{"title":"顺磁铜（II）化合物中超细耦合张量的固态 1H、13C、17O NMR 和周期 DFT 综合研究。","authors":"Yizhe Dai , Victor Terskikh , Gang Wu","doi":"10.1016/j.ssnmr.2024.101945","DOIUrl":null,"url":null,"abstract":"<div><p>We report solid-state <sup>1</sup>H, <sup>13</sup>C, and <sup>17</sup>O NMR determination of hyperfine coupling tensors (<em>A</em>-tensors) in several paramagnetic Cu(II) (<em>d</em><sup>9</sup>, <em>S</em> = 1/2) complexes: <em>trans</em>-Cu(DL-Ala)<sub>2</sub>·H<sub>2</sub><sup>17</sup>O, Cu([1–<sup>13</sup>C]acetate)<sub>2</sub>·H<sub>2</sub>O, Cu([2–<sup>13</sup>C]acetate)<sub>2</sub>·H<sub>2</sub>O, and Cu(acetate)<sub>2</sub>·H<sub>2</sub><sup>17</sup>O. Using these new experimental results and some <em>A</em>-tensor data available in the literature for <em>trans</em>-Cu(L-Ala)<sub>2</sub> and K<sub>2</sub>CuCl<sub>4</sub>·2H<sub>2</sub>O, we were able to examine the accuracy of <em>A</em>-tensor computation from a periodic DFT method implemented in the BAND program. We evaluated <em>A</em>-tensors on <sup>1</sup>H (<em>I</em> = 1/2), <sup>13</sup>C (<em>I</em> = 1/2), <sup>14</sup>N (<em>I</em> = 1), <sup>17</sup>O (<em>I</em> = 5/2), <sup>39</sup>K (<em>I</em> = 3/2), <sup>35</sup>Cl (<em>I</em> = 3/2), and <sup>6</sup><sup><sup>3</sup></sup>Cu (<em>I</em> = 3/2) nuclei over a range spanning more than 3 orders of magnitude. We found that the BAND code can reproduce reasonably well the experimental results for both <em>A</em>-tensors and nuclear quadrupole coupling tensors.</p></div>","PeriodicalId":21937,"journal":{"name":"Solid state nuclear magnetic resonance","volume":null,"pages":null},"PeriodicalIF":1.8000,"publicationDate":"2024-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S0926204024000316/pdfft?md5=ae64e66e28bb0afa12d18d1f523805f6&pid=1-s2.0-S0926204024000316-main.pdf","citationCount":"0","resultStr":"{\"title\":\"A combined solid-state 1H, 13C, 17O NMR and periodic DFT study of hyperfine coupling tensors in paramagnetic copper(II) compounds\",\"authors\":\"Yizhe Dai , Victor Terskikh , Gang Wu\",\"doi\":\"10.1016/j.ssnmr.2024.101945\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>We report solid-state <sup>1</sup>H, <sup>13</sup>C, and <sup>17</sup>O NMR determination of hyperfine coupling tensors (<em>A</em>-tensors) in several paramagnetic Cu(II) (<em>d</em><sup>9</sup>, <em>S</em> = 1/2) complexes: <em>trans</em>-Cu(DL-Ala)<sub>2</sub>·H<sub>2</sub><sup>17</sup>O, Cu([1–<sup>13</sup>C]acetate)<sub>2</sub>·H<sub>2</sub>O, Cu([2–<sup>13</sup>C]acetate)<sub>2</sub>·H<sub>2</sub>O, and Cu(acetate)<sub>2</sub>·H<sub>2</sub><sup>17</sup>O. Using these new experimental results and some <em>A</em>-tensor data available in the literature for <em>trans</em>-Cu(L-Ala)<sub>2</sub> and K<sub>2</sub>CuCl<sub>4</sub>·2H<sub>2</sub>O, we were able to examine the accuracy of <em>A</em>-tensor computation from a periodic DFT method implemented in the BAND program. We evaluated <em>A</em>-tensors on <sup>1</sup>H (<em>I</em> = 1/2), <sup>13</sup>C (<em>I</em> = 1/2), <sup>14</sup>N (<em>I</em> = 1), <sup>17</sup>O (<em>I</em> = 5/2), <sup>39</sup>K (<em>I</em> = 3/2), <sup>35</sup>Cl (<em>I</em> = 3/2), and <sup>6</sup><sup><sup>3</sup></sup>Cu (<em>I</em> = 3/2) nuclei over a range spanning more than 3 orders of magnitude. We found that the BAND code can reproduce reasonably well the experimental results for both <em>A</em>-tensors and nuclear quadrupole coupling tensors.</p></div>\",\"PeriodicalId\":21937,\"journal\":{\"name\":\"Solid state nuclear magnetic resonance\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.8000,\"publicationDate\":\"2024-06-25\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://www.sciencedirect.com/science/article/pii/S0926204024000316/pdfft?md5=ae64e66e28bb0afa12d18d1f523805f6&pid=1-s2.0-S0926204024000316-main.pdf\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Solid state nuclear magnetic resonance\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S0926204024000316\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Solid state nuclear magnetic resonance","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0926204024000316","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
摘要
我们报告了几种顺磁性 Cu(II) (d9, S = 1/2) 复合物：反式-Cu(DL-Ala)2-H217O、Cu([1-13C]乙酸酯)2-H2O、Cu([2-13C]乙酸酯)2-H2O 和 Cu(乙酸酯)2-H217O 中超细耦合张量（A-张量）的固态 1H、13C 和 17O NMR 测定结果。利用这些新的实验结果以及文献中关于反式-Cu(L-Ala)2 和 K2CuCl4-2H2O 的一些 A 张量数据，我们得以检验 BAND 程序中实施的周期 DFT 方法计算 A 张量的准确性。我们对 1H（I = 1/2）、13C（I = 1/2）、14N（I = 1）、17O（I = 5/2）、39K（I = 3/2）、35Cl（I = 3/2）和 63Cu（I = 3/2）原子核的 A 张量进行了评估，范围超过 3 个数量级。我们发现 BAND 代码可以合理地再现 A 张量和核四极耦合张量的实验结果。
A combined solid-state 1H, 13C, 17O NMR and periodic DFT study of hyperfine coupling tensors in paramagnetic copper(II) compounds
We report solid-state 1H, 13C, and 17O NMR determination of hyperfine coupling tensors (A-tensors) in several paramagnetic Cu(II) (d9, S = 1/2) complexes: trans-Cu(DL-Ala)2·H217O, Cu([1–13C]acetate)2·H2O, Cu([2–13C]acetate)2·H2O, and Cu(acetate)2·H217O. Using these new experimental results and some A-tensor data available in the literature for trans-Cu(L-Ala)2 and K2CuCl4·2H2O, we were able to examine the accuracy of A-tensor computation from a periodic DFT method implemented in the BAND program. We evaluated A-tensors on 1H (I = 1/2), 13C (I = 1/2), 14N (I = 1), 17O (I = 5/2), 39K (I = 3/2), 35Cl (I = 3/2), and 63Cu (I = 3/2) nuclei over a range spanning more than 3 orders of magnitude. We found that the BAND code can reproduce reasonably well the experimental results for both A-tensors and nuclear quadrupole coupling tensors.
期刊介绍：
The journal Solid State Nuclear Magnetic Resonance publishes original manuscripts of high scientific quality dealing with all experimental and theoretical aspects of solid state NMR. This includes advances in instrumentation, development of new experimental techniques and methodology, new theoretical insights, new data processing and simulation methods, and original applications of established or novel methods to scientific problems.
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