NMR‐based analysis of structure of heteroleptic triple‐decker (phthalocyaninato) (porphyrinato) lanthanides in solutions
NMR‐based analysis of structure of heteroleptic triple‐decker (phthalocyaninato) (porphyrinato) lanthanides in solutions
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基于 NMR 的溶液中杂配三层（酞菁）（卟啉）镧系元素结构分析
DOI：
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发表时间：
2010
期刊：
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通讯作者：
A. Tsivadze
中科院分区：
文献类型：
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作者：
K. P. Birin;Yulia G. Gorbunova;A. Tsivadze
发展了一种新的方法用于溶液中混配三层德克尔（卟啉）（酞菁）镧系元素（III）的结构分析。所开发的方法包括考虑镧系元素诱导位移（LIS）数据集的复合物几何形状的分子力学（MM+）优化。对一系列对称配合物[An 4P]Ln[（15 C5）4Pc]Ln[An 4P]（其中An 4P 2-为5，10，15，20-四（4-甲氧基苯基）卟啉阴离子，[（15 C5）4Pc]2-为2，3，9，10，16，17，24，25-四（15-冠-5）酞菁阴离子，Ln = La，Ce，Pr，Nd，Sm，Eu）的1H NMR谱中共振峰的利斯进行了分析.利斯的分析显示分子中有两组质子，具有相反的移位符号。利斯的双核分析证明了尽管镧系离子收缩，但溶液中整个系列研究的络合物的同构性。使用单核技术对利斯的接触和偶极贡献进行无模型分离，在研究系列中未显示接触和偶极项的变化。MM+分子结构的优化允许解释每个特定质子组的LIS特征。使用LIS的结构依赖性偶极贡献值对MM +优化的分子模型进行参数化，可以开发溶液中三层德克尔复合物的精确结构模型。这种方法可以确定夹心大环四吡咯配合物的几何形状和结构，以及溶液中柔性外围取代基的构象分析。所开发的方法可以应用于与其他类型的镧系元素（III）配合物的结构参数的测定与tetraphyrrolic配体和超分子系统的基础上，他们的微小修改。版权所有© 2010约翰威利父子有限公司.
A novel approach for the structural analysis of heteroleptic triple‐decker (porphyrinato)(phthalocyaninato) lanthanides(III) in solutions is developed. The developed approach consists in molecular mechanics (MM+) optimization of the geometry of the complex taking into account the lanthanide‐induced shift (LIS) datasets. LISs of the resonance peaks in 1H NMR spectra of a series of symmetric complexes [An4P]Ln[(15C5)4Pc]Ln[An4P], where An4P2− is 5,10,15,20‐tetrakis(4‐methoxyphenyl)porphyrinato‐dianion, [(15C5)4Pc]2− is 2,3,9,10,16,17,24,25‐tetrakis(15‐crown‐5)phthalocyaninato‐dianion and Ln = La, Ce, Pr, Nd, Sm, Eu, are analyzed. Analysis of LISs showed two sets of protons in the molecule with opposite signs of shift. Two‐nuclei analysis of LISs testifies isostructurality of the whole series of investigated complexes in solution despite contraction of the lanthanide ions. Model‐free separation of contact and dipolar contributions of LISs was performed with one‐nucleus technique and did not show changes in contact and dipolar terms within the investigated series. MM+ optimization of the molecular structure allowed the interpretation of features of LIS for each particular group of protons. Parameterization of MM + ‐optimized model of molecule with values of structure‐dependent dipolar contributions of LIS allows the development of the precise structural model of the triple‐decker complex in solution. This approach allows the determination of the geometry and structure of the sandwich macrocyclic tetrapyrrolic complexes together with conformational analysis of flexible peripheral substituents in solutions. The developed method can be applied with minor modifications for the determination of structural parameters of other types of lanthanides(III) complexes with tetrapyrrolic ligands and also supramolecular systems based on them. Copyright © 2010 John Wiley & Sons, Ltd.