A novel di-compartmental bis-(2-hydroxyisophtalamide) macrocyclic ligand and its mononuclear Cu(II) and Ni(II) complexes.

摘要: The synthesis and characterisation of the new di-compartmental bis-(2-hydroxyisophtalamide) macrocyclic pro-ligand, LH6, which comprises two phenol-diamide units linked by ethylene bridges, is herein reported, together with its corresponding di-phenolate salt, [NBu4]2[LH4]. three compounds, [LH4(OMe)2] (protected ligand), LH6 [LH4][NBu4]2 were fully characterised including X-ray crystallography for results solid-state solution studies have indicated that macrocycle can adopt specific conformations, are influenced H-bonding interactions as well deviation amide carbonyl relative to phenol plane. reacts MII(acetate)2·(H2O)6 (M = Ni, Cu) in a 1:1 ratio presence 4 eq [NBu4](OH) methanol afford dianionic [M(LH2)]2− complexes, 12− 22−, respectively. crystallography, EPR, NMR UV-vis spectroscopic data, combined DFT calculations, indicate 22− unique unsymmetrical square planar mononuclear complexes intramolecularly H-bonded. Thus, one compartment contains MII–N2O2 centre resulting from tetra-anionic di-phenolato di-amidato ligation; other possesses protonated N–H groups H-bonded coordinated phenolate O atoms. This represents example both appears unusually strong revealed N(H/D) exchange experiments; may be responsible stability complex, difficulty isolating dinuclear complex [M2(L)]2−.