CN108384017B - Chiral Ni (II) amino acid Schiff base coordination polymer and preparation method thereof - Google Patents
Chiral Ni (II) amino acid Schiff base coordination polymer and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a chiral Ni (II) amino acid Schiff base coordination polymer and a preparation method thereof, belonging to the technical field of coordination chemistry; the chemical formula of the amino acid Schiff base coordination polymer is [ C12H18N3O2NiCl]n is the same as the formula (I). The coordination polymer is prepared by reacting ligand and metal precursor in mixed solvent such as methanol and water, ethanol and water or acetonitrile and water at 60-80 deg.C for 24-30 hr, and crystallizing to obtain target product; the ligand is Schiff base obtained by condensation and reduction reaction of leucine and p-aldehyde pyridine. The method has the advantages of mild reaction conditions, simple post-treatment, higher yield, good chemical stability and very good potential application in the fields of gas adsorption and separation, catalysis, recognition, optics and the like.
Description
Technical Field
The invention relates to a chiral Ni (II) amino acid Schiff base coordination polymer and a preparation method thereof, belonging to the technical field of coordination chemistry.
Background
The discovery of schiff bases dates back to the nineteenth century, the products with a methoimine structure formed by the addition-elimination (condensation) of an amine and a reactive carbonyl group. In Schiff base, various functional groups can be introduced through condensation reaction to be derivatized, and the size and the position of the connected group are changed, so that the complex with properties of electricity, magnetism and the like is obtained.
Amino acid is an important physiologically active substance, is a basic structural unit which forms protein, enzyme and the like in an organism, participates in various biochemical processes in the organism, has biological activities such as antivirus, bacteriostasis, anticancer and the like and better oxygen carrying and catalytic properties, has wide application prospect in the fields of agriculture, medicine, catalysis, materials, bioscience and the like, and has been widely concerned by people. Thus, other groups of different structures and activities are introduced by reaction. Therefore, a new amino acid Schiff base ligand and a metal complex thereof are synthesized, the structure, the property and the biological activity of the ligand are researched, and the ligand has important significance for guiding the synthesis and the application of the complex.
L-leucine is one of more than 20 amino acids abundantly present in nature. The Schiff base ligand contains active amino and carboxylic acid groups, the structure is easy to modify into amino acid derivatives, and Schiff base coordination derived from the amino acid derivatives is a good flexible ligand. The ligand has carboxyl, pyridine and amino, on one hand, the ligand has rich coordination modes and configurations, on the other hand, the carboxyl can be used as a donor of a hydrogen bond and an acceptor of the hydrogen bond, and the formation of the hydrogen bond and a multidimensional structure is facilitated.
Disclosure of Invention
One of the technical tasks of the invention is to make up the defects of the prior art, and provide a preparation method of a coordination polymer crystal material with pyridine-4-methyl-leucine hydrochloride as a ligand and nickel ions as metal ions. The method has the advantages of low cost of raw materials, simple preparation process, low reaction energy consumption and industrial application prospect.
The technical scheme of the invention is as follows:
1. a chiral Ni (II) amino acid Schiff base coordination polymer, the chemical formula of the chiral Ni (II) amino acid Schiff base coordination polymer is [ C12H17N2O2NiCl]n; belongs to a monoclinic system; space group P21; unit cell parameters are α =6.0068(16) °, β =16.540(4) °, and γ =9.314(3) °; one structural unit is represented by the formula C12H17N2O2A negative ion of ligand (I) and a negative ion of Cl (I) are coordinated with a positive ion of Ni (II).
The ligand (I) negative ions have the following chemical structural formula:
2. the preparation method of the chiral Ni (II) amino acid Schiff base coordination polymer comprises the following steps:
adding 0.5mmol of chiral ligand and 0.5-1.0mmol of metal salt into an autoclave, adding 7-9mL of mixed solvent, and stirring until the chiral ligand and the metal salt are completely dissolved;
putting the sealed autoclave into an oven, heating to 60-80 ℃, keeping the temperature constant for 12-18 hours, then cooling to room temperature, filtering, and washing solid substances with ethanol to obtain a chiral Ni (II) amino acid Schiff base coordination polymer;
the metal salt is selected from one of the following: nickel nitrate, nickel sulfate, nickel chloride and nickel acetate;
the mixed solvent is prepared by blending an organic solvent and water according to the volume ratio of 1:1, wherein the organic solvent is selected from one of the following solvents: methanol, ethanol, acetonitrile;
the chiral Ni (II) amino acid Schiff base coordination polymer crystal is a flaky single crystal, and the size of the crystal is 0.1-0.2 mm.
3. The preparation method of the chiral Ni (II) amino acid Schiff base coordination polymer comprises the following steps:
blending 0.5mmol of chiral ligand with 2-4mL of water, adding 0.1-0.2mmol of sodium carbonate, stirring to obtain a clear solution, continuously adding 0.5-1.0mmol of metal salt, uniformly mixing, adding 2-4mL of ethanol, uniformly mixing, standing for 10-30 seconds, enabling the mixed solution to become turbid, continuously standing for 5 minutes, centrifugally separating the mixed solution, washing with water, and drying at 60 ℃ to obtain a chiral Ni (II) amino acid Schiff base coordination polymer;
the crystal grain size of the chiral Ni (II) amino acid Schiff base coordination polymer is 80-90nm, and the crystal grain belongs to coordination polymer nanocrystals;
the metal salt is selected from one of the following: nickel nitrate, nickel sulfate, nickel chloride and nickel acetate.
4. The chiral ligand is as described above, and the synthesis steps are as follows:
dissolving 0.5mol of L-leucine and 0.25mol of sodium carbonate in 250mL of water to prepare an aqueous solution of L-leucine; dissolving 0.5mol of 4-pyridine benzaldehyde in 100mL of methanol to prepare a methanol solution of the 4-pyridine benzaldehyde; adding 4-pyridine benzaldehyde into an aqueous solution of L-leucine, and stirring at room temperature for 1 hour; cooling the mixed solution in ice bath for 30 minutes, adding a newly prepared sodium borohydride aqueous solution of 150mL and 5mol/L under the condition of continuing cooling in ice bath, and stirring for 1 hour; adjusting the pH of the reaction solution to 4-6 by using hydrochloric acid with the mass fraction of 15%, stirring for 2 hours, and performing rotary evaporation to obtain solid powder; adding 150mL of methanol into solid powder obtained by rotary evaporation, heating and refluxing, filtering liquid, carrying out rotary evaporation on filtrate, and drying the obtained solid at 60 ℃ to obtain the chiral ligandC12H18N2O2。
The beneficial technical effects of the invention are as follows:
(1) the raw material used in the preparation method is low-cost L-leucine, and a hydrothermal method is adopted to synthesize the chiral amino acid Schiff base complex polymer single crystal with a chiral space group of P21.
(2) The chiral amino acid Schiff base compound polymer nanocrystal is quickly prepared by adopting a room temperature blending method, only adding sodium carbonate, regulating and controlling the feeding sequence and blending at room temperature, and has the advantages of low raw material cost, simple preparation process, low reaction energy consumption and industrial application prospect.
(3) The preparation of the chiral Ni (II) amino acid Schiff base coordination polymer monocrystal and nanocrystal has simple post-treatment, and the yield of the obtained complex reaches 70-85%; the chiral amino acid Schiff base coordination polymer monocrystal and the nanocrystal are insoluble in water and common organic solvents, such as methanol, ethanol, acetonitrile, acetone and the like, and have good chemical stability; thermogravimetric analysis shows that the thermal stability of the material is above 260 ℃, and the material has potential application value in the fields of gas adsorption and separation, catalysis, recognition, optics and the like.
Detailed Description
Reference will now be made in detail to the embodiments of the present invention, the following examples of which are intended to be illustrative only and are not to be construed as limiting the scope of the invention.
EXAMPLE 1 Synthesis of chiral ligand
Dissolving 0.5mol of L-leucine and 0.25mol of sodium carbonate in 250mL of water to prepare an aqueous solution of L-leucine; dissolving 0.5mol of 4-pyridine benzaldehyde in 100mL of methanol to prepare a methanol solution of the 4-pyridine benzaldehyde; adding 4-pyridine benzaldehyde into an aqueous solution of L-leucine, and stirring at room temperature for 1 hour; the mixed solution is cooled for 30 minutes in an ice bath, and a newly prepared 150mL and 5mol/L sodium borohydride aqueous solution is added under the condition of continuing cooling in the ice bathStirring for 1 hour; adjusting the pH of the reaction solution to 4-6 by using hydrochloric acid with the mass fraction of 15%, stirring for 2 hours, and performing rotary evaporation to obtain solid powder; adding 150mL of methanol into solid powder obtained by rotary evaporation, heating and refluxing, filtering liquid, carrying out rotary evaporation on filtrate, and drying the obtained solid at 60 ℃ to obtain chiral ligand C12H18N2O2。
Example 2 preparation of chiral Ni (II) amino acid Schiff base coordination polymer
Adding 0.5mmol of the chiral ligand prepared in the example 1 and 0.5mmol of nickel nitrate into an autoclave, adding 7mL of mixed solvent, and stirring until the chiral ligand and the nickel nitrate are completely dissolved; the mixed solvent is prepared by blending methanol and water according to the volume ratio of 1: 1;
putting the sealed autoclave into an oven, heating to 60 ℃, keeping the temperature constant for 12 hours, then cooling to room temperature, filtering, and washing solid substances with ethanol to obtain chiral amino acid Schiff base coordination polymer crystals;
the chiral amino acid Schiff base coordination polymer crystal is a flaky single crystal, and the size of the crystal is 0.1-0.2 mm.
Example 3 preparation of chiral Ni (II) amino acid Schiff base coordination polymer
Adding 0.5mmol of chiral ligand prepared in example 1 and 1.0mmol of nickel sulfate into an autoclave, adding 9mL of mixed solvent, and stirring until the chiral ligand and the nickel sulfate are completely dissolved;
putting the sealed autoclave into an oven, heating to 80 ℃, keeping the temperature constant for 18 hours, then cooling to room temperature, filtering, and washing solid substances with ethanol to obtain chiral amino acid Schiff base coordination polymer crystals;
the mixed solvent is prepared by blending ethanol and water according to the volume ratio of 1: 1;
the chiral amino acid Schiff base coordination polymer crystal is a flaky single crystal, and the size of the crystal is 0.1-0.2 mm.
Example 4 preparation of chiral Ni (II) amino acid Schiff base coordination polymer
Adding 0.5mmol of chiral ligand prepared in example 1 and 0.75 mmol of nickel acetate into an autoclave, adding 8 mL of mixed solvent, and stirring until the chiral ligand and the nickel acetate are completely dissolved;
putting the sealed autoclave into an oven, heating to 70 ℃, keeping the temperature for 15 hours, then cooling to room temperature, filtering, and washing solid substances with ethanol to obtain chiral Ni (II) amino acid Schiff base coordination polymer crystals;
the mixed solvent is prepared by blending acetonitrile and water according to the volume ratio of 1: 1;
the chiral Ni (II) amino acid Schiff base coordination polymer crystal is a flaky single crystal, and the size of the crystal is 0.1-0.2 mm.
Example 5 preparation of chiral Ni (II) amino acid Schiff base coordination polymer nanocrystals
And (2) blending 0.5mmol of chiral ligand prepared in example 1 with 2mL of water, adding 0.1 mmol of sodium carbonate, stirring to obtain a clear solution, continuously adding 0.5mmol of nickel nitrate, uniformly mixing, adding 2mL of ethanol, uniformly mixing, standing for 10 seconds, enabling the mixed solution to become turbid, continuously standing for 5 minutes, centrifugally separating the mixed solution, washing with water, and drying at 60 ℃ to obtain chiral amino acid Schiff base coordination polymer crystals with the particle size of 80-90 nm.
Example 6 preparation of chiral Ni (II) amino acid Schiff base coordination polymer nanocrystals
And (2) blending 0.5mmol of chiral ligand prepared in example 1 with 4mL of water, adding 0.2mmol of sodium carbonate, stirring to obtain a clear solution, continuously adding 1.0mmol of nickel acetate, uniformly mixing, adding 4mL of ethanol, uniformly mixing, standing for 30 seconds, enabling the mixed solution to become turbid, continuously standing for 5 minutes, centrifugally separating the mixed solution, washing with water, and drying at 60 ℃ to obtain chiral amino acid Schiff base coordination polymer crystals with the particle size of 80-90 nm.
Example 7 preparation of chiral Ni (II) amino acid Schiff base coordination polymer nanocrystals
And (2) blending 0.5mmol of chiral ligand prepared in example 1 with 3 mL of water, adding 0.15 mmol of sodium carbonate, stirring to obtain a clear solution, continuously adding 0.75 mmol of nickel sulfate, uniformly mixing, adding 3 mL of ethanol, uniformly mixing, standing for 20 seconds, enabling the mixed solution to become turbid, continuously standing for 5 minutes, centrifugally separating the mixed solution, washing with water, and drying at 60 ℃ to obtain chiral Ni (II) amino acid Schiff base coordination polymer crystals with the particle size of 80-90 nm.
Example 8
Examples 2-7 chiral Ni (II) amino acid Schiff base coordination polymers of formula [ C12H17N2O2NiCl]n; belongs to a monoclinic system; space group P21; unit cell parameters are α =6.0068(16) °, β =16.540(4) °, and γ =9.314(3) °; one structural unit is represented by the formula C12H17N2O2A negative ion of ligand (I) and a negative ion of Cl (I) are coordinated with a positive ion of Ni (II).
The ligand (I) negative ions have the following chemical structural formula:
Claims (4)
1. a chiral Ni (II) amino acid Schiff base coordination polymer is characterized in that the chemical formula of the chiral Ni (II) amino acid Schiff base coordination polymer is [ C12H17N2O2NiCl]n; belongs to a monoclinic system; space group P21; the unit cell parameters are 6.0068(16) °, β 16.540(4) °, γ 9.314(3) °; one structural unit is represented by the formula C12H17N2O2A negative ion of ligand (I) and a negative ion of Cl (I) are coordinated with a positive ion of Ni (II); the ligand (I) negative ions have the following chemical structural formula:
2. the method for preparing chiral Ni (II) amino acid Schiff base coordination polymer according to claim 1, which comprises the following steps:
adding 0.5mmol of chiral ligand and 0.5-1.0mmol of metal salt into an autoclave, adding 7-9mL of mixed solvent, and stirring until the chiral ligand and the metal salt are completely dissolved;
putting the sealed autoclave into an oven, heating to 60-80 ℃, keeping the temperature constant for 12-18 hours, then cooling to room temperature, filtering, and washing solid substances with ethanol to obtain a chiral Ni (II) amino acid Schiff base coordination polymer;
the metal salt is selected from nickel chloride;
the mixed solvent is prepared by blending an organic solvent and water according to the volume ratio of 1:1, wherein the organic solvent is selected from one of the following solvents: methanol, ethanol, acetonitrile;
the chiral Ni (II) amino acid Schiff base coordination polymer crystal is a flaky single crystal, and the size of the crystal is 0.1-0.2 mm.
3. The method for preparing chiral Ni (II) amino acid Schiff base coordination polymer according to claim 1, which comprises the following steps:
blending 0.5mmol of chiral ligand with 2-4mL of water, adding 0.1-0.2mmol of sodium carbonate, stirring to obtain a clear solution, continuously adding 0.5-1.0mmol of metal salt, uniformly mixing, adding 2-4mL of ethanol, uniformly mixing, standing for 10-30 seconds, enabling the mixed solution to become turbid, continuously standing for 5 minutes, centrifugally separating the mixed solution, washing with water, and drying at 60 ℃ to obtain a chiral Ni (II) amino acid Schiff base coordination polymer;
the crystal grain size of the chiral Ni (II) amino acid Schiff base coordination polymer is 80-90nm, and the crystal grain belongs to a coordination polymer nanocrystal; the metal salt is selected from nickel chloride.
4. The method for preparing the chiral Ni (II) amino acid Schiff base coordination polymer according to claim 1, wherein the chiral ligand is synthesized by the following steps:
dissolving 0.5mol of L-leucine and 0.25mol of sodium carbonate in 250mL of water to prepare an aqueous solution of L-leucine; dissolving 0.5mol of 4-pyridine benzaldehyde in 100mL of methanol to prepare a methanol solution of the 4-pyridine benzaldehyde; adding 4-pyridine benzaldehyde into an aqueous solution of L-leucine, and stirring at room temperature for 1 hour; then the mixed solution is cooled for 30 minutes in an ice bath, and under the condition of continuing cooling in the ice bath, newly prepared 150mL of 5mol/L hydroboration is addedStirring the aqueous solution of sodium for 1 hour; adjusting the pH of the reaction solution to 4-6 by using hydrochloric acid with the mass fraction of 15%, stirring for 2 hours, and performing rotary evaporation to obtain solid powder; adding 150mL of methanol into solid powder obtained by rotary evaporation, heating and refluxing, filtering liquid, carrying out rotary evaporation on filtrate, and drying the obtained solid at 60 ℃ to obtain chiral ligand C12H18N2O2。
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| CN103331151A (en) * | 2013-07-04 | 2013-10-02 | 山东师范大学 | Non-interpenetrating chiral MOF stationary phase, its preparation method and application in enantiomer separation in HPLC |
| CN107286201A (en) * | 2017-07-29 | 2017-10-24 | 昆明学院 | Stable chain Ni (II) complexes of amino acid with fluorescence property and preparation method thereof |
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| CN103331151A (en) * | 2013-07-04 | 2013-10-02 | 山东师范大学 | Non-interpenetrating chiral MOF stationary phase, its preparation method and application in enantiomer separation in HPLC |
| CN107286201A (en) * | 2017-07-29 | 2017-10-24 | 昆明学院 | Stable chain Ni (II) complexes of amino acid with fluorescence property and preparation method thereof |
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