Dielectric Relaxation Triggered by Guest Water Molecule Based on the {(Me2NH2)2[Fe2(ox)2Cl4 ]•H2 O}n(ox=oxalate)

doi:10.6023/A20080397

Abstract

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

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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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Fig. & Tab. 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

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

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

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

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

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.

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

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

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