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探究异三核双（草酰胺基）型配合物中末端铜离子之间的磁超交换耦合作用。

Probing the magnetic superexchange couplings between terminal Cu ions in heterotrinuclear bis(oxamidato) type complexes.

作者信息

Abdulmalic Mohammad A, Weheabby Saddam, Meva Francois E, Aliabadi Azar, Kataev Vladislav, Büchner Bernd, Schleife Frederik, Kersting Berthold, Rüffer Tobias

机构信息

Department of Inorganic Chemistry, Faculty of Natural Sciences, Chemnitz University of Technology, Strasse der Nationen 62, D-09111 Chemnitz, Germany.

Department of Pharmaceutical Sciences, Faculty of Medicine and Pharmaceutical Sciences, University of Douala, BP 2701, Cameroon.

出版信息

Beilstein J Nanotechnol. 2017 Apr 6;8:789-800. doi: 10.3762/bjnano.8.82. eCollection 2017.

DOI:10.3762/bjnano.8.82
PMID:28487822
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5389195/
Abstract

The reaction of one equivalent of [-BuN][Ni(opboR)] with two equivalents of [Cu(pmdta)(X)] afforded the heterotrinuclear CuNiCu containing bis(oxamidato) type complexes [CuNi(opboR)(pmdta)]X (R = Me, X = NO (); R = Et, X = ClO (); R = Pr, X = NO (); opboR = -phenylenebis(NR-substituted oxamidato); pmdta = ,,',","-pentamethyldiethylenetriamine). The identities of the heterotrinuclear complexes - were established by IR spectroscopy, elemental analysis and single-crystal X-ray diffraction studies, which revealed the cationic complex fragments [CuNi(opboR)(pmdta)] as not involved in any further intermolecular interactions. As a consequence thereof, the complexes - possess terminal paramagnetic [Cu(pmdta)] fragments separated by [Ni(opboR)] bridging units representing diamagnetic = 0 states. The magnetic field dependence of the magnetization () of - at = 1.8 K has been determined and is shown to be highly reproducible with the Brillouin function for an ideal paramagnetic spin = / system, verifying experimentally that no magnetic superexchange couplings exists between the terminal paramagnetic [Cu(pmdta)] fragments. Susceptibility measurements versus temperature of - between 1.8-300 K were performed to reinforce the statement of the absence of magnetic superexchange couplings in these three heterotrinuclear complexes.

摘要

一当量的[-BuN][Ni(opboR)]与两当量的[Cu(pmdta)(X)]反应，得到了含双(草酰胺基)型配合物[CuNi(opboR)(pmdta)]X的异三核CuNiCu（R = 甲基，X = 硝酸根（）；R = 乙基，X = 高氯酸根（）；R = 丙基，X = 硝酸根（）；opboR = -亚苯基双(NR-取代草酰胺基)；pmdta = ,,',","-五甲基二亚乙基三胺）。通过红外光谱、元素分析和单晶X射线衍射研究确定了异三核配合物 - 的结构，结果表明阳离子配合物片段[CuNi(opboR)(pmdta)]不参与任何进一步的分子间相互作用。因此，配合物 - 具有由[Ni(opboR)]桥连单元隔开的末端顺磁性[Cu(pmdta)]片段，代表抗磁性 = 0态。已测定了 - 在 = 1.8 K时磁化强度()对磁场的依赖性，结果表明其与理想顺磁性自旋 = / 系统的布里渊函数高度可重复，实验验证了末端顺磁性[Cu(pmdta)]片段之间不存在磁超交换耦合。对 - 在1.8 - 300 K之间进行了磁化率随温度的测量，以强化这三种异三核配合物中不存在磁超交换耦合的说法。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/740d/5389195/3c11e5ba1e62/Beilstein_J_Nanotechnol-08-789-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/740d/5389195/370801ec2818/Beilstein_J_Nanotechnol-08-789-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/740d/5389195/a81033fbacad/Beilstein_J_Nanotechnol-08-789-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/740d/5389195/45caf94c748f/Beilstein_J_Nanotechnol-08-789-g012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/740d/5389195/fdb2737036d5/Beilstein_J_Nanotechnol-08-789-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/740d/5389195/58fb5ebb9470/Beilstein_J_Nanotechnol-08-789-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/740d/5389195/7f32e48706fa/Beilstein_J_Nanotechnol-08-789-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/740d/5389195/a07565c85773/Beilstein_J_Nanotechnol-08-789-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/740d/5389195/ba95a259f8bd/Beilstein_J_Nanotechnol-08-789-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/740d/5389195/0f93d46a448d/Beilstein_J_Nanotechnol-08-789-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/740d/5389195/7ac575e61ec3/Beilstein_J_Nanotechnol-08-789-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/740d/5389195/3c11e5ba1e62/Beilstein_J_Nanotechnol-08-789-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/740d/5389195/370801ec2818/Beilstein_J_Nanotechnol-08-789-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/740d/5389195/a81033fbacad/Beilstein_J_Nanotechnol-08-789-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/740d/5389195/45caf94c748f/Beilstein_J_Nanotechnol-08-789-g012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/740d/5389195/fdb2737036d5/Beilstein_J_Nanotechnol-08-789-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/740d/5389195/58fb5ebb9470/Beilstein_J_Nanotechnol-08-789-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/740d/5389195/7f32e48706fa/Beilstein_J_Nanotechnol-08-789-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/740d/5389195/a07565c85773/Beilstein_J_Nanotechnol-08-789-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/740d/5389195/ba95a259f8bd/Beilstein_J_Nanotechnol-08-789-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/740d/5389195/0f93d46a448d/Beilstein_J_Nanotechnol-08-789-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/740d/5389195/7ac575e61ec3/Beilstein_J_Nanotechnol-08-789-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/740d/5389195/3c11e5ba1e62/Beilstein_J_Nanotechnol-08-789-g011.jpg

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Dalton Trans. 2013 Feb 7;42(5):1798-809. doi: 10.1039/c2dt32259e. Epub 2012 Nov 20.
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