Novel mixed-valence Cu compounds formed by Cu(II) dimers with double oximato bridges: in situ formation of anionic layer [Cu2(SCN)3]n(n-).

Two new N3O donor ketoxime Schiff bases (HL(1) and HL(2)) have been synthesized by condensing N,N-dimethylethylenediamine with diacetylmonoxime and benzilmonoxime, respectively in a 1:1 ratio. Reaction of Cu(ClO4)2·6H2O with HL(1) resulted in a discrete oximato-bridged dinuclear Cu(II) complex [Cu2(L(1))2(H2O)2](ClO4)2 (1). The same reaction in presence of NaSCN affords the complex {[Cu(II)2(L(1))2][Cu(I)4(µ(1,3)-SCN)4(µ(1,1,3)-SCN)2]}n (2), where partial Cu(II)→Cu(I) reduction is observed. In 2, arrays of [Cu(II)2(L(1))2](2+) cationic units are inserted in between 2D {[Cu(I)4(SCN)6](2-)}n layers and connected via µ(1,1,3)-SCN(-) links, thus forming a 3D network. On the other hand, reaction of Cu(CH3COO)2 and HL(2) in the presence of NaSCN gave rise to a mixed-valence pentanuclear cluster {[Cu(II)2(L(2))2(NCS)]2[Cu(I)(SCN)(µ(1,1)-SCN)(µ(1,3)-SCN)]} (3) where Cu(II) is also partly reduced to Cu(I). In compound 3, two cationic [Cu(II)2(L(2))2(NCS)](+) units are bridged by the anionic [Cu(I)(SCN)3](2-) unit through long Cu-SCN linkages. The ligands and the complexes have been characterized by elemental analysis, UV/Vis and IR spectroscopy. The complexes are further characterized by single crystal X-ray diffraction and variable temperature magnetic (VTM) studies. Finally a complete magneto-structural correlation has been established between compounds 1-3 and all the characterized Cu dimers with a double NO bridge.

Isolation of four new CoII/CoIII and NiII complexes with a pentadentate Schiff base ligand: syntheses, structural descriptions and magnetic studies.

In this paper we report the temperature and pH dependent syntheses and systematic characterization of four new Co(II)/Co(III) and Ni(II) complexes with a pentadentate Schiff base ligand H(3)L obtained by condensing 1,3,-diaminopropan-2-ol with 2-hydroxyacetophenone in 1:2 molar ratio. The room temperature syntheses involving Co(II) and Ni(II) nitrates and the ligand H(3)L lead to the isolation of the dinuclear species [Co(2)L(2)(H(2)O)] (1), and the mononuclear complex [Ni(LH)] (3), respectively, whereas refluxing at basic pH leads to the tetranuclear complexes, [Co(II)(2)Co(III)(2)L(2)(µ(3)-OMe)(2)(NO(3))(H(2)O)(2)]NO(3)·2(H(2)O) (2), and [Ni(4)L(2)(µ(3)-OMe)(2)(H(2)O)(2)]·2H(2)O (4). 1 is found to be a simple mono alkoxo-bridged Co(III) dinuclear species, whereas 2 and 4 are both rhomb-like tetrameric complexes with double oxo bridges and µ(3)-methoxo bridges, derived from the methanol solvent, in an open dicubane arrangement. Moreover 2 shows six coordinate ordered Co(II) and Co(III) ions and 4 has both six- and five-coordinate Ni(II) centers. Compound 3 is assigned a tentative mononuclear structure based on IR, UV-Vis spectroscopic, (1)H-NMR and ESI mass study results and is supposed to have one Ni(II) center coordinated with a ligand fragment in square planar geometry. The variable temperature magnetic susceptibility study for 2 and 4 is performed which indicate for both 2 and 4 the presence of intracluster dominant ferromagnetic interactions.