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The ketone/gem-diol (L1H2) and bis(gem-diol) (L2H4) forms of the ligand 2,6-di-(2-pyridylcarbonyl)pyridine in Mn cluster chemistry have afforded the new complexes [MnII4MnIII2(N3)6Cl4(L1)2(DMF)4] and [MnII4MnIII6O2(N3)12(L1)2(L2H)2(DMF)6].

The first application of 1-methyl-1H-pyrrole-2-carbaldehyde oxime as a ligand for the coordination of paramagnetic transition metal ions has afforded a new {Mn(III)25} barrel-like cluster linked via Na(+) cations into a 1D polymeric topology that exhibits single-molecule magnetic behaviour.

The employment of 2-pyrrolyloximes in high-nuclearity transition-metal cluster chemistry has provided access to unprecedented decanuclear and dodecanuclear Fe(III) cagelike clusters bearing the anion of pyrrole-2-carboxaldehyde oxime (praoH(2)), the simplest member of this new family of ligands; the identity of the products depends on the nature of the counteranion present in the starting materials.