The synthesis, X-ray crystal structures and magnetic properties of two new types of dimers of multinuclear manganese aggregates are described. [Mn3O(O2CPh)6(py)2] 2(4,4′-bpy) is prepared from the reaction of the trinuclear starting material [Mn3O(O2CPh)6(py)2(H2O)] with 4,4′-bipyridine. This compound can be described as a dimer of trinuclear units and has been characterized crystallographically as part of a unit cell which also contains a monomeric, trinuclear species. Dimers of enneanuclear manganese complexes linked by two bifunctional units (4,4′-bipyridine or trans-1,2-bis(4-pyridylethene)) may be prepared from the tetranuclear starting material, (nBu4N) [Mn4O2-(O2CR)9(H2O)], where R=Ph or C6H4-p-OMe. The new octadecanuclear complex [Mn9O7(O2CC6H 4-p-OMe)13(4,4′-bpy)]2 has been structurally characterized. This complex shows magnetic behavior which can be fit by considering only magnetic interactions within the individual Mn9O7 units.
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