Electron spin resonance study of Cu(II)-crown ether complexes with 3dX(X=Z2) ground state doublet in solution.
スポンサーリンク
概要
- 論文の詳細を見る
Copper(II) chloride and crown ethers (12-crown-4, 15-crown-5 and 18-crown-6) formed orange or orangeyellow complexes in dry chloroform. We found that the ESR <I>g</I>-anisotropy of the complexes was greatly dependent on the numbers of donor oxygens and the ring-numbers. The complexes obtained from 12-crown-4 and 18-crown-6 showed <I>g</I>-anisotropy (<I>g</I><SUB>⁄⁄</SUB>><I>g</I><SUB>⊥</SUB>); these are well characterized by the 3d<SUB>x<SUP>2</SUP>−y<SUP>2</SUP></SUB>, or 3d<SUB>xy</SUB> ground state. On the other hand, the complexes of 15-crown-5 and its benzo derivatives exhibited the reverse <I>g</I>-anisotropy (<I>g</I><SUB>⁄⁄</SUB><<I>g</I><SUB>⊥</SUB>); these are characterized by the 3d<SUB>z<SUP>2</SUP></SUB> ground state with S=1/2. The electron nuclear dipolar term and the Fermi's isotropic term were estimated from the ESR parameters based on Bleaney's calculation. The chlorine superhyperfine splittings were observed in the g<SUB>⁄⁄</SUB>- component. The MO bonding parameters were estimated by assuming the compressed octahedral, the trigonal bipyramidal, and pentagonal bipyramidal geometry at the paramagnetic site. The bonding nature was studied on the basis of the observed ligand spin densities.
- 公益社団法人 日本化学会の論文