative unsaturation) can be used as precursor when induced by external stimuli (including solvent, pH, temperature, etc.). Some degree of disaggregation of external CoCl 2 and dpbt molecules from the {Co 14 } precursor was found in our recent research, − while the basic backbone remained partially stable. Thus, considering the selection of excess paramagnetic homo-CoCl 2 salts or diamagnetic hetero-Cd­(OAc) 2 using appropriate solvothermal condition is conducive to the hierarchical construction of sophisticated aggregations of {Co 24 } and {Co 12 Cd 12 } with defined skeletons and magnetic difference.…”

“…In our systematic study, we obtained {Co 14 } cluster-based MOLs (metal–organic layers) from {Co 14 } precursors and a giant {Co 24 } supercluster from {Co 13 } precursors, respectively. , Recently, a heterometallic {Co 11 Cd 6 } cluster-based aggregation was hierarchically built, along with the stepwise capture of Cd 2+ ions in {Co 14 } precursors . The reassembly capability based on {Co 14 } prompted our interest for further exploration.…”

“…22,23 Recently, a heterometallic {Co 11 Cd 6 } cluster-based aggregation was hierarchically built, along with the stepwise capture of Cd 2+ ions in {Co 14 } precursors. 24 The reassembly capability based on {Co 14 } prompted our interest for further exploration. The use of preformed {Co 14 } precursors, in combination with homo/heterometals, may promote the directed generation of other sophisticated aggregations with defined cores.…”