ABSTRACT
An end-on azido bridged Mn(III) coordination chain polymer [Mn(5-Clsalpn)N3]n (complex 1) and its dimeric polymorph, [Mn(5-Clsalpn)N3]2 (complex 2), where 5-Clsalpn is N,N'-bis(5-chlorosalicylidene)-1,3-diaminopropane, were prepared. Complex 1, which is obtained as two concomitant polymorphs (1a and 1b) with nearly identical molecular structures but different crystal packing, has µ-1,1(end-on) azido bridges. This single atom bridge is unsymmetrical and leads to a -1 cm(-1) antiferromagnetic interaction among Mn(III) centers of the one-dimensional coordination polymer. Mn(III) anisotropy is manifested through Jahn-Teller elongation along the N(azido)-Mn-N(azido) axis, and results in single-chain magnet behavior. The phenoxo-bridged dimer (complex 2) has terminal azido ligands and a ferromagnetic interaction is mediated by the unsymmetrical bis-phenoxo bridge. Mn(III) anisotropy is manifested through Jahn-Teller elongation along an N-Mn-O axis, and results in single molecule magnet behavior. The dimers are organized into a two-dimensional network structure via Cl···Cl and Cl···H-phenyl interactions which are also ferromagnetic.
ABSTRACT
The present paper is devoted to the study of original trinuclear (CuII, LnIII, CuII) complexes (Ln = La, Ce, Gd). They derive from the polydentate ligands H2Li (i = 1, 3, 4) represented in Figure 1. The crystal and molecular structures of two complexes have been determined at room temperature. The (Cu, Gd, Cu) complex of H2L1 1Gd and the (Cu, Ce, Cu) complex of H2L3 3Ce crystallize in the triclinic space group P1 (no. 2) with the following cell parameters: a = 14.005(2) A, b = 14.7581(13) A, c = 11.3549(13) A, alpha = 96.273(9) degrees, beta = 97.648(11) degrees, gamma = 72.946(9) degrees, V = 2217.7(4) A3, and Z = 2 for 1Gd and a = 11.226(2) A, b = 16.927(3) A, c = 11.010(2) A, alpha = 108.67(2) degrees, beta = 110.48(1) degrees, gamma = 92.35(2) degrees, V = 1828.7(5) A3, and Z = 2 for 3Ce. Regarding possible supports for magnetic interactions, it may be noted that, in both complexes, each of the main bridging pathways between the equatorial positions of a copper(II) ion and the related lanthanide ion is double and not symmetrical. It involves a phenolato oxygen atom and an oximato nitrogen-oxygen pair of atoms. The resulting Cu(O,N-O)Gd networks are not planar, but 3Ce displays much larger deviations than does 1Gd. Determination of the thermal dependence of chi M (molar susceptibility) and the field variations of M (magnetization) show that in 3Gd and 4Gd the Cu-Gd interactions are antiferromagnetic while more "usual" ferromagnetic interactions are observed for 1Gd. The possibility of a relationship between structural and magnetic parameters is considered.
ABSTRACT
The monometallic precursor L1Cu (L1H2 standing for 1,3-bis((3-methoxysalicylidene)amino)-2,2'-dimethylpropane) reacts with GdC13 x 6H2O to afford a dinuclear complex which crystallizes in the orthorhombic space group Pca2(1) (No. 29) in a cell having the dimensions a = 9.0246(11) A, b = 16.5198(14) A, c = 20.286(2) A, and Z = 4. Analysis of the structural data shows that it may be formulated as [L1CuCl2Gd(H2O)4]Cl x 2H2O. The cationic dinuclear unit possesses a CuO2Gd bridging core which is almost planar. The complex displays a ferromagnetic interaction (10.1 cm(-1) which is the largest yet reported for a structurally characterized dinuclear (Cu-Gd) complex. Lower magnetic interactions are observed for neutral L1CuGdX3 x H2O complexes (X = N3C2, CF3COO). Consideration of the magnetic and structural data obtained for various dinuclear (Cu-Gd) complexes leads to a correlation between the magnitude of the magnetic interaction and the exponential of the dihedral angle between the two halves of the CuO2Gd bridging core.
ABSTRACT
Two original dinuclear (Cu(II),Gd(III)) complexes (1 and 2) deriving from polydentate nonsymmetrical Schiff base ligands LiH2 have been prepared. Formally they differ by the length of the diamino chain. They crystallize in the orthorhombic Pbca (No. 61) (1) and in the monoclinic P2(1/n) (No. 14) (2) space groups. The cell parameters are a = 12.6295(7) A, b = 20.7894(9) A, c = 18.3301(13) A, and Z = 8 for 1 and a = 12.7246(16) A, b = 13.5691(17) A, c = 14.5310(19) A, beta = 94.629(16) degrees , and Z = 4 for 2. These structural studies show that in both complexes the CuII and GdIII ions are doubly bridged by a phenolato oxygen atom and an oximato (N-O) pair. The bridging network is not planar. The more important distortions are observed for the complex having the larger diamino chain. Unexpectedly the latter complex presents an antiferromagnetic interaction, but the related J value is small (J approximately equal to -0.49 cm(-1)). In the former complex the interaction is ferromagnetic (J approximately equal to 3.5 cm(-1)) as it is for complexes containing (CuO2Gd) bridging cores which yield J values varying from 1.4 to 10.1 cm(-1).
ABSTRACT
Starting from a single precursor, bis(3-methoxysalicylaldehydato)copper (II), which contains an O(4)Cu chromophore, three routes to discrete dinuclear Cu(II)/Ln(III) complexes (Ln = Pr, Eu, Gd, Yb) are described. The pairs of chromophores occurring in the resulting complexes are either O(4)Cu/O(4)Ln or O(2)N(2)Cu/O(4)Ln, the coordination sphere of the Ln ions being completed, in both cases, with six oxygen atoms afforded by three nitrato ions. Two Cu/Gd complexes involving either two tridentate ligands (2) or one hexadentate ligand (7) have been structurally characterized. They crystallize in the monoclinic space groups P2(1)/n (No. 14) (2) and P2(1)/c (No. 14) (7). The cell parameters are a = 9.7185(7) Å, b = 16.7839(12) Å, c = 14.8868(8) Å, beta = 97.445(5) degrees, and Z = 4 (2) and a = 9.7656(9) Å, b = 19.889(2) Å, c = 15.870(2) Å, beta = 95.512(9) degrees, and Z = 4 (7) respectively. The magnetic properties of six Cu/Ln complexes have been determined. A quantitative analysis of the magnetic properties of the Cu/Gd complexes shows that the interaction is of the ferromagnetic type with a J constant varying from 4.8 to 7.0 cm(-)(1). The decrease of the interaction parallels the variation of the dihedral angle between the two halves (OCuO and OGdO) of the bridging core.