Construction of High-Nuclearity Manganese-Cluster–Organic Frameworks by Using a Tripodal Alcohol Ligand

Two novel cluster–organic frameworks based on the 12-nuclearity manganese-cluster secondary building unit (SBU), [Mn III 4 Mn II 8 (L) 4 (Ac) 8 (MeO) 2 (μ 5 -O) 2 (H 2 O) 4 ](Ac) 2 ·16H 2 O ( 1 ) and [Mn III 4 Mn II 8 (L) 4 (Ac) 8 (MeO) 2 (μ 5 -O) 2 (H 2 O) 4 ](Ac) 2 ·12H 2 O ( 2 ), where Ac = CH 3 COO – and MeO = CH 3 O, have been constructed from solvothermal reactions of the 3-nuclearity manganese cluster [Mn 3 (μ 3 -O)(Ac) 6 (py) 3 ](ClO 4 ) ( Mn 3, where py = pyridine) with a tripodal alcohol ligand containing a 4-pyridyl group. 1 and 2 represent the first examples of metal–organic frameworks containing 12-nuclearity manganese-cluster SBUs. In addition, 1 exhibits an integration of the porosity and magnetic properties from both the framework and cluster in a porous material.