Aggregation of a Giant Bean-like {Mn26Dy6} Heterometallic Oxo-Hydroxo-Carboxylate Nanosized Cluster from a Hexanuclear {Mn6} Precursor

Starting from a well-known hexanuclear mixed-valent manganese cluster, we report a synthetic protocol for its extension toward very large 3d-4f clusters. The exemplary case study demonstrates that a combination of such {Mn6} clusters with a DyIIIsalt and an auxiliary triazine-type ligand yields a large bean-like, heterometallic dotriacontanuclear mixed-valent nanocluster [Mn26Dy6O16(OH)12(O2CCHMe2)42]. This compound, which possesses a molecular C2symmetry and crystallizes in a dense packing arrangement without inclusion of solvents, comprises 16 MnIII, 10 MnII, and 6 DyIIIions, thus leading to a plurality of intracluster magnetic exchange interactions. Interestingly, this results in the highest-nuclearity Mn–Dy cluster that shows a single-molecule magnetic (SMM) behavior.