Synthesis, structural characterizations and magnetic properties of a series of mono-, di- and polynuclear manganese pyridinecarboxylate compounds

• Seven new manganese(II, III, IV) pyridinecarboxylate compounds (Et4N)[MnCl2(pic)(2)] (1, Hpic = picolinic acid) [MnCl(Pic)(2)(H2O)].H2O (2), [MnCl(pic)(H2O)2](n) (3), [Mn(Pic)(2)](n) (4), [MnCl(pic)](n) (5), [MnCl2(4-C5H4NHCOO)](n) (6) and [Mn2O2(pic)(4)] (7) were synthesized and structurally characterized. The picolinate ligand coordinates to the Mn ion forming a chelating five-membered ring which constructs diverse architectures by various bridging modes, such as mu-Cl, mu(1,1)(-) and mu(1,3)-carboxylate bridges (syn-syn and syn-anti modes). The interaction between the pyridyl rings is discussed, displaying a face-to-face pi-pi stacking for complex 6 and a T-shaped C-H...pi attraction for complex 4. Complex 3 has an infinite zigzag chain structure in which two neighboring Mn ions are linked by a carboxylate bridge in a syn-anti mode. In complex 4, the Mn(pic)(2) fragments are joined to each other by double mu(1,1)-carboxylate bridges, forming a 2D layer structure. Complex 5 contains Mn4O4 square subunits which are connected by double mu-Cl bridges to form a grid-like 2D structure. The isonicotinate complex 6 has a zigzag chain structure containing mixed double mu-Cl and mu(1,3)-carboxylate bridges in a syn-syn mode. Protonation at the pyridyl-N position was found and identified by the IR and magnetic properties of 6. The participation of an oxidizing agent like MnO4- leads to complexes containing higher valent manganese (1, 2 and 7). The IR spectra of these complexes are discussed and found to be consistent with the structural features. The magnetic properties of complexes 4, 5 and 6 have been investigated. Antiferromagnetic coupling interactions were observed and satisfactory fitting results were obtained with J values ranging from -0.63 cm(-1) to -2.35 cm(-1). The magnetic parameters of these complexes, together with the parameters of other Mn complexes with comparable structures, are compared and discussed based on the bridging modes. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004).

Nyckelord

carboxylate ligands

coordination polymers

magnetic properties

manganese

X-ray diffraction

oxygen-evolving complex

crystal-structure

photosystem-ii

coordination polymers

metal-complexes

model complexes

picolinic-acid

zigzag chain

mn cluster

water

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