Solvent dependent reactivities of di-, tetra- and hexanuclear manganese complexes: syntheses, structures and magnetic properties.

An unusual solvent effect on the synthesis of five manganese complexes [Mn2(L1)2(Py)4](), [Mn2(L1)2(DMSO)4](), [Mn4(L2)4(OH)4](), [Mn4(L3)2(DMSO)7(H2O)](), and [Mn6O2(L4)4(OAc)2(OMe)2(DMSO)4]·MeOH] (), (H3L1 = 5-(2-oxyphenyl)-pyrazole-3-carboxylic acid; H2L2 = 5-(2-oxyphenyl)-pyrazole-3-carboxylic acid amide; H4L3 = di-[5-(2-oxyphenyl)-pyrazole]-3-hydroxamic ether; and H2L4 = 5-(2-oxyphenyl)-pyrazole-3-carboxylic acid methyl ester) has been reported. Five complexes have been characterized by X-ray single crystal diffraction, IR, element analysis, thermogravimetric analysis and UV-vis spectra. The analysis reveals that complexes and are isostructural with a bimetallic six-membered ring and L1 from the decomposition of the original H4ppha (H4ppha = 5-(2-hydroxyphenyl)-pyrazole-3-hydroxamic acid) ligand. Complexes and are two tetranuclear clusters, and possesses an aza12-metallacrown-4 core with L2 from the amide functionalization of the decomposition L1; while represents a novel linear [Mn4N8O2] core with L3 from the condensation of L1 and H4ppha. Complex is the first Mn6 cluster linked by two stacked, off-set 8-azametallacrown-3 subunits with [M-N-N-M-N-N-M-O] connectivity, and L4 derived from the esterification of L1. The magnetic behaviour of complexes show the dominant antiferromagnetic interactions between metal centers, whereas complex further reveals the coexistence of antiferromagnetic and ferromagnetic interactions, and slow magnetic relaxation at T < 6 K with S = 4 ground state, as well as field induced magnetization saturation.