Chemical Assembling of Heterometallic {Cd-M} (M=Li, Mg, Eu, Tb) Molecules with 3,5-Di-tert-butylbenzoate Bridges and N-Donor Ligands

摘要

It was shown that the reaction of potassium 3,5-di-tert-butylbenzoate (Kbzo) and Cd(NO3)(2)in EtOH gave the [Cd-3(H2O)(EtOH)(3)(bzo)(6)].EtOH complex (I). The use of Li(bzo) or Mg(bzo)(2)salts in this reaction in the presence of excess 2,4-lutidine or a stoichiometric amount of 1,10-phenanthroline initiated the crystallization of the polymer [CdLi2(H2O)(EtOH)(2)(bzo)(4)](n)(II) containing no N-donor ligands or trinuclear complexes [Cd2Mg(bzo)(6)(L)(2)].Solv (L, Solv=lut, 2EtOH (III); phen, 6CH(2)Cl(2)(IV)) that included coordinated N-donors. The use of Eu(bzo)(3)as the source of Ln ions in the presence of a stoichiometric amount of lut gave trinuclear carboxylates [EuCd2(H2O)(2)(EtOH)(2)(bzo)(7)].3EtOH (V) and [TbCd2(H2O)(EtOH)(3)(bzo)(7)].2EtOH.2.7H(2)O (VI) containing no lut molecules. It was found that the incorporation of coordinated N-donors was observed only if a 10-fold excess of pyridine or a stoichiometric amount of 2,2'-dipyridyl was added to the reaction medium in the presence of Ln(NO3)(3).6H(2)O (Ln=Eu, Tb) or Ln(bzo)(3), respectively. In these cases, trinuclear {Cd-Ln} complexes were formed, which contained a terminal N-donor ligand, [LnCd(2)(bzo)(6)(NO3)(py)(4)].1.5MeCN (Ln=Eu (VII), Tb (VIII)), [EuCd2(H2O)(bzo)(7)(bpy)(2)].2THF.3H(2)O.MeCN (IX) and [TbCd2(H2O)(bzo)(7)(bpy)(2)] (X)). The structures of the new compounds were determined by single-crystal X-ray diffraction analysis. The complexes were characterized by luminescence spectroscopy, IR spectra, CHN-analysis and fluorescence analysis.