Gupta Nidhi, Gupta Rachna, Chandra Sulekh, Bawa S S
National Physical Laboratory, Dr. K.S. Krishnan Marg, New Delhi-110012, India.
Spectrochim Acta A Mol Biomol Spectrosc. 2005 Apr;61(6):1175-80. doi: 10.1016/j.saa.2004.06.038.
A series of new mono and binuclear copper (II) complexes [Cul]X(2)and [Cu(2)lX(2)] where 1 = L(1), L(2) and L(3) are the macrocyclic ligands. In mononuclear complexes the geometry of Cu(II) ion is distorted squareplanar and in binuclear complexes the geometry of Cu(II) is tetragonal. The synthesized complexes were characterized by spectroscopic (IR,UV-vis and ESR) techniques. Electrochemical studies of the complexes reveals that all the mononuclear Cu(II) complexes show a single quasireversible one-electron transfer reduction wave (E(pc) = -0.76 to -0.84V) and the binuclear complexes show two quasireversible one electron transfer reduction waves (E(pc)(1) = -0.86 to -1.01V, E(pc)(2) = -1.11 to -1.43V) in cathodic region. The ESR spectra of mononuclear complexes show four lines with nuclear hyperfine splittings with the observed g(11) values in the ranges 2.20-2.28, g( perpendicular) = 2.01-2.06 and A(11) = 125-273. The binuclear complexes show a broad ESR spectra with g = 2.10-2.11. The room temperature magnetic moment values for the mononuclear complexes are in the range [mu(eff) = 1.70-1.72BM] and for the binuclear complexes the range is [mu(eff) = 1.46-1.59BM].
一系列新的单核和双核铜(II)配合物[Cul]X(2)和[Cu(2)lX(2)],其中1 = L(1)、L(2)和L(3)为大环配体。在单核配合物中,Cu(II)离子的几何构型为扭曲的平面正方形,在双核配合物中,Cu(II)的几何构型为四方的。通过光谱(红外、紫外可见和电子自旋共振)技术对合成的配合物进行了表征。配合物的电化学研究表明,所有单核Cu(II)配合物在阴极区域均显示出一个准可逆的单电子转移还原波(E(pc)= -0.76至-0.84V),而双核配合物显示出两个准可逆的单电子转移还原波(E(pc)(1)= -0.86至-1.01V,E(pc)(2)= -1.11至-1.43V)。单核配合物的电子自旋共振光谱显示有四条带有核超精细分裂的谱线,观察到的g(11)值在2.20 - 2.28范围内,g(垂直)= 2.01 - 2.06,A(11)= 125 - 273。双核配合物显示出g = 2.10 - 2.11的宽电子自旋共振光谱。单核配合物在室温下的磁矩值范围为[μ(eff)= 1.70 - 1.72BM],双核配合物的范围为[μ(eff)= 1.46 - 1.59BM]。