1. Halogen substitution effects on crystal structures and magnetic properties in nickel dithiolate molecular crystals.
- Author
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Chen, Xuan-Rong, Chen, Xiao-Yu, Wei, Yi-Ting, Yu, Yan-She, Xu, Jing-Wen, Lai, Jia, and Yao, Yu-Feng
- Subjects
MAGNETIC structure ,MOLECULAR crystals ,MAGNETIC crystals ,CRYSTAL structure ,MAGNETIC properties - Abstract
A series of nickel dithiolene molecular crystals [Et
3 N(CH2 )3 X][Ni(mnt)2 ] (1: X = H, 2: X = Cl, 3: X = Br and 4: X = I and Br; mnt2− = maleonitriledithiolate) were prepared by introducing triethylpropylammonium derivatives (X–CH2 CH2 CH2 –NEt3 + ) into [Ni(mnt)2 ]− building blocks. 1 crystallizes in a monoclinic system with the space group P21 /n at 293 K, and the cations and anions in 1 are arranged in columnar segregated stacks along the a-axis direction. Crystals 2 and 3 also belong to monoclinic systems with space groups P21 /n and P21 /c, but 4 crystallizes in a triclinic system with the space group P1¯. Interactions between [Ni(mnt)2 ]− ions in all crystals are antiferromagnetic, and the magnitudes of the interactions are qualitatively consistent with the strength of intermolecular interactions estimated from transfer integrals, where interactions between [Ni(mnt)2 ]− ions are greater than the others in all crystals. The magnetic measurement data demonstrate that antiferromagnetic behavior was observed in 1 and can be fitted well through the 1D alternating linear chain model. Crystal 2 shows spin dimer magnetic behavior, and the magnetic susceptibilities of 3 and 4 show Curie–Weiss-type paramagnetic character in the whole temperature regions. This study showed that halogen substitution on the cations has significant effects on the arrangement and magnetic behavior of [Ni(mnt)2 ]− . [ABSTRACT FROM AUTHOR]- Published
- 2024
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