Synthesis, characterization and electrochemical properties of bis(μ2-perchlorato)tricopper(ii) complexes derived from succinoyldihydrazones
作者:R. Borthakur、A. Kumar、A. Lemtur、R. A. Lal
DOI:10.1039/c3ra42048e
日期:——
Three new homotrimetallic copper(II) complexes ([Cu3(Ln)(ClO4)2(H2O)m] with H4Ln = H4L1 â H4L3, m = 0, 3) have been synthesized from substituted succinoyldihydrazones (H4Ln) in methanol. The composition of the complexes has been established on the basis of data obtained from analytical and mass spectral studies and molecular weight determination in DMSO. The structure of the complexes has been discussed in the light of molar conductance, magnetic moment data and electronic, EPR, IR and FT-IR spectral studies. The molar conductance values for the complexes in the region of 1.2â1.7 Ωâ1 cm2 molâ1 in DMSO indicate that the complexes are nonelectrolytes. The magnetic moment values for the complexes suggest considerable metalâmetal interaction in the structural unit of the complexes. Copper centres have square planar and square pyramidal stereochemistry. The EPR parameters of complexes 1 and 3 indicate that the copper centre has a doublet ground state, while for complex 2, the ground state is a mixture of both doublet and quartet states. Electron transfer reactions of the complexes have been investigated by cyclic voltammetry.
三种新的均相三金属铜(II)配合物([Cu3(Ln)(ClO4)2(H2O)m],其中H4Ln = H4L1至H4L3,m = 0, 3)已通过在甲醇中使用取代的琥珀酰肼(H4Ln)合成。通过分析和质谱研究以及在DMSO中测定分子量的数据,确定了这些配合物的组成。根据摩尔电导率、磁矩数据以及电子、EPR、IR和FT-IR光谱研究的结果,对配合物的结构进行了讨论。这些配合物在DMSO中的摩尔电导率值在1.2–1.7 Ω⁻¹ cm² mol⁻¹的范围内,表明这些配合物是非电解质。配合物的磁矩值表明在配合物的结构单元中存在显著的金属间相互作用。铜中心具有平面正方形和方锥形的立体化学。配合物1和3的EPR参数表明,铜中心具有双重基态,而配合物2的基态则是双重态和四重态的混合。通过循环伏安法研究了这些配合物的电子转移反应。