Structural studies of the whole series of lanthanide double-decker compounds with mixed 2,3-naphthalocyaninato and octaethylporphyrinato ligands
Structural studies of the whole series of lanthanide double-decker compounds with mixed 2,3-naphthalocyaninato and octaethylporphyrinato ligands
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DOI：
10.1039/b209882m
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发表时间：
2003-01-01
影响因子：
3.3
通讯作者：
Jiang, JZ
中科院分区：
文献类型：
--
作者：
Bian, YZ;Wang, DQ;Jiang, JZ
用X-射线单晶衍射法测定了9个镧系（Ⅲ）（2，3-萘酞菁）（八乙基卟啉）双层混合配合物M（Nc）（OEP）（M = La，Pr，Nd，Tb，Dy，Ho，Er，Tm，Yb）的分子结构。所有这些化合物连同Sm、Eu、Gd、Y、Lu和Ce类似物（它们的结构已经在前面解决）一起在相同的斜方晶系Pnma中结晶，Z = 4。所有这些化合物的分子结构是同构的，表现出轻微扭曲的正方形反棱柱几何形状与两个圆顶配体。M（Nc）（OEP）的金属中心分别由Nc和OEP环的异吲哚和吡咯的八个氮原子配位。由两个N-4平均平面定义的两个圆顶状配体之间的环-环间距由于镧系收缩而沿La至Lu系列从3.056埃沿着单调减小至2.652埃。该面间距以及M（Nc）（OEP）（M = Ce除外）的平均M-N（Nc）和M-N（OEP）键长与金属中心的离子半径呈线性关系。两个大环之间的斜/扭角几乎保持不变，约为。45度，对于整个系列的镧系络合物，无论金属中心的大小。
The molecular structures of a series of nine mixed (2,3-naphthalocyaninato)(octaethylporphyrinato) double-decker complexes of lanthanide(III), M(Nc)(OEP) (M = La, Pr, Nd, Tb, Dy, Ho, Er, Tm, Yb), have been determined by single-crystal X-ray diffraction analysis. All these compounds together with the Sm, Eu, Gd, Y, Lu and Ce analogues, whose structures have been solved previously, crystallize in the same orthorhombic system, Pnma, Z = 4. The molecular structures of all these compounds are isostructural, exhibiting a slightly distorted square antiprismatic geometry with two domed ligands. The metal centre of M( Nc)( OEP) is coordinated by eight nitrogen atoms from the isoindole and pyrrole of the Nc and OEP rings, respectively. The ring-to-ring separation between the two domed ligands, as defined by the two N-4 mean planes, decreases monotonically from 3.056 to 2.652 Angstrom along the series of La to Lu as a result of lanthanide contraction. This interplanar distance as well as the average M-N(Nc) and M-N( OEP) bond lengths of M(Nc)(OEP) (except M = Ce) show a linear relationship with the ionic radius of the metal centre. The skew/twist angle between the two macrocyclic rings remains almost unchanged, ca. 45degrees, for the whole series of lanthanide complexes, regardless of the size of the metal centre.