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The New Functional Complexes Based on Tartaric Acid

Author: LiuWen
Tutor: ZhengYueQing
School: Ningbo University
Course: Inorganic Chemistry
Keywords: Functional complex Tartaric acid Crystal structure Second harmonic generation Ferroelectricity
CLC: O621.13
Type: Master's thesis
Year: 2009
Downloads: 105
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Abstract


In the first part of this dissertation, the complexes based on tartaric acid and metal ions were reviewed, including the variety, structures, synthesis methods and properties. Especially, the characteristic of structures and the physical property such as dielectricity, magnetism, ferroelectricity and unsymmetric catalysis, etc, were emphasized. Then 5 noncentrosymmetrical complexes based on chiral tartaric acid:[Zn(H2O)(C4H4O6)2/2]·2H2O 1, [Cd2(H2O)(C4H4O6)2]·3H2O 2, [Tb(C4H5O6)(C4H4O6)·3H2O] 3, [Mn(2,2’-bpy)(C4H4O6)]·5H2O 4, (4,4’-Hbpy)(C4H5O6)·H2O 5, (C4H4O62-=tartrate anion, C4H5O6-=hydrogen tartrate anion,2,2’-bpy=2,2’-bipyridine,4,4’-Hbpy=4,4’-bipyridine), were presented and their X-ray single crystal diffraction, X-ray powder diffraction, IR spectra, TG-DTA analyses, powder second harmonic generaton, ferroelectricity and magnetic analyses were also demonstrated.X-ray crystallography reveals that complex 1 crystalizes in the chiral C2 space group, and the Zn2+ ions are bridged by tartrate ions to form neutral two-dimensional (2D) layer parallel to (001). The physical propery test indicates that the complex 1 exhibits a second harmonic generation (SHG) effect of about 0.6 times as large as that of KDP, and the unhydrous powder of 1 has a SHG effect of about 0.4 times as large as that of KDP. Complex 1 and the unhydrous powder of 1 display good ferroelectric property with the saturation spontaneous polarizaton (Ps) of 0.46μC·cm-2 and 0.43μC·cm-2, respectively, which are significantly higher than that for the typical ferroelectric compound:Rochelle salt (NaKC4H4O6·H2O) with Ps=0.25μC·cm-2Complex 2 belongs to P21space group and exhibits a novel three-dimensional (3D) metal-organic network with a topology notation{4;8^2}{4;8^4;10}. Its physical properties were also examed. The results show that the complex 2 exhibits a second harmonic generation (SHG) effect of about 1.1 times as large as that of KDP, and the unhydrous powder of 2 has a SHG effect of about 0.6 times as large as that of KDP. Complex2 and the unhydrous powder of 2 display weak ferroelectric property with the saturation spontaneous polarizaton (Ps) of 0.026μC·cm-2 and 0.0080μC·cm-2, respectively, which are significantly lower than that for Rochelle salt.Complex 3 crystalizes in the chiral P41space group, and the Zn2+ ions are bridged by tartrate ions to form neutral two-dimensional (2D) layer parallel to (001). However, there is no obvious SHG efficiencies, and the parameter of ferroelectricity Ps=0.065μC·cm-2 which is lower than that for Rochelle salt. The complex 4 presents one-dimensional (1D) chains with a chiral space group P212121. Given that the complex 4 is noncentrosymmetrical, the SHG efficiencies were studied. The results from the powdered sample indicate that complex 4 displays weak powder SHG efficiencies. There is an electric hysteresis loop which is a typical ferroelectric feature wih a saturation spontaneous polarization Ps=6.05×10-3μC·cm-2, which are much lower than that for Rochelle salt. The magnetic susceptibility were also demonstratedThe complex 5 with a chiral space group P21 is a cocrystal constructed by tartaric acid,4,4’-bipyridine and water moleculars. The resuts of physical propery test indicate that complex 5 displays weak powder SHG efficiencies with the saturation spontaneous polarizaton (Ps) of 0.026μC·cm-2, which are significantly lower than that for Rochelle salt.

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