{"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}
引用次数: 0
Abstract
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.