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.
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.
Reactions of hydrated zinc(II) trifluoroacetate and sodium azide with two tridentate Schiff bases HL 1 (2-((E)-(2-(dimethylamino)ethylimino)methyl)-4-chlorophenol) and HL 2 (2-((E)-(2-(dimethylamino)ethylimino)methyl)-4-bromophenol) under the same reaction conditions yielded two dinuclear isostructural zinc(II) complexes, [Zn(L 1 )(N 3 )] 2 (1) and [Zn(L 2 )(N 3 )] 2 (2), respectively. The complexes were characterized systematically by elemental analysis, UV-Vis, FT-IR and 1 H NMR spectroscopic methods. Single crystal X-ray diffraction studies reveal that each of the dinuclear complexes consists of two crystallographically independent zinc(II) ions connected by double bridging phenoxides. All zinc(II) ions in 1 and 2 are surrounded by similar donor sets and display distorted square pyramidal coordination geometries. The ligands and complexes reveal intra-ligand 1 (π→π*) flourescence. The enhancement of the fluorescence intensities for the complexes compared to the ligands indicates their potential to serve as photoactive materials.
A new trinuclear heterometallic complex, [(CuL)Na(CuL)]·ClO4 (1), has been prepared using a Schiff base, H2L (where H2L=N,N′-(1,2-phenylene)-bis(3-methoxysalicylideneimine) and characterized by elemental analysis, Fourier transform infra-red (FT-IR) spectroscopy, UV/Vis, magnetic, electrochemical, and single crystal X-ray diffraction methods. The structure analysis reveals that two metallo-ligand [(CuL)] units are connected to each other by a sodium ion resulting in the cationic unit [(CuL)Na(CuL)]+. Both the copper(II) ions display an almost square planar geometry while the sodium ion adopts a trigonal-dodecahedral coordination geometry. The spectroscopic and other physicochemical studies are in good agreement with the crystal structure of the complex.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.