CN106397788B - cobalt coordination polymer of dicarboxylic acid ligand and preparation method thereof - Google Patents
cobalt coordination polymer of dicarboxylic acid ligand and preparation method thereof Download PDFInfo
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- CN106397788B CN106397788B CN201610855925.3A CN201610855925A CN106397788B CN 106397788 B CN106397788 B CN 106397788B CN 201610855925 A CN201610855925 A CN 201610855925A CN 106397788 B CN106397788 B CN 106397788B
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Abstract
The invention provides cobalt coordination polymers of dicarboxylic acid ligands and a preparation method thereof, wherein the molecular formula is C11H13CoO6.5. The coordination polymer is a trigonal system,R‑3 space groups. Cell parametersa=16.0381(2) Å，b=16.0381Å，c=24.1947(4) Å，a=90°，β=90°，γ=120°，v=5389.60(16) Å3. The cobalt coordination polymer of the dicarboxylic acid ligand is easy to prepare under hydrothermal conditions, has good stability, and the synthesized material has few defects and high crystallinity. The cobalt coordination polymer of the dicarboxylic acid ligand has a very good potential application prospect in the field of molecular magnets.
Description
Technical Field
The invention belongs to the field of coordination chemistry, and relates to a cobalt coordination polymer of dicarboxylic acid ligands and a preparation method thereof.
Background
In recent years, has attracted much attention, and the abundant and diverse coordination modes of carboxylic acid groups mainly include monodentate coordination, bidentate chelate coordination and the like, and can be used as hydrogen bond acceptors and donors to perform coordination bond and hydrogen bond driven supramolecular self-assembly and enhance the stability of compound structures, because carboxyl has unique electronic structures to form interesting topologies, the negative charge density of the carboxyl is high, the coordination capacity with metal ions is strong, and various coordination polymers can be formed, thereby further promoting the development of carboxylic acid coordination polymers (W.Meng, S.Xu, Z.Zhang, S.yu, J.Yu, L.Dai, L.Wang, H.Hou, [ J.Dau ] J.].Inorg. Chem. Commun.2016,65, 45-48; A. Y. Robin, K. M. Fromm, [J].Coord. Chem. Rev.2006,250, 2127-2157; B. Y. Li, F. Yang, G. H. Li, D. Liu, Q. Zhou, Z.Shi, S. H. Feng, [J].Cryst. Growth Des.2011,11, 1475-1485; J. H. Wang, G. M.Tang, Y. T. Wang, T. X. Qin, S. W. Ng, [J].CrystEngComm2014,16, 2660-2683）。
Disclosure of Invention
The invention provides cobalt coordination polymers of dicarboxylic acid ligands and a preparation method thereof.
The technical problem to be solved by the invention is realized by the following technical scheme that cobalt coordination polymers of dicarboxylic acid ligands have a molecular formula of C11H13CoO6.5. The coordination polymer is of a trigonal system,R-3 space groups. Cell parametersa=16.0381(2) Å，b=16.0381Å，c=24.1947(4) Å，a=90°，β=90°，γ=120°，V=5389.60(16) Å3。
cobalt coordination polymer of dicarboxylic acid ligand is prepared through mixing 4-carboxymethyl-2-ethoxybenzoic acid (RGAA) with metallic cobalt salt in proportion, dissolving in water solvent, adding amount of sodium hydroxide, sealing in polytetrafluoro ethylene tube, loading in stainless steel reactor, crystallizing at 160 deg.C for 3 days in GZX-9030 MBE electrothermal blower, and natural cooling to room temp to obtain plum-red crystal.
In the process of synthesizing the metal cobalt coordination polymer, the 4-carboxymethyl-2-ethoxybenzoic acid (RGAA) carboxylic acid is completely deprotonated, and the monodentate and chelating coordination modes are adopted. Constructing the coordination polymer with three-dimensional network structure and good stability.
The invention has the beneficial effects that: the cobalt coordination polymer of the invention has reduced viscosity of the solution obtained under the condition of hydrothermal synthesis, is beneficial to the diffusion, transportation and transfer of reactants, greatly improves the reaction activity and can avoid the decomposition of organic ligands under the reaction condition. Is favorable for growing few defects, has good orientation and obtains perfect crystals. The polymer of the dicarboxylic acid ligand has very good potential application prospect in the field of molecular magnets.
Drawings
FIG. 1, cobalt coordination Polymer C of dicarboxylic acid ligands according to the invention11H13CoO6.5The coordination environment of Co at the metal center is shown.
FIG. 2 cobalt coordination Polymer C of dicarboxylic acid ligands according to the invention11H13CoO6.5A three-dimensional network diagram of coordination of Co as a metal center.
FIG. 3 cobalt coordination Polymer C of dicarboxylic acid ligands according to the invention11H13CoO6.5The coordination topological diagram of metal center Co.
FIG. 4, Infrared spectrum of a cobalt coordination polymer of bis-carboxylic acid ligands of the present invention.
FIG. 5 is a graph of the magnetic susceptibility of cobalt coordination polymers of dicarboxylic acid ligands of the present invention.
Detailed Description
The present invention will be described in detail with reference to examples, which are only preferred embodiments of the present invention and are not intended to limit the present invention.
Example 1 (C)11H13CoO6.5）
4-carboxymethyl-2-ethoxybenzoic acid (0.2 mmol), sodium hydroxide (0.3 mmol) and Co (NO)3)2·6H2Dissolving O (0.2 mmol) in 8mL of distilled water, putting the solution into a polytetrafluoroethylene reaction kettle, and putting the reaction kettle into a GZX-9030 MBE electric heating blower. The temperature was set at 160 ℃ and the mixture was heated for 3 days. Then, the temperature was lowered to room temperature at 5 ℃ per hour, and the mixture was filtered to obtain a cobalt complex polymer (complex 1).
Then carrying out structural characterization on the cobalt coordination polymer of the dicarboxylic acid ligand
The cobalt coordination polymer of the bis-carboxylic acid ligand was diffracted by single crystal structure and completed on a PC machine using SHELXTL program package. The crystallographic parameters of complex 1 are shown in table 1 (table 1 crystallographic parameters of cobalt coordination polymer of dicarboxylic acid ligand).
FIG. 1 shows the single crystal diffraction method to obtain C11H13CoO6.5The asymmetric unit contains Co (II) ions, RGAA ligands and 1.5 free water molecules, the Co (II) ions are six coordinated by six O atoms in a six coordinated slightly tilted octahedral configuration, the six oxygen ions are derived from the carboxylic acid oxygen atoms of five independent RGAA ligands, and the bond length distances of Co-O are in the range of 2.0358(18) -2.2115 (17) Å.
FIG. 2 is a three-dimensional network of coordination of Co at the metal center, shown as employing every RGAA ligandsμ 5-η 1:η 2:η 1:η 1:η 1The coordination mode connects five adjacent metal cobalt ions and forms a three-dimensional network structure.
FIG. 3 is a three-dimensional topology of coordination of Co at the metal center, as shown, 5 metallic cobalt ions are attached per RGAA ligands and 5 ligands are attached per metallic cobalt ions, so the topological sign of the coordination polymer of metallic cobalt is (5,5) linkage (4^4.6^3.8^3) (4^ 7.6^ 3).
FIG. 4 is an infrared spectrum of a cobalt coordination polymer containing kinds of dicarboxylic acid ligands and an infrared spectrum of a cobalt metal coordination polymer (KBr, cm)-1) 3458 (br), 2978(w), 1604 (vs), 1481 (w),1433(s), 1404(m), 1363(s), 1222 (m), 1172 (m), 1103 (w), 1083 (w), 1026 (m), 972 (w), 881(w), 852(w), 790(m), 732 (m), 665 (m), 578 (w), 497 (w). It has a characteristic peak ofv as(CO2 -) Is 1604 cm−1，v s(CO2 -) At 1433 and 1363cm−1,v(-OH) 3435 cm−1。
FIG. 5 is a temperature swing susceptibility curve for a three-dimensional cobalt coordination polymer containing a dicarboxylic acid ligand. The experimental results were measured at temperatures of 2-300K, with the addition of a 2000Oe magnetic field. As shown in FIG. 5, the product of molar magnetic susceptibility of the complex and temperature: (at 300K)χ m T) is 3.237 cm3mol-1K, and the literature reported cobalt: (S= 3/2，g= 2.0) the product of molar magnetic susceptibility and temperature is low. From 300K to 2K, the coordination polymer has a temperature of 14K,χ m the T value reaches the minimum value of 2.3103 cm3mol-1K. After a temperature of 14K, as the temperature decreases,χ m the T value is gradually increased to 2.557 cm when reaching 3K3mol-1K. And then to the end of the 2K,χ m the T value is reduced to 2.5092 cm3mol-1K. In the temperature range of 2-300K, coordination polymer is subjected to locally-external lawχ m -1Linear fitting with T curve to obtain local constantCIs 3.350cm3mol-1K, Weiss temperatureθis-10.450K. Due to the fact thatθThe value is negative, which further indicates weak antiferromagnetic coupling between cobalt ions, the temperature-change magnetic susceptibility curve of the complex indicates that the compound has a higher magnetic permeability than the compoundGood magnetic properties.
The above-mentioned embodiments only express the embodiments of the present invention, and the description is more specific and detailed, but not understood as the limitation of the patent scope of the present invention, but all the technical solutions obtained by using the equivalent substitution or the equivalent transformation should fall within the protection scope of the present invention.
Claims (3)
1, cobalt coordination polymers of dicarboxylic acid ligands, characterized by the chemical formula C11H13CoO6.5；
The coordination polymer is a trigonal system, R-3 space group, unit cell parameters of a =16.0381(2) Å, b =16.0381 Å, c =24.1947(4) Å, a =90 °, β =90 °, gamma =120 °, V =5389.60(16) Å3；
The Co (II) ions of the coordination polymer are coordinated by six O atoms in a six-coordinate slightly-inclined octahedral configuration, six oxygen ions are derived from five independent carboxylic acid oxygen atoms of the 4-carboxymethyl-2-ethoxybenzoic acid ligand, and the bond length distance of the Co-O is in the range of 2.0358(18) to 2.2115(17) Å.
2. The method for producing a metal cobalt coordination polymer according to claim 1, characterized in that: 0.2mmol of 4-carboxymethyl-2-ethoxybenzoic acid and 0.2mmol of Co (NO)3)2·6H2Dissolving O in 8ml of water, adding 0.3mmol of sodium hydroxide, sealing in a polytetrafluoroethylene tube, placing in a stainless steel reaction kettle, placing the reaction kettle in a GZX-9030 MBE electric heating blower, crystallizing at 160 ℃ for 3 days, naturally cooling to room temperature, and separating out a plum red blocky crystal.
3. Use of a cobalt coordination polymer of a dicarboxylic acid ligand according to claim 1 in the field of molecular magnetics.
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