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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Distinction between Light and Heavy Lanthanide(III) Ions Based on the ~1H NMR Spectra of Heteroleptic TRripole-Decker Phthalocyaninato Sandwich Complexes
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Distinction between Light and Heavy Lanthanide(III) Ions Based on the ~1H NMR Spectra of Heteroleptic TRripole-Decker Phthalocyaninato Sandwich Complexes

机译：基于异特异三聚体TRripole-Decker酞菁夹心复合物的〜1H NMR谱区分轻质和重质镧系元素（III）离子

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The ~1H NMR specra of two series of heteroleptic triple-decker phthalocyaninato sandwich complexes of the rare earth(III) ions have been recorded. The ligands comprise unsubstituted phthalocyanine (Pc) and 2,3,9,-10,16,17,23,24-octakis(1'-octyloxy)phthalocyanine (Pc~*), and the complexes are of the form PcMPc~*MPc (series 1) and PcMPc~*MPc~* (series 2), where M = Pr - Tm (except Pm, Gd). In some cases, the homoleptic complexes Pc~*MPc~*MPc~* ( series 3) were also available. The chemical shifts of five proton positions in series 1, and 10 positions in series 2 were compared with the shifts for the analogous complexes of the diamagnetic yttrium(III) ion. The experimental lanthanide-induced shifts (FIS) were separated into the contact and dipolar contributions using the crystal-field dependent methods of Reilley and co-workers. This work represents the first analysis of LIS in triple-decker phthalocyaninato lanthanide complexes. The results showed a dominance of dipolar contributions but also revealed that contact influences cannot be ignored, even for protons located in the peripheral alkoxzy substituents. Analysis by graphical and matrix methods indicates that there is a clear discontinuity in the data between terbium and dysprosium, whereby the metals Nd, Sm, Eu and Tb possess a positive hyperfine coupling term F_i, and the later metals Dy, Ho (limited data), Er and Tm require a negative contact term. This change is coincident with a near-halving of the dipolar term G_i centre dot A_2~0 for the later metals. The properties of preaseodymium are anomalous, in that its complexes are readily demetalated, and its NMR behavior places it in the second group of metal ions, despite its early position in the lanthanide series. Use of crystal-field independent analysis shows that the discontinuity near the middle of the series is related to variation in both the hyperfine electron-nuclear coupling constant and the crystal-field properties of the metal ions, rather than to gross changes in geometry.
机译：记录了稀土（III）离子的两个杂合的三层三邻苯二甲酸酞菁至三明治夹心复合物的〜1 H NMR谱。配体包含未取代的酞菁（Pc）和2,3,9，-10,16,17,23,24-辛基（1'-辛氧基）酞菁（Pc〜*），并且配合物的形式为PcMPc〜* MPc（系列1）和PcMPc〜* MPc〜*（系列2），其中M = Pr-Tm（Pm，Gd除外）。在某些情况下，也可以使用均纯复合物Pc〜* MPc〜* MPc〜*（系列3）。将系列1中五个质子位置和系列2中10个位置的化学位移与反磁性钇（III）离子类似络合物的位移进行了比较。使用Reilley及其同事的晶体场相关方法，将实验性镧系元素引起的位移（FIS）分为接触贡献和偶极贡献。这项工作是对三层酞菁氰镧系镧系元素络合物中LIS的首次分析。结果表明偶极贡献占主导地位，但同时也表明即使对于位于周围烷氧基取代基中的质子，接触影响也不能忽略。通过图形和矩阵方法进行的分析表明，ter和之间的数据存在明显的不连续性，因此金属Nd，Sm，Eu和Tb具有超精细耦合项F_i，而后期的金属Dy，Ho（有限数据） ，Er和Tm需要负接触项。该变化与后面的金属的偶极项G_i中心点A_2〜0 几乎减半一致。前ase的性质是异常的，因为它的配合物很容易被脱金属，并且尽管它在镧系元素中处于早期位置，它的NMR行为仍将其置于第二组金属离子中。使用与晶体场无关的分析表明，在系列中间附近的不连续性与超细电子-核耦合常数和金属离子的晶体场性质的变化有关，而不是与几何形状的总体变化有关。

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