对一个大单轴磁各向异性镍(Ⅱ)配合物中的磁跃迁的直接观察  

Direct Observation of Magnetic Transitions in a Nickel(Ⅱ)Complex with Large Anisotropy

作　　者：Chelsea N.Widener Alexandria N.Bone Mykhaylo Ozerov Rachael Richardson 路正光 Komalavalli Thirunavukkuarasu Dmitry Smirnov 陈学太 薛子陵 Chelsea N.Widener;Alexandria N.Bone;Mykhaylo Ozerov;Rachael Richardson;LU Zheng-Guang;Komalavalli Thirunavukkuarasu;Dmitry Smirnov;CHEN Xue-Tai;XUE Zi-Ling(Department of Chemistry,University of Tennessee,Knoxville,Tennessee 37996,United States;National High Magnetic Field Laboratory,Florida State University,Tallahassee,Florida 32310,United States;Department of Physics,Florida A&M University,Tallahassee,Florida 32307,United States;State Key Laboratory of Coordination Chemistry,School of Chemistry and Chemical Engineering,Nanjing University,Nanjing 210023,China)

机构地区：[1]田纳西大学化学系,诺克斯维尔市37996,美国 [2]国家高磁场实验室,佛罗里达州立大学,塔拉哈西市32310,美国 [3]佛罗里达农工大学物理系,塔拉哈西市32307,美国 [4]南京大学化学化工学院配位化学国家重点实验室,南京210023

出　　处：《无机化学学报》2020年第6期1149-1156,共8页Chinese Journal of Inorganic Chemistry

基　　金：Supported by U.S.National Science Foundation(No.CHE-1633870,CHE-1900296)。

摘　　要：最近Ruamps和同事发现三角双锥构型的Ni(Ⅱ)配合物[Ni(Me6tren)Cl]ClO4(1,Me6tren=tris(2-(dimethylamino)ethyl)amine)具有大的单轴磁各向异性(J. Am. Chem. Soc., 2013,135:3017-3026)。他们利用HF-EPR研究获得横向零场分裂(ZFS)参数E=1.56(5)cm-1但未能确定轴向零场分裂参数D。在本工作中,我们利用0~17.5 T和5 K的变磁场远红外光谱(FIRMS)来检测自旋基态S=1中的MS=±1和MS=0态之间的磁跃迁。在FIRMS中直接观察到Zeeman分裂态之间的跃迁,得出轴向ZFS参数D=-110.7(3) cm-1。我们对1的晶体结构进行了Hirshfeld表面分析,揭示了1分子中的阳离子与阴离子之间以及分子之间的相互作用。Trigonal bipyramidal Ni(Ⅱ)complex[Ni(Me6 tren)Cl](ClO4)(1,Me6 tren=tris(2-(dimethylamino)ethyl)amine)has recently been shown by Ruamps and coworkers to possess large,uniaxial magnetic anisotropy(J.Am.Chem.Soc.,2013,135:3017-3026).Their HF-EPR studies gave rhombic zero-field-splitting(ZFS)parameter E=1.56(5)cm-1 for 1.However,the axial ZFS parameter D has not been determined.We have used far-IR magnetic spectroscopy(FIRMS)at 0~17.5 T and 5 K to probe the magnetic transitions between the MS=±1 and MS=0 states of the ground spin state S=1 in 1.Direct observation of the transitions between Zeeman-split states in FIRMS gives axial ZFS parameter D=-110.7(3)cm-1.Hirshfeld surface analysis of the crystal structure of 1 has been performed,revealing the interactions between the cation and anion in a molecule of 1 as well as among the molecules of 1 in crystals.

关 键 词：镍配合物 零场分裂磁跃迁 单轴磁各向异性 远红外光谱 

分 类 号：O614.81[理学—无机化学]