Beyond Bleaney's Theory: Experimental and Theoretical Analysis of Periodic Trends in Lanthanide-Induced Chemical Shift
Beyond Bleaney's Theory: Experimental and Theoretical Analysis of Periodic Trends in Lanthanide-Induced Chemical Shift
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超越布莱尼的理论：镧系元素引起的化学位移周期性趋势的实验和理论分析
DOI：
10.1002/ange.201706931
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发表时间：
2017
影响因子：
--
通讯作者：
Suturina E
中科院分区：
文献类型：
--
作者：
Suturina E
顺磁NMR位移的一系列同构镧系元素配合物相对于PARASHIFT造影剂的详细分析揭示了磁化率各向异性的意想不到的趋势，不能解释的常用的Bleaney的理论。从头计算表明，Bleaney的理论的主要假设，即热能大于配位场分裂，并不适用于镧系元素络合物的问题，并可能为大部分的镧系元素络合物一般。这使得磁化率张量的取向在具有相同配体的不同镧系元素的络合物之间显着不同：关于同构镧系元素系列的最流行的假设之一是错误的。
A detailed analysis of paramagnetic NMR shifts in a series of isostructural lanthanide complexes relavant to PARASHIFT contrast agents reveals unexpected trends in the magnetic susceptibility anisotropy that cannot be explained by the commonly used Bleaney's theory. Ab initio calculations reveal that the primary assumption of Bleaney's theory—that thermal energy is larger than the ligand field splitting—does not hold for the lanthanide complexes in question, and likely for a large fraction of lanthanide complexes in general. This makes the orientation of the magnetic susceptibility tensor differ significantly between complexes of different lanthanides with the same ligand: one of the most popular assumptions about isostructural lanthanide series is wrong.