阅读说明：本技术 一种手性L-酒石酸CuII22CeIII4簇合物及其合成方法 (Chiral L-tartaric acid CuII22CeIII4Cluster compound and synthesis method thereof ) 是由 不公告发明人 于 2019-10-04 设计创作，主要内容包括：本发明公开了一种手性L-酒石酸Cu～(II)-(22)Ce～(III)-4簇合物及其合成方法。所述手性簇合物具有如下化学式组成：[K-(16)Cu-(22)Ce-4(CH-3COO)-8(L)-(16)]·82H-2O,其中,L为L-酒石酸。上述手性簇合物以L-酒石酸为配体,以醋酸铜、硝酸铈为金属盐,将三者加入适量浓度的醋酸/醋酸钾缓冲溶液中,在相应条件下反应而得。本发明所述方法简单,节能环保,产率高,原料易得且价格低廉；本发明所述L-酒石酸Cu～(II)-(22)Ce～(III)-4簇合物是一类具有轮状结构的手性磁性材料,具有预期的手性和磁性；作为一种新型的手性材料在手性分离、手性识别、非对称催化和手性磁体方面有潜在的应用前景。(The invention discloses chiral L-tartaric acid Cu II 22 Ce III 4 Cluster compound and its synthesis process. The chiral cluster compound has the following chemical formula: [ K ] 16 Cu 22 Ce 4 (CH 3 COO) 8 (L) 16 ]·82H 2 O, wherein L is L-tartaric acid. The chiral cluster compound is obtained by adding L-tartaric acid serving as a ligand, copper acetate and cerium nitrate serving as metal salts into acetic acid/potassium acetate buffer solution with a proper concentration and reacting under corresponding conditions. The method is simple, energy-saving and environment-friendly, and has high yield, easily available raw materials and low price; the L-tartaric acid Cu of the invention II 22 Ce III 4 The cluster compound is a chiral magnetic material with a wheel-shaped structure and has expected chirality and magnetism; the chiral material has potential application prospect in the aspects of chiral separation, chiral recognition, asymmetric catalysis and chiral magnets as a novel chiral material.)

1. Chiral L-tartaric acid Cu₂₂Ce₄Cluster compound, characterized in that the chiral L-tartaric acid Cu₂₂Ce₄The cluster compound has the following chemical formula composition: [ K ]₁₆Cu₂₂Ce₄(CH₃COO)₈(L)₁₆]·82H₂O, wherein L represents L-tartaric acid;

the L-tartaric acid Cu₂₂Ce₄The cluster structure can be seen as that the cluster structure is composed of L-tartaric acid, acetic acid and Cu²⁺、Ce³⁺Cu formed by ion coordination₂₂Ce₄Wheel-like structure with [ CeCu₃O₄]Is a structural unit of 2 pieces of [ CeCu₃O₄]Structural elementFrom Cu²⁺Bridging to form [ CeCu₃O₄]₂Unit, 4 pieces of [ CeCu₃O₄]₂The units are bridged to form a wheel structure, a K⁺Two Cu at the center of wheel-shaped structure²⁺Located at both ends of the center hub.

2. The chiral Cu L-tartrate of claim 1₂₂Ce₄A cluster characterized by: single crystal structure analysis showed that its crystallization was tetragonal, I422 space group, a =23.212(3) a, b =23.212(3) a, c =18.090(3) a, α = β = γ = 90.00 °, V =9747(3) a³Z =1, and Flack value =0.09 (5).

Technical Field

The invention belongs to the technical field of inorganic functional materials, and particularly relates to chiral L-Cu tartrate^II ₂₂Ce^III ₄Cluster compound and its synthesis process.

Background

The synthesis and properties of chiral metal clusters have been the focus of research by researchers at home and abroad, especially on chiral 3d-4f metal clusters. The attractive part of the molecule exists in an elegant structure, and chirality is introduced into the metal cluster, so that the metal cluster has good application prospects in the fields of nonlinear optics, chiral magnetic materials, chiral separation, chiral identification and the like.

Among the chiral clusters reported at present, many studies on chiral polyacid-based heteronuclear metal clusters are available. But a chiral 3d-4f metal cluster with nanometer dimensions may be called phoenix unicorn. Due to the appropriate reaction conditions, internal connection modes and metal core number in a complex system during the synthesis of the metal cluster compound, the preparation of the heteronuclear chiral 3d-4f metal cluster compound becomes a difficult point and a hot point in the field of inorganic synthesis; in addition, under the necessary form of advocating green and sustainable chemistry, synthetic chemists are pursuing a lower-consumption and higher-efficiency way to synthesize functional materials, adopt an environment-friendly solvent (such as water) to replace the traditional organic solvent, react at normal temperature and normal pressure, and have very important significance in the aspects of environmental protection and safe production, energy conservation and emission reduction.

With the rapid development of material preparation technology, researchers have made higher requirements on chiral materials and various performance parameters thereof. More and more chiral materials are being synthesized, but no chemical formula [ K ] is available at present₁₆Cu₂₂Ce₄(CH₃COO)₈(L)₁₆]·82H₂Cu of O^II ₂₂Ce^III ₄Is a report of chiral magnetic materials for motifs.

Disclosure of Invention

The technical problem to be solved by the invention is to provide a novel L-Cu tartrate^II ₂₂Ce^III ₄Cluster compounds, and methods for their synthesis.

The L-tartaric acid Cu of the invention^II ₂₂Ce^III ₄A cluster compound having the formula: [ K ]₁₆Cu₂₂Ce₄(CH₃COO)₈(L)₁₆]·82H₂O。

Wherein L is L-tartaric acid.

The L-tartaric acid Cu of the invention^II ₂₂Ce^III ₄The cluster can be viewed as: prepared from L-tartaric acid, acetic acid and Cu²⁺、Ce³⁺Cu formed by ion coordination₂₂Ce₄Wheel-like structure with [ CeCu₃O₄]Is a structural unit of 2 pieces of [ CeCu₃O₄]The structural element is composed of Cu²⁺Bridging to form [ CeCu₃O₄]₂Unit, 4 pieces of [ CeCu₃O₄]₂The units are bridged to form a wheel structure, a K⁺Two Cu at the center of wheel-shaped structure²⁺Located at both ends of the center hub.

TABLE 1 [ K ]₁₆Cu₂₂Ce₄(CH₃COO)₈(L)₁₆]·82H₂Crystallographic parameters of O

The research of the applicant finds that the L-Cu tartrate of the invention^II ₂₂Ce^III ₄The cluster compound has the following chiral optical properties: the solution circular dichroism spectrum shows the Koton effect at 215nm (-), 220 nm (+), 240nm (-), and 280nm (+).

The above-mentioned L-tartaric acid Cu^II ₂₂Ce^III ₄The preparation method of the cluster compound comprises the following steps: taking L-tartaric acid, copper acetate and cerium nitrate as initial raw materials, adding the initial raw materials and the initial raw materials into acetic acid/potassium acetate buffer solution with a proper concentration and pH value, stirring and reacting for a certain time at room temperature, filtering, standing and evaporating for several days at room temperature, washing a product with absolute ethyl alcohol, and drying in a vacuum drying oven to obtain the L-type chiral cluster compound.

In the preparation method, the molar ratio of the L-tartaric acid to the copper acetate is 1-10, and the molar ratio of the L-tartaric acid to the cerium nitrate is 1-10; in the preparation method, the concentration of the acetic acid/potassium acetate buffer solution is 0.5-5.0M/L, the pH value is 3.0-7.0, and the dosage is 2-100 ml.

In the preparation method, the room temperature reaction time is 1-24 hours, the filtration is carried out, and the filtrate is kept still at room temperature for evaporation for 1-30 days; washing the product with absolute ethyl alcohol for 3 times, and drying the product in a vacuum drying oven at 60 ℃ for 12 hours to obtain the L-type chiral cluster compound.

The L-tartaric acid Cu of the invention^II ₂₂Ce^III ₄The cluster compound is prepared from L-tartaric acid, acetic acid and Cu²⁺、Ce³⁺Formed by coordination of ionsCu₂₂Ce₄Wheel-like structure with [ CeCu₃O₄]Is a structural unit of 2 pieces of [ CeCu₃O₄]The structural element is composed of Cu²⁺Bridging to form [ CeCu₃O₄]₂Unit, 4 pieces of [ CeCu₃O₄]₂The units are bridged to form a wheel structure, a K⁺Two Cu at the center of wheel-shaped structure²⁺Located at both ends of the center hub.

Compared with the prior art, the invention provides the novel L-Cu tartrate^II ₂₂Ce^III ₄Cluster Compound [ K₁₆Cu₂₂Ce₄(CH₃COO)₈(L)₁₆]·82H₂O and a process for producing the same, the L-tartaric acid Cu^II ₂₂Ce^III ₄The chiral optical properties of (a) are: the solution circular dichroism spectrum shows the Ketton effect at 215nm (-), 220 nm (+), 240nm (-), and 280nm (+); the method disclosed by the invention is simple, energy-saving and environment-friendly, high in yield, easily available in raw materials and low in price.

Description of the drawings:

FIG. 1. L-tartaric acid Cu^II ₂₂Ce^III ₄Cluster Compound [ K₁₆Cu₂₂Ce₄(CH₃COO)₈(L)₁₆]·82H₂A single crystal structure of O.

FIG. 2. L-tartaric acid Cu^II ₂₂Ce^III ₄Cluster Compound [ K₁₆Cu₂₂Ce₄(CH₃COO)₈(L)₁₆]·82H₂Of O [ CeCu₃O₄]And (5) structural primitive graphs.

FIG. 3. L-tartaric acid Cu^II ₂₂Ce^III ₄Cluster Compound [ K₁₆Cu₂₂Ce₄(CH₃COO)₈(L)₁₆]·82H₂Solution CD spectrum of O.

FIG. 4. L-tartaric acid Cu^II ₂₂Ce^III ₄Cluster Compound [ K₁₆Cu₂₂Ce₄(CH₃COO)₈(L)₁₆]·82H₂Of Oχ _M T-TFigure (a).

FIG. 5. L-tartaric acid Cu^II ₂₂Ce^III ₄Cluster Compound [ K₁₆Cu₂₂Ce₄(CH₃COO)₈(L)₁₆]·82H₂Of Oχ′_M -TFigure (a).

FIG. 6. L-tartaric acid Cu^II ₂₂Ce^III ₄Cluster Compound [ K₁₆Cu₂₂Ce₄(CH₃COO)₈(L)₁₆]·82H₂Of Oχ′′_M-TFigure (a).

FIG. 7. L-tartaric acid Cu^II ₂₂Ce^III ₄Cluster Compound [ K₁₆Cu₂₂Ce₄(CH₃COO)₈(L)₁₆]·82H₂Infrared spectrum of O.

Detailed Description

The present invention will be further described in detail below with reference to specific examples for better understanding of the present invention, but the present invention is not limited to the following examples.

Example 1: weighing 0.251g L-tartaric acid, 0.207g copper acetate and 0.309g cerium nitrate, adding into 14ml of 2.1M/L, pH =6.9 acetic acid/potassium acetate buffer solution, stirring at room temperature for reaction for 7h, filtering, standing at room temperature for evaporation for 15 days, filtering to obtain blue strip crystals, washing with anhydrous ethanol for 3 times, and drying in a vacuum drying oven at 60 ℃ for 12h to obtain the L-Cu tartrate^II ₂₂Ce^III ₄A cluster compound.

The product obtained in example 1 was characterized:

1) and (3) analyzing a crystal structure:

selecting blue strip crystals with intact structure, determining the crystal structure by X-ray single crystal diffraction, wherein the obtained crystal structure data is shown in the table 1, the chemical structure of the obtained blue strip crystals is shown in figure 1, and the obtained blue strip crystals are determined to be L-Cu tartrate^II ₂₂Ce^III ₄Cluster Compound [ K₁₆Cu₂₂Ce₄(CH₃COO)₈(L)₁₆]·82H₂O, wherein L is L-tartaric acid.

The L-tartaric acid Cu of the invention^II ₂₂Ce^III ₄The cluster compound is prepared from L-tartaric acid, acetic acid and Cu²⁺、Ce³⁺Cu formed by ion coordination₂₂Ce₄Wheel-like structure with [ CeCu₃O₄]Is a structural unit of 2 pieces of [ CeCu₃O₄]The structural element is composed of Cu²⁺Bridging to form [ CeCu₃O₄]₂Unit, 4 pieces of [ CeCu₃O₄]₂The units are bridged to form a wheel structure, a K⁺Two Cu at the center of wheel-shaped structure²⁺At the ends of the center hub as shown in figure 2.

2) Determination of optical Properties:

0.010g of Cu L-tartrate prepared in this example was taken^II ₂₂Ce^III ₄Cluster Compound [ K₁₆Cu₂₂Ce₄(CH₃COO)₈(L)₁₆]·82H₂O was tabletted with 0.600g KBr and tested on solid CD, which is shown in FIG. 3.

3) Magnetic property determination:

0.022g of Cu L-tartrate prepared in this example was taken^II ₂₂Ce^III ₄Cluster Compound [ K₁₆Cu₂₂Ce₄(CH₃COO)₈(L)₁₆]·82H₂O grinding, and performing magnetic test on the magnetic property tester to obtain a magnetic property test curve as shown in FIG. 4 (for magnetic material)χ _M T–TFIG. 5 (magnetic material at 1.8-15K)χ′_M–TFIG. 6 (magnetic material at 1.8-15K)χ′′_M–TFigure) is shown.

As can be seen from FIG. 4, the L-tartaric acid Cu of the present invention^II ₂₂Ce^III ₄Cluster compound at room temperatureχ _M TIs 10.77 cm³ K mol^-1As the temperature is lowered, the temperature of the alloy is lowered,χ _M Tgradually increase until 6011.31 cm at K³ K mol^-1(ii) a Then as the temperature is lowered,χ _M Trapidly increasing to 14.47 cm at 5K³ K mol^-1。

As can be seen from FIGS. 5 to 6, the L-tartaric acid Cu of the present invention^II ₂₂Ce^III ₄The ac signal of the cluster showed that it did not have monomolecular magnetic properties.

4) Infrared characterization:

Cu-L-tartrate obtained in this example was subjected to Fourier exchange Infrared Spectroscopy (KBr pellet) using a Perkinelmer Spectrum 100 FT-IR model^II ₂₂Ce^III ₄Cluster Compound [ K₁₆Cu₂₂Ce₄(CH₃COO)₈(L)₁₆]·82H₂O is subjected to infrared analysis, and the spectrograph range is 400-^-1The obtained infrared spectrum is shown in FIG. 7.

Example 2: weighing 0.193g L-tartaric acid, 0.310g copper acetate and 0.320g cerium nitrate, adding into 11ml of 2.2M/L, pH =6.1 acetic acid/potassium acetate buffer solution, stirring at room temperature for 12h, filtering, standing at room temperature for evaporation for 13 days, filtering to obtain blue strip crystals, washing with anhydrous ethanol for 3 times, and drying in a vacuum drying oven at 60 ℃ for 12h to obtain L-Cu tartrate^II ₂₂Ce^III ₄A cluster compound.