Naphthalene-Bridged ansa-Nickelocene: Synthesis, Structure, Electrochemical, and Magnetic Measurements†
Naphthalene-Bridged ansa-Nickelocene: Synthesis, Structure, Electrochemical, and Magnetic Measurements†
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萘桥安萨镍茂：合成、结构、电化学和磁性测量†
DOI：
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发表时间：
2012
期刊：
影响因子：
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通讯作者：
D. Görlitz
中科院分区：
文献类型：
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作者：
S. Trtica;Enno Meyer;M. Prosenc;J. Heck;T. Böhnert;D. Görlitz
萘-1，8-二基双（环戊二烯基钠）（1）与镍的三层化合物[Ni 2Cp 3] BF 4反应，得到顺磁性的柄型镍茂1，1 ′-（萘-1 ″，8 ″-二基）镍茂（2）。或者，2可以通过二钠盐1与六氨合二氯化镍（II）[Ni（NH3）6] Cl 2的盐复分解反应直接获得。对于磁性稀释实验，通过二钠盐1与三氯四（二甲基亚砜）钌（II）的反应合成了相应的但抗磁性的柄型茂3。通过单晶X射线衍射分析确定了2和3的固态分子结构，并揭示了弯曲的三明治复合物。2的循环伏安法研究表明三种氧化态。配合物2的电子结构已通过变温1H NMR光谱，磁性测量和DFT计算进行了研究。超导量子干涉仪（SQUID）的磁测量已经进行了纯和稀释样品2。2的纯晶体材料显示出反铁磁行为，而磁稀释样品的磁化率在T <4K时达到饱和。这一性质与化合物2的体材料中的分子间反铁磁相互作用和通过破缺对称性（BS）-DFT计算计算的三重态基态一致。
The reaction of naphthalene-1,8-diylbis(cyclopentadienylsodium) (1) with the nickel triple-decker compound [Ni2Cp3]BF4 affords the paramagnetic ansa-nickelocene 1,1′-(naphthalene-1″,8″-diyl)nickelocene (2). Alternatively, 2 can directly be obtained by a salt metathesis reaction of the disodium salt 1 with hexaammine nickel(II) dichloride [Ni(NH3)6]Cl2. For magnetic dilution experiments, the corresponding but diamagnetic ansa-ruthenocene 3 was synthesized by reaction of the disodium salt 1 with dichloridotetrakis(dimethyl sulfoxide)ruthenium(II). The solid-state molecular structures of 2 and 3 were determined by single-crystal X-ray diffraction analysis and revealed bent sandwich complexes. Cyclic voltammetry studies of 2 indicate three oxidation states. The electronic structure of complex 2 has been investigated by variable-temperature 1H NMR spectroscopy, magnetic measurements, and DFT calculations. Superconducting quantum interference device (SQUID) magnetometry has been performed for the neat and diluted samples of 2. The neat crystalline material of 2 displays antiferromagnetic behavior, whereas the susceptibility of the magnetically diluted sample runs into saturation at T < 4 K. This property is in agreement with an intermolecular antiferromagnetic interaction in the bulk material of compound 2 and the triplet ground state calculated by broken-symmetry (BS)-DFT calculations.