{(Me2NH2)2[Fe2(ox)2Cl4]•H2O} n (ox=oxalate)中客体水分子诱导的介电弛豫行为

doi:10.6023/A20080397

摘要/Abstract

以双齿配位的草酸根为配体和FeCl₃反应得到了化合物{(Me₂NH₂)₂[Fe₂(ox)₂Cl₄]•H₂O} _n (ox=oxalate) ( 1•H₂O). 在真空和加热的条件下, 1•H₂O脱水发生单晶到单晶的转变, 得到了化合物{(Me₂NH₂)₂[Fe₂(ox)₂Cl₄]} _n ( 1). 磁性研究表明客体水分子存在与否对化合物磁相互作用没有明显影响. 介电性质研究表明客体水分子的存在可影响化合物中客体胺和氢原子的动态弛豫过程. 化合物 1•H₂O在250 K, 80 K和50 K呈现三个介电弛豫过程, 而化合物 1仅在80 K表现出单一弛豫过程.

关键词: 介电弛豫, 单晶-单晶转化, 水, 磁性

It is well known that water is one of the most important chemical constituent in the nature, and thus is regarded as the genesis of life. Meanwhile, water plays an irreplaceable role in biology process, such as regulating the affinity between fatty acids and alkyl chains and controlling the conformation of DNA. In the crystal chemistry, water molecules in compounds will also significantly affect its structure, physical and chemical properties. Among them, single crystal to single crystal (SCSC) transformations induced by water molecules have attracted great attention, because those transformations often change the physical properties such as magnetic, dielectric and proton conduction. More importantly, it is facile to obtain detailed structural information, which leads to more directly and better understanding the transformation mechanism and structure-properties relationship. In this work, we report the SCSC transformation in the compound of {(Me₂NH₂)₂- [Fe₂(ox)₂Cl₄]•H₂O} _n (ox=oxalate) ( 1•H₂O), which was prepared through the hydrothermal reaction of oxalate and FeCl₃ in the presence of dimethylamine chloride. Under vacuum and heating conditions, 1•H₂O underwent SCSC transformations, formed compound 1. 1•H₂O and 1 were characterized by X-ray single-crystal diffraction, powder X-ray diffraction, magnetic, dielectric and thermogravimetric analysis. Magnetic studies on 1•H₂O and 1 show that the presence or absence of guest water molecules had no significant effect on their magnetic interaction. Investigation on the dielectric properties of 1•H₂O and 1 reveals that the presence of guest water molecules can influence the dynamic relaxation process of guest amine and water in the compound. Compound 1•H₂O exhibited three dielectric relaxations at 250 K, 80 K and 50 K respectively, while 1 only showed a single relaxation process at 80 K. This work sheds light on the further exploration of SCSC transformations associated with the dielectric relaxation.

Key words: dielectric relaxation, SCSC structural transformation, water, magnetism

引用此文

王宾, 唐雯, 赵海霞, 龙腊生, 郑兰荪. {(Me₂NH₂)₂[Fe₂(ox)₂Cl₄]•H₂O} _n (ox=oxalate)中客体水分子诱导的介电弛豫行为[J]. 化学学报, 2021, 79(1): 119-125.

Bin Wang, Wen Tang, Haixia Zhao, Lasheng Long, Lansun Zheng. Dielectric Relaxation Triggered by Guest Water Molecule Based on the {(Me₂NH₂)₂[Fe₂(ox)₂Cl₄]•H₂O}_n(ox=oxalate)[J]. Acta Chimica Sinica, 2021, 79(1): 119-125.

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图/表 8

	1•H₂O		1
温度/K	100(2)	293(2)	173(2)	293(2)
分子式	C₈H₁₈O₉N₂Fe₂Cl₄	C₈H₁₈O₉N₂Fe₂Cl₄	C₈H₁₆O₈N₂Fe₂Cl₄	C₈H₁₆O₈N₂Fe₂Cl₄
相对分子质量	539.74	539.74	521.73	521.73
晶体颜色	黄色	黄色	黄色	黄色
晶系	Monoclinic	Monoclinic	Monoclinic	Monoclinic
空间群	P2₁/ c	P2₁/ c	P2₁/ c	P2₁/ c
a/nm	1.08360(4)	1.09541(6)	1.08592(3)	1.09188(6)
b/nm	1.37526(6)	1.40077(8)	1.35867(3)	1.37243(6)
c/nm	1.35486(6)	1.35620(8)	1.36300(3)	1.36689(7)
α/(°)°	90	90	90	90
β/(°)°	107.116(5)	107.474(6)	108.379(3)	108.439(6)
γ/(°)°	90	90	90	90
V/nm³	1.92963(15)	1.9849(2)	1.90840(8)	1.94316(17)
Z	4	4	4	4
D _c/(g•cm^–3)	1.853	1.806	1.816	1.783
GOOFs	1.074	1.092	1.006	1.028
R ₁ [ I>2 σ( I)]	0.0380	0.0486	0.0320	0.0391
wR ₂ (all data)	0.1091	0.1336	0.0578	0.0964

表1. 化合物1•H2O和1在不同温度的单晶结构信息

Table 1. Crystallographic data of 1•H2O and 1 at different temperatures

图1. (a) 化合物1•H2O在293 K的结构片段; (b) 化合物1在293 K的结构片段. 为了图示清晰, 所有的氢原子都均被忽略

Figure 1. ORTEP drawing of a fragment of the chain motif in 1•H2O (a) and 1 (b) at 293 K. All H atoms are omitted for clarity

图2. (a) 1•H2O到1的转换的粉末颜色变化; (b) 1•H2O和1的热重数据; (c) 1•H2O和1的粉末XRD数据

Figure 2. (a) The color change in powder of 1•H2O transfer to 1. (b) TG of 1•H2O and 1. (c) PXRD of 1•H2O and 1

图3. 化合物1•H2O (a)和 1 (b)在293 K的不对称单元图. 为了图示清晰, 所有非氢键的氢原子均被忽略

Figure 3. The asymmetric unit of 1•H2O (a) and 1 (b) at 293 K, respectively. The non-hydrogen bonded H atoms are omitted for clarity

图4. 1•H2O的变温介电温谱图. (a) 不同频率下的介电实部图, 内插图为低温区介电实部图; (b) 不同频率下的介电损耗图; 在50 K (c), 250 K (d)附近, 不同频率下的介电虚部图, 内插图为基于阿伦尼乌斯公式的拟合图.

Figure 4. Variable-temperature permittivity spectrum of 1•H2O. The real part (ε') of the dielectric constant (a) and dielectric loss (b) dependence on temperature at different frequency for 1•H2O, inset is the real part (ε') of the dielectric constant (a) and dielectric loss (b) at low temperature. The imaginary parts of dielectric constant dependence on different frequency near 50 K (c) and 250 K (d) of 1•H2O, inset is the fitting diagram of Arrhenius formula.

图5. 化合物1的变温介电温谱图. (a) 不同频率下的介电实部图, 内插图为低温区介电实部图; (b) 不同频率下的介电损耗图, 内插图为80 K附近的介电损耗图; (c) 不同频率下的介电虚部图, 内插图为基于阿伦尼乌斯公式的拟合图.

Figure 5. Variable-temperature permittivity spectrum of 1. The real part (ε') of the dielectric constant (a) and dielectric loss (b) dependence on temperature at different frequency for 1, inset is the dielectric loss at around 80 K. (c) The imaginary parts of dielectric constant dependence on different frequency, inset is the fitting diagram of Arrhenius formula.

弛豫	1•H₂O		1
弛豫	E _a	τ ₀	E _a	τ ₀
α-弛豫	0.521 eV	9.0×10^–15 s
β-弛豫	0.148 eV	5.88×10^–14 s	0.1768 eV	1.58×10^–15 s
γ-弛豫	0.0855 eV	2.07×10^–12 s

表2. 化合物1•H2O和1在弛豫过程中的E a和τ 0

Table 2. Activation energy (E a) and relaxation time (τ 0) for each relaxation process in 1•H2O and 1

图6. (a) 1•H2O的变温磁化率测试和(b) 1的变温磁化率测试

Figure 6. Plots of χmT and χm –1 versus T for 1•H2O(a) and 1 (b)

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{(Me₂NH₂)₂[Fe₂(ox)₂Cl₄]•H₂O} _n (ox=oxalate)中客体水分子诱导的介电弛豫行为

Dielectric Relaxation Triggered by Guest Water Molecule Based on the {(Me₂NH₂)₂[Fe₂(ox)₂Cl₄]•H₂O}_n(ox=oxalate)

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