Synthesis, Structure and Magnetic Properties of Some Copper(II) Complexes Supported by Pendant Calix[4]arene Ligands

The synthesis and characterization of three new calix[4]arene ligands bearing two pendant acylhydrazone arms and some of their Cu2+ complexes, namely [Cu(L1-2H)(MeOH)] (3), [Cu(L1'-H)(Cl)(2-hydroxy-1-naphthaldehyde)] (4), [Cu2(L2-2H)2] (5) and [Cu4(L3-2H)2(OH)2(ClO4)2] (6) are described. The ligands are obtained by simple imine condensation reactions between calix[4]arene-1,3-bis-acyl-hydrazides and the corresponding carbaldehydes. The Cu2+ ions are always situated in 5-membered chelate rings, either in a deprotonated -O-CR=N-N=CHR (enolate) or a neutral O=CR-NH-N=CHR (keto) form. In 3 and 4 a 5-membered chelate ring is formed through interaction of the Cu2+ ion with the naphtholato group. Additional MeOH, chlorido or naphthaldehyde ligands complete the planar (3) or square pyramidal (4) coordination spheres. The thiophenes in 5 do not interact with the Cu2+ ions and dimerization of [CuL] entities occurs to produce centrosymmetric 2 : 2 complexes with four-coordinated Cu2+ ions. In 6, two dinuclear [Cu2(L3-2H)(OH)] subunits are connected by mu 1,3-bridging ClO4- ions. The magnetic properties of polycrystalline samples of 5 and 6 were studied by variable temperature magnetic susceptibility measurements. The chi ''(T) vs T plots indicate antiferromagnetic exchange interactions. The exchange interactions in 6 (J=-4.8 cm-1) were found to be stronger than in 5 (J=-0.54 cm-1). This is also supported by broken symmetry DFT calculations. The synthesis of three new calix[4]arene ligands bearing pendant acylhydrazone arms and some of their Cu2+ complexes has been achieved. X-ray crystallographic and spectroscopic studies show that the Cu2+ are always coordinated by the pendant acylhydrazone arms giving rise to mononuclear and polynuclear assemblies.image