Determination of the Structural Parameters of Heteronuclear (Phthalocyaninato)bis(crownphthalocyaninato)lanthanide(III) Triple-Deckers in Solution by Simultaneous Analysis of NMR and Single-Crystal X‑ray Data

Application of a
general and convenient approach to the synthesis of heteronuclear
crown-substituted triple-decker phthalocyaninates afforded two series
of complexes containing one dia- and one paramagnetic Ln­(III) ion
(for Y and almost the whole lanthanide family), [(15C5)4Pc]­M*­[(15C5)4Pc]­M­(Pc) (or [M*,M] for brevity sake), where
(15C5) is 15-crown-5; (Pc2–) is phthalocyaninato
dianion; and M ≠ M* = Y, Nd, Eu, Tb, Dy, Ho, Er, Tm, Yb. This
approach consists of using LaPc2 as an efficient Pc2– source. The solid-state structures of two complexes
([Tm*,Y] and [Yb*,Y]) were studied by single-crystal X-ray diffraction
analysis, providing therefore a structural model for the assignment
and analysis of 1H NMR spectra of the complexes, which
is strongly affected by the presence of paramagnetic lanthanide ions.
Model validation was performed on complexes containing two different
paramagnetic ions[Dy*,Gd] and [Gd*,Dy] as well as [Tb*,Tm]
and [Tm*,Tb]synthesized by the above-mentioned method.

采用一种通用且便捷的方法合成杂冠醚取代的三夹层酞菁配合物，得到两个系列的配合物，每个系列均包含一个抗磁离子与一个顺磁镧系(III)离子（Ln(III)），覆盖钇（Y）以及几乎全部镧系元素，对应通式为[(15C5)₄Pc]M*[(15C5)₄Pc]M(Pc)（简称[M*,M]）；其中15-冠-5（15-crown-5）为15-冠-5醚环，酞菁二价阴离子（phthalocyaninato dianion）记为(Pc²⁻)，且M ≠ M* = Y、钕（Nd）、铕（Eu）、铽（Tb）、镝（Dy）、钬（Ho）、铒（Er）、铥（Tm）、镱（Yb）。
该合成方法以二酞菁合镧(LaPc₂)作为高效的酞菁二价阴离子源。
通过单晶X射线衍射分析（single-crystal X-ray diffraction analysis）解析了两个配合物（[Tm*,Y]与[Yb*,Y]）的固态结构，以此作为结构模型对配合物的氢核磁共振（¹H NMR）谱进行归属与分析——此类谱图受顺磁性镧系离子的影响极为显著。
采用上述方法合成了包含两种不同顺磁离子的配合物——[Dy*,Gd]、[Gd*,Dy]以及[Tb*,Tm]、[Tm*,Tb]——并据此完成了模型验证。