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首页> 外文期刊>European journal of inorganic chemistry >Structures of Rare Earth Homodinuclear Macrocyclic Complexes with the Polyamine Polycarboxylic Ligand 1,4,7,10,14,17,20,23-Octaazacyclohexacosane-1,4,7,10,14,17,20,23-octaacetic Acid (H_8OHEC) in the Crystal and in Solution
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Structures of Rare Earth Homodinuclear Macrocyclic Complexes with the Polyamine Polycarboxylic Ligand 1,4,7,10,14,17,20,23-Octaazacyclohexacosane-1,4,7,10,14,17,20,23-octaacetic Acid (H_8OHEC) in the Crystal and in Solution

机译：带有多胺多元羧酸配体的1,4,7,10,14,17,20,23-八氮杂环己烷-1,4,7,10,14,17,20,23-八乙酸的稀土高纯核大环配合物的结构（H_8OHEC ）在晶体和溶液中

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摘要

The solid-state structures of the four homodinuclear chelate complexes, [Na_2(Y_2OHEC)(H_2O)_2] centre dot 7 H_2O centre dot C_2H_5OH (1), [Na_2(Gd_2OHEC)(H_2O)_2] centre dot 12 H_2O (2), [Na_2(Eu_2OHEC)(H_2O)_2] centre dot 11 H_2O (3), and [Cs_2(La_2OHEC)(H_2O)_2] centre dot 14 H_2O (4) (H_8OHEC = 1,4,7,10,14,17,20,23-octaazacyclohexacosane-1,4,7,10,14,17,20,23-octaacetic acid), were determined by X-ray crystal structure analysis. Each lanthanide(III) ion is ninefold coordinated by eight donor atoms of the ligand system and the oxygen atoms of one water molecule. The structurea are compared with those of DOTA- and TETA-coordinated complexes and the conformation of the OHEC ligand system with that of the parent amine and its dinuclear copper complex. NMR investigations of the diamagnetic complex 1 indicate a very similar environment of the lanthanide cations in solution and in the solid state. Low-temperature and variable-temperature ~1H-NMR measurements prove the existence of two isomers of 1 (3.5:1 ratio) which undergo conformational processes. The rate constants of these processes were deduced from a complete line shape analysis and were used to determine the activation parameters.
机译：[Na_2（Y_2OHEC）（H_2O）_2]中心点7 H_2O中心点C_2H_5OH（1），[Na_2（Gd_2OHEC）（H_2O）_2]中心点12 H_2O（2）的四种同核螯合物的固态结构，[Na_2（Eu_2OHEC）（H_2O）_2]中心点11 H_2O（3）和[Cs_2（La_2OHEC）（H_2O）_2]中心点14 H_2O（4）（H_8OHEC = 1,4,7,10,14，通过X射线晶体结构分析确定了17,20,23-八氮杂环己烷-1,4,7,10,14,17,20,23-八乙酸）。每个镧系元素（III）离子由配体系统的八个供体原子和一个水分子的氧原子配成九倍的配位。将其结构与DOTA和TETA配位的配合物以及OHEC配体系统与母体胺及其双核铜配合物的构象进行比较。抗磁性络合物1的NMR研究表明溶液和固态中镧系元素阳离子的环境非常相似。低温和可变温度〜1H-NMR测量证明存在两个构象过程为1（3.5：1的比率）的异构体。这些过程的速率常数由完整的线形分析得出，并用于确定激活参数。

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