Magnetic Properties and Second Harmonic Generation of Noncentrosymmetric Cyanido-Bridged Ln(III)-W(V) Assemblies
Magnetic Properties and Second Harmonic Generation of Noncentrosymmetric Cyanido-Bridged Ln(III)-W(V) Assemblies
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非中心对称氰基桥Ln(III)-W(V)组件的磁性能和二次谐波产生
DOI：
10.1021/acs.inorgchem.1c01113
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发表时间：
2021
影响因子：
4.6
通讯作者：
Ohkoshi Shin-ichi
中科院分区：
文献类型：
--
作者：
Kumar Kunal;Stefanczyk Olaf;Chilton Nicholas F.;Nakabayashi Koji;Imoto Kenta;Winpenny Richard E. P.;Ohkoshi Shin-ichi
在N，N-二甲基乙酰胺(DMA)存在下，稀土(III)离子与八氰基钨酸根(V)阴离子自组装，合成了一维锯齿形氰基桥联配位聚合物。所有化合物均在非中心对称空间群P21中结晶，分子式为[LnⅢ(Dma)5][WV(CN)8][Ln=Gd(1)，Tb(2)，Dy(3)，Ho(4)，Er(5)，Tm(6)，Yb(7)，Lu(8)或Y(9)]。磁性研究表明，在很低的温度下，通过LnIII-NC-WV桥的反铁磁相互作用很弱，并形成了亚铁磁性耦合链。此外，用Ln(III)离子的晶场参数对磁化率的温度依赖关系进行了拟合，这些参数是由从头计算确定的，得到了−1-−5 cm-1范围内的磁耦合常数。用固体吸收光谱测定了1-9的宽光学透明度。由于存在非线性光学极化率张量元(χijk)χzxx，χzyy，χzzz，χzxy，χyyz，χyzx，χxyz和χxzx，对应于P21空间群，样品表现出二次谐波产生性质，SH磁化率在4.7×10-12到9.4×10-11esu之间。测定值还与理论计算和前人报道的结果进行了比较，表明稀土离子的类型与SH强度之间存在潜在的关系。
One-dimensional zigzag cyanido-bridged coordination polymers have been prepared as a result of self-assembly of lanthanide(III) ions with octacyanidotungstate(V) anions in the presence ofN,N-dimethylacetamide (dma). All compounds crystallized in noncentrosymmetric space groupP21with a molecular formula of [LnIII(dma)5][WV(CN)8] [Ln = Gd (1), Tb (2), Dy (3), Ho (4), Er (5), Tm (6), Yb (7), Lu (8), or Y (9)]. Magnetic studies revealed weak antiferromagnetic interactions through LnIII–NC–WVbridges and the formation of ferrimagnetically coupled chains at very low temperatures. Moreover, temperature dependencies of magnetic susceptibilities were fitted using the crystal field parameters for Ln(III) ions, determined by theab initiocalculations, yielding magnetic coupling constants in the range of −1 to −5 cm–1. The wide optical transparency of1–9has been determined using solid state absorption spectroscopy. Samples exhibited second harmonic (SH) generation properties with SH susceptibilities ranging from 4.7 × 10–12to 9.4 × 10–11esu due to the presence of nonlinear optical susceptibility tensor elements (χijk)χzxx,χzyy,χzzz,χzxy,χyyz,χyzx, χxyz, andχxzx, corresponding to space groupP21. The determined values were also compared with the results of theoretical calculations and previous reports, indicating a potential relationship between the type of lanthanide ion and the SH intensity.