Study of 1H NMR spectra of dinuclear complexes of heavy lanthanides with phthalocyanines based on separation of the effects of two paramagnetic centers

被引:53
作者
Ishikawa, N [1 ]
Iino, T [1 ]
Kaizu, Y [1 ]
机构
[1] Tokyo Inst Technol, Dept Chem, Meguro Ku, Tokyo 1528551, Japan
关键词
D O I
10.1021/jp034971n
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Experimental and theoretical study of nuclear magnetic resonance (NMR) spectra of dinuclear complexes of paramagnetic trivalent Tb, Dy, Ho, Er, Tm, or Yb ions with phthalocyanine ligands is presented. The H-1 NMR paramagnetic shifts of the dinuclear Pc triple-decker complexes PcLnPcLnPc* (abbreviated as [Ln, Ln]; Pc is the dianion of phthalocyanine and Pc* is the dianion of 2,3,9,10,16,17,23,24-octabutoxyphthalo-cyanine) were measured in CDCl3 solution at 303 K. These values are analyzed using the corresponding data of two series of heterodinuclear complexes with a single paramagnetic ion, namely PcYPcLnPc* ([Y, Ln]) and PcLnPcYPc* ([Ln, Y]). The paramagnetic shifts in [Y, Ln] and [Ln, Y] were reproduced solely by the magnetic dipolar (pseudo-contact) term, using a geometric structure that was obtained by a density functional theory (DFT) calculation with a moderate modification. Each paramagnetic shift value of [Ln, Ln] is shown to be sum of those of [Y, Ln] and [Ln, Y]. The independence of the paramagnetic shift contributions of the two Ln ions is explained by the small interaction between f-electronic systems in [Ln, Ln]. The shifts in an [Ln, Ln] complex have the same sign, because all the protons are positioned in the same region of the contour map of the dipolar contributions of the two paramagnetic sites.
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页码:7879 / 7884
页数:6
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