CN107746409B - Non-core structure zinc complex and preparation method thereof - Google Patents
Non-core structure zinc complex and preparation method thereof Download PDFInfo
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- 239000011701 zinc Substances 0.000 title claims abstract description 70
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 61
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 238000010668 complexation reaction Methods 0.000 title description 2
- VYWYYJYRVSBHJQ-UHFFFAOYSA-N 3,5-dinitrobenzoic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 VYWYYJYRVSBHJQ-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- -1 3, 5-dinitrobenzoate anion Chemical class 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000003751 zinc Chemical class 0.000 claims abstract description 27
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000013078 crystal Substances 0.000 claims abstract description 23
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 18
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 13
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 13
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 13
- 239000010935 stainless steel Substances 0.000 claims abstract description 13
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 6
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 48
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 39
- 239000008367 deionised water Substances 0.000 claims description 30
- 229910021641 deionized water Inorganic materials 0.000 claims description 30
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 24
- 239000000725 suspension Substances 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 18
- RZLVQBNCHSJZPX-UHFFFAOYSA-L zinc sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Zn+2].[O-]S([O-])(=O)=O RZLVQBNCHSJZPX-UHFFFAOYSA-L 0.000 claims description 15
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 12
- 239000011592 zinc chloride Substances 0.000 claims description 12
- 235000005074 zinc chloride Nutrition 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 238000001914 filtration Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 8
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 125000004430 oxygen atom Chemical group O* 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 239000003513 alkali Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 238000007789 sealing Methods 0.000 abstract 1
- 230000000747 cardiac effect Effects 0.000 description 10
- 238000007605 air drying Methods 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 239000003446 ligand Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002447 crystallographic data Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005283 ground state Effects 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 1
- VYWYYJYRVSBHJQ-UHFFFAOYSA-M 3,5-dinitrobenzoate Chemical compound [O-]C(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1 VYWYYJYRVSBHJQ-UHFFFAOYSA-M 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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Abstract
The invention provides a non-heart structure zinc complex, the chemical formula of which is as follows: [ Zn (3,5-DNB)2(4,4-bipy) ] n, 3,5-DNB is 3, 5-dinitrobenzoate anion, 4,4-bipy is 4,4-bipyridine, n is polymerization degree, and the complex belongs to the orthorhombic system, Pca21(No.29) space group. The invention relates to a preparation method of a non-core structure zinc complex, which comprises the steps of dissolving 3,5-dinitrobenzoic acid, 4-bipyridine, a metal zinc salt and an inorganic base in water, sealing the water in a stainless steel reaction kettle with a polytetrafluoroethylene lining, heating the reaction kettle to the temperature of 130-150 ℃, maintaining the temperature for 72-96 hours, collecting colorless needle-shaped large crystals, and sequentially washing and drying the crystals to obtain the one-dimensional chain-shaped non-core structure complex.
Description
Technical Field
The invention relates to the technical field of complex preparation, in particular to a non-cardiac structure zinc complex and a preparation method thereof.
Background
3,5-Dinitrobenzoic acid, namely 3,5-Dinitrobenzoic acid (3,5-DNB) with the English name, is used as a flexible and variable organic ligand with a conjugated effect, has different coordination modes, can form a complex with transition or rare earth metal ions, and the formed metal complex has important potential application prospects in the aspects of functional materials such as magnetism, catalysis, luminescence and the like, and can be developed as a novel functional material. 4,4-Bipyridine, namely 4, 4-dipyridine (4,4-bipy) in English name, is a common rigid ligand, can form coordinate bonds with transition and rare earth metal ions, and can effectively regulate and control the structure of the complex, thereby influencing the performance of the complex.
At present, researchers have studied more deeply on the luminescent properties of metal complexes, and common luminescence is fluorescence and phosphorescence, and relatively speaking, the study on fluorescence emission is more common and deeper. The main difference between fluorescence and phosphorescence is that fluorescence is light emitted by a substance transitioning from a first excited singlet level to a ground state after absorbing light energy (S1 → S0), and phosphorescence is light emitted by a substance transitioning from a first excited triplet level to a ground state after absorbing light energy (T1 → S0). The multidentate ligand is used for designing and assembling metal complexes, such as polycarboxylic acid and nitrogen-containing heterocyclic organic molecules, and the complexes mainly comprise physical properties of nonlinear optics, ferroelectric materials, dielectric materials and the like, so that the metal complexes have important application in the aspects of photoelectric devices, information storage, nonlinear devices and the like. The non-centrosymmetric complex is mainly prepared by taking a chiral organic ligand as a raw material, and the non-centrosymmetric complex prepared by the non-chiral ligand has certain contingency.
Disclosure of Invention
Technical problem to be solved
The invention provides a noncardial zinc complex and a preparation method thereof in order to overcome the defect that the noncardial zinc complex can only be prepared by taking a chiral ligand as a raw material.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme:
the non-core structure zinc complex is formed by carrying out hydrothermal reaction on soluble zinc salt, 4-bipyridine, 3,5-dinitrobenzoic acid and inorganic base, and has a chemical formula as follows: [ Zn (3,5-DNB)2(4,4-bipy)]n3,5-DNB is 3, 5-dinitrobenzoate anion, 4,4-bipy is 4,4-bipyridine, and n is the degree of polymerization.
Further, the crystal of the complex is in an orthorhombic system, Pca21Space group (No. 29).
Further, the basic structure of the complex is a one-dimensional chain spiral structure, the basic unit contains a central zinc ion, two 3, 5-dinitrobenzoates and a 4,4-bipyridine molecule, the central zinc ion is in a tetrahedron configuration in a four-coordination mode, two oxygen atoms in the four coordination atoms are respectively from the carboxylic acid group oxygen atoms in the two 3, 5-dinitrobenzoates, and the other two nitrogen atoms are respectively from the two 4,4-bipyridine molecules.
A preparation method of a non-core structure zinc complex comprises the following steps:
s1, selecting soluble zinc salt, 4-bipyridine, 3,5-dinitrobenzoic acid and inorganic base, wherein the soluble zinc salt, the 4,4-bipyridine, the 3,5-dinitrobenzoic acid and the inorganic base are selected according to a molar ratio of 1:1: 1-2;
s2, dissolving the selected soluble zinc salt, 4-bipyridine, 3,5-dinitrobenzoic acid and inorganic base in 1000 parts of deionized water, and stirring for 60 minutes at room temperature to obtain a white suspension;
s3, adding the white suspension obtained in the step S2 into a stainless steel reaction kettle with a polytetrafluoroethylene lining;
s4, slowly heating the reaction kettle to 130-150 ℃ in a blast drying oven, maintaining the temperature for 72-96 hours, closing the drying oven, naturally cooling the reaction kettle to room temperature to obtain colorless needle-like large crystals, filtering, washing with deionized water for several times, and drying at room temperature to obtain the non-core zinc complex.
Further, the soluble zinc salt is one or a combination of zinc sulfate heptahydrate, zinc nitrate hexahydrate and zinc dichloride.
Further, the inorganic base in the step S2 is sodium hydroxide or potassium hydroxide.
(III) advantageous effects
The invention has the beneficial effects that: a zinc complex with non-core structure and its preparation method, the complex is formed by soluble zinc salt, 4-bipyridine, 3,5-dinitrobenzoic acid, inorganic base through the hydrothermal reaction, the crystal of the complex is the orthorhombic system, Pca21 space group (No. 29); the coordination compound basic unit contains one Zn (I) ion, two 3, 5-dinitrobenzoate radicals and one 4, 4-bipyridyl molecule, the Zn (I) ion forms a 21-spiral chain structure in the c-axis direction through the 4, 4-bipyridyl molecule, and the 4, 4-bipyridyl molecule is twisted in the process of forming a coordination bond with a zinc ion to form a one-dimensional chain spiral noncentral structure; the adjacent chain structures are crossed by pi … pi between benzene rings in 3, 5-dinitrobenzoate.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a flow chart of the preparation method of the present invention;
FIG. 2 is a diagram of the asymmetric unit structure of a zinc complex;
FIG. 3 is a one-dimensional spiral chain diagram of a zinc complex viewed along the c-axis direction;
FIG. 4 is an infrared spectrum of a zinc complex;
FIG. 5 is a graph showing simulated contrast of X-ray powder diffraction and X-ray single crystal diffraction of a zinc complex;
FIG. 6 is a thermogravimetric analysis of a zinc complex;
FIG. 7 is a differential scanning curve of a zinc complex;
FIG. 8 is a graph of phosphorescence emission from zinc complex solids.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The non-core zinc complex is formed by simple hydrothermal reaction of soluble zinc salt, 4-bipyridine, 3,5-dinitrobenzoic acid and inorganic base, and the chemical reaction equation is as follows:
the chemical formula of the complex is as follows: [ Zn (3,5-DNB)2(4,4-bipy)]n, 3,5-DNB is 3, 5-dinitrobenzoate anion, 4,4-bipy is 4,4-bipyridine, and n is the degree of polymerization. The crystal of the noncardial zinc complex is orthorhombic, and Pca21 space group (No. 29). The basic structure of the zinc complex is a one-dimensional chain-like spiral structure, and the basic unit contains a central Zn (I) ion, two 3,5-dinitrobenzoic acid radicals and one 4,4-bipyridine molecule.The central zinc ion is in a tetrahedral configuration in a four-coordination mode, two oxygen atoms in four coordination atoms are respectively from carboxylic acid group oxygen atoms in two 3, 5-dinitrobenzoates, and the other two nitrogen atoms are respectively from two 4,4-bipyridine molecules. Zn (I) ions form a 21-helical chain structure in the c-axis direction through 4,4-bipyridine molecules, and the 4,4-bipyridine molecules are twisted in the process of forming coordinate bonds with zinc ions, which is also the reason why zinc complexes form noncardial structures. Adjacent chain structures are connected by a pi.. pi (center distance:
) The action is piled up into a macroscopic structure. FIG. 2 is a diagram of the asymmetric unit structure of a zinc complex; FIG. 3 is a one-dimensional spiral chain diagram of a zinc complex as viewed along the c-axis direction.
With reference to fig. 1, a method for preparing a non-cardiac zinc complex comprises the following steps:
s1, selecting soluble zinc salt, 4-bipyridine, 3,5-dinitrobenzoic acid and inorganic base, wherein the soluble zinc salt, the 4,4-bipyridine, the 3,5-dinitrobenzoic acid and the inorganic base are selected according to a molar ratio of 1:1: 1-2;
s2, dissolving the selected soluble zinc salt, 4-bipyridine, 3,5-dinitrobenzoic acid and inorganic base in 1000 parts of deionized water, and stirring for 60 minutes at room temperature to obtain a white suspension;
s3, adding the white suspension obtained in the step S2 into a stainless steel reaction kettle with a polytetrafluoroethylene lining;
s4, slowly heating the reaction kettle to 130-150 ℃ in a blast drying oven, maintaining the temperature for 72-96 hours, closing the drying oven, naturally cooling the reaction kettle to room temperature to obtain colorless needle-like large crystals, filtering, washing with deionized water for several times, and drying at room temperature to obtain the non-core zinc complex.
Wherein the soluble zinc salt is one or a combination of zinc sulfate heptahydrate, zinc nitrate hexahydrate and zinc dichloride; the inorganic base in the step S2 is sodium hydroxide or potassium hydroxide. The adding amount of the soluble zinc salt, the 4, 4-bipyridyl, the 3,5-dinitrobenzoic acid and the inorganic base is10 mL of deionized water, and 0.1mmol of the zinc salt, 0.1mmol of the 4, 4-bipyridyl, 0.1-0.2 mmol of the 3,5-dinitrobenzoic acid and 0.1-0.2 mmol of the inorganic base are added.
Example 1:
a preparation method of a non-core structure zinc complex comprises the following steps:
s1, selecting zinc sulfate heptahydrate (0.1mmol), 4-bipyridine (0.1mmol), 3,5-dinitrobenzoic acid (0.2mmol) and sodium hydroxide (0.2mmol), and selecting zinc sulfate heptahydrate, 4-bipyridine, 3,5-dinitrobenzoic acid and sodium hydroxide according to the molar ratio of 1:1:2: 2;
s2, dissolving zinc sulfate heptahydrate, 4-bipyridine, 3,5-dinitrobenzoic acid and sodium hydroxide into 1000 parts of deionized water, and stirring for 60 minutes at room temperature to obtain a white suspension;
s3, adding the white suspension obtained in the step S2 into a 30mL stainless steel reaction kettle with a polytetrafluoroethylene lining, adding 10mL deionized water, and stirring for 60 minutes at room temperature;
s4, slowly heating the reaction kettle to 130 ℃ in a forced air drying oven, maintaining the temperature for 72 hours, closing the oven, naturally cooling the reaction kettle to room temperature to obtain colorless needle-shaped large crystals, filtering, washing with deionized water for a plurality of times, and drying at room temperature to obtain the noncardial zinc complex with the yield of 45%.
Example 2:
a preparation method of a non-core structure zinc complex comprises the following steps:
s1, selecting zinc sulfate heptahydrate (0.1mmol), 4-bipyridine (0.1mmol), 3,5-dinitrobenzoic acid (0.1mmol) and potassium hydroxide (0.1mmol), and selecting zinc sulfate heptahydrate, 4-bipyridine, 3,5-dinitrobenzoic acid and potassium hydroxide according to the molar ratio of 1:1:1: 1;
s2, dissolving zinc sulfate heptahydrate, 4-bipyridine, 3,5-dinitrobenzoic acid and potassium hydroxide into 500 parts of deionized water, and stirring for 60 minutes at room temperature to obtain a white suspension;
s3, adding the white suspension obtained in the step S2 into a 30mL stainless steel reaction kettle with a polytetrafluoroethylene lining, adding 10mL deionized water, and stirring for 60 minutes at room temperature;
s4, slowly heating the reaction kettle to 150 ℃ in a forced air drying oven, maintaining the temperature for 96 hours, closing the oven, naturally cooling the reaction kettle to room temperature to obtain colorless needle-shaped large crystals, filtering, washing with deionized water for a plurality of times, and drying at room temperature to obtain the noncardial zinc complex with the yield of 35%.
Example 3:
a preparation method of a non-core structure zinc complex comprises the following steps:
s1, selecting zinc nitrate hexahydrate (0.1mmol), 4-bipyridine (0.1mmol), 3,5-dinitrobenzoic acid (0.2mmol) and potassium hydroxide (0.2mmol), and selecting zinc nitrate hexahydrate, 4-bipyridine, 3,5-dinitrobenzoic acid and potassium hydroxide according to the molar ratio of 1:1:2: 2;
s2, dissolving the selected zinc nitrate hexahydrate, 4-bipyridine, 3,5-dinitrobenzoic acid and potassium hydroxide in 1000 parts of deionized water, and stirring for 60 minutes at room temperature to obtain a white suspension;
s3, adding the white suspension obtained in the step S2 into a 30mL stainless steel reaction kettle with a polytetrafluoroethylene lining, adding 10mL deionized water, and stirring for 60 minutes at room temperature;
s4, slowly heating the reaction kettle to 150 ℃ in a forced air drying oven, maintaining the temperature for 84 hours, closing the oven, naturally cooling the reaction kettle to room temperature to obtain colorless needle-shaped large crystals, filtering, washing with deionized water for a plurality of times, and drying at room temperature to obtain the noncardial zinc complex with the yield of 42%.
Example 4:
a preparation method of a non-core structure zinc complex comprises the following steps:
s1, selecting zinc chloride (0.1mmol), 4-bipyridyl (0.1mmol), 3,5-dinitrobenzoic acid (0.2mmol) and sodium hydroxide (0.2mmol), and selecting the zinc chloride, the 4, 4-bipyridyl, the 3,5-dinitrobenzoic acid and the sodium hydroxide according to the molar ratio of 1:1:2: 2;
s2, dissolving the selected zinc chloride, 4-bipyridine, 3,5-dinitrobenzoic acid and sodium hydroxide in 750 parts of deionized water, and stirring for 60 minutes at room temperature to obtain a white suspension;
s3, adding the white suspension obtained in the step S2 into a 30mL stainless steel reaction kettle with a polytetrafluoroethylene lining, adding 10mL deionized water, and stirring for 60 minutes at room temperature;
s4, slowly heating the reaction kettle to 140 ℃ in a forced air drying oven, maintaining the temperature for 84 hours, closing the oven, naturally cooling the reaction kettle to room temperature to obtain colorless needle-shaped large crystals, filtering, washing with deionized water for a plurality of times, and drying at room temperature to obtain the noncardial zinc complex with the yield of 40%.
Example 5:
a preparation method of a non-core structure zinc complex comprises the following steps:
s1, selecting zinc chloride (0.05mmol), zinc nitrate hexahydrate (0.05mmol), 4-bipyridyl (0.1mmol), 3,5-dinitrobenzoic acid (0.2mmol) and sodium hydroxide (0.2mmol), and selecting zinc chloride, zinc nitrate hexahydrate, 4-bipyridyl, 3,5-dinitrobenzoic acid and sodium hydroxide according to the molar ratio of 1:1:2:4: 4;
s2, dissolving the selected zinc chloride, zinc nitrate hexahydrate, 4-bipyridine, 3,5-dinitrobenzoic acid and sodium hydroxide in 1000 parts of deionized water, and stirring for 60 minutes at room temperature to obtain a white suspension;
s3, adding the white suspension obtained in the step S2 into a 30mL stainless steel reaction kettle with a polytetrafluoroethylene lining, adding 10mL deionized water, and stirring for 60 minutes at room temperature;
s4, slowly heating the reaction kettle to 130 ℃ in a forced air drying oven, maintaining the temperature for 96 hours, closing the oven, naturally cooling the reaction kettle to room temperature to obtain colorless needle-shaped large crystals, filtering, washing with deionized water for a plurality of times, and drying at room temperature to obtain the noncardial zinc complex with the yield of 48%.
Example 6:
a preparation method of a non-core structure zinc complex comprises the following steps:
s1, selecting zinc sulfate heptahydrate (0.05mmol), zinc nitrate hexahydrate (0.05mmol), 4-bipyridyl (0.1mmol), 3,5-dinitrobenzoic acid (0.2mmol) and potassium hydroxide (0.2mmol), and selecting zinc sulfate heptahydrate, zinc nitrate hexahydrate, 4-bipyridyl, 3,5-dinitrobenzoic acid and potassium hydroxide according to the molar ratio of 1:1:2:4: 4;
s2, dissolving selected zinc sulfate heptahydrate, zinc nitrate hexahydrate, 4-bipyridine, 3,5-dinitrobenzoic acid and potassium hydroxide in 500 parts of deionized water, and stirring for 60 minutes at room temperature to obtain a white suspension;
s3, adding the white suspension obtained in the step S2 into a 30mL stainless steel reaction kettle with a polytetrafluoroethylene lining, adding 10mL deionized water, and stirring for 60 minutes at room temperature;
s4, slowly heating the reaction kettle to 150 ℃ in a forced air drying oven, maintaining the temperature for 72 hours, closing the oven, naturally cooling the reaction kettle to room temperature to obtain colorless needle-shaped large crystals, filtering, washing with deionized water for a plurality of times, and drying at room temperature to obtain the noncardial zinc complex with the yield of 36%.
Example 7:
a preparation method of a non-core structure zinc complex comprises the following steps:
s1, selecting zinc sulfate heptahydrate (0.05mmol), zinc chloride (0.05mmol), 4-bipyridyl (0.1mmol), 3,5-dinitrobenzoic acid (0.2mmol) and potassium hydroxide (0.2mmol), and selecting zinc sulfate heptahydrate, zinc chloride, 4-bipyridyl, 3,5-dinitrobenzoic acid and potassium hydroxide according to the molar ratio of 1:1:2:4: 4;
s2, dissolving zinc sulfate heptahydrate, zinc chloride, 4-bipyridine, 3,5-dinitrobenzoic acid and potassium hydroxide in 500 parts of deionized water, and stirring for 60 minutes at room temperature to obtain a white suspension;
s3, adding the white suspension obtained in the step S2 into a 30mL stainless steel reaction kettle with a polytetrafluoroethylene lining, adding 10mL deionized water, and stirring for 60 minutes at room temperature;
s4, slowly heating the reaction kettle to 140 ℃ in a forced air drying oven, maintaining the temperature for 80 hours, closing the oven, naturally cooling the reaction kettle to room temperature to obtain colorless needle-shaped large crystals, filtering, washing with deionized water for a plurality of times, and drying at room temperature to obtain the noncardial zinc complex with the yield of 39%.
The non-core structure zinc complex prepared by the embodiment of the invention is further characterized as follows:
(1) and (3) determining the crystal structure of the non-core zinc complex:
selecting a transparent single crystal with a proper size to carry out an X-ray diffraction experiment at room temperature. Collecting diffraction data on a Bruker SMART Apex I-X-ray single crystal diffractometer using MoKalpha rays
And collecting data in an omega scanning mode, reducing the diffraction data by a SAINT program, performing empirical absorption correction, solving a crystal structure by a direct method by adopting a SHELXS-97 program, refining non-hydrogen atoms by adopting anisotropic thermal parameters, and finally determining the position of the hydrogen atoms by a theoretical hydrogenation method, wherein detailed crystallographic parameters are shown in Table 1.
Table 1: crystallographic parameters of non-cardiac zinc complexes
(2) Infrared spectrum characterization of the non-cardiac zinc complex:
the IR spectrum (KBr pellet) of the non-cardiac zinc complex is shown in FIG. 4. (instrument model: Nicolet IS10 Infrared Spectroscopy).
(3) Powder X-ray diffraction phase purity characterization of non-cardiac zinc complexes:
the powder X-ray diffraction pattern of the non-core zinc complex is completely consistent with the single crystal data simulation pattern, and the figure is shown in figure 5, which shows that the obtained non-core zinc complex is pure phase and provides reliable guarantee for the application of the non-core zinc complex as a polar material. (instrument model: Rigaku Ultima I V X-ray powder diffractometer).
(4) Characterization of thermal stability of non-cardiac zinc complexes:
thermogravimetric analysis and characterization of the non-core zinc complex show that the non-core zinc complex still stably exists at room temperature to about 290 ℃, see fig. 6, and prove that the non-core zinc complex has very good thermal stability, provides reliable guarantee for the applicability of the non-core zinc complex, and finally all organic matters are lost along with the temperature rise. (apparatus model: TA Q5000 IR).
(5) Differential scanning profile of non-cardiac zinc complexes:
the differential scanning curve of the non-cardiac zinc complex shows that the non-cardiac zinc complex has phase change at about 0 ℃, and the enthalpy of phase change is 1.043J/g, which is shown in figure 7. (instrument model: DSCQ 2000).
(6) Solid fluorescence properties of non-core zinc complexes:
solid fluorescence measurements were performed on non-core zinc complex crystal samples at room temperature: the noncardial complex was at 540nm (excitation wavelength 450nm), as shown in FIG. 8. (Instrument model: FLUOROLOG-3-TAU type fluorescence spectrometer).
The above embodiments are illustrative of the present invention, and other embodiments of the present invention are possible. The soluble zinc salt, the chemical reagents such as 4, 4-bipyridyl, 3,5-dinitrobenzoic acid, inorganic base (sodium hydroxide and potassium hydroxide) and the like and the stainless steel reaction kettle with polytetrafluoroethylene for carrying out the reaction can be purchased and obtained in the market, and the reaction kettle has the advantages of sufficient raw material source, low cost, high compound yield, high purity and good repeatability.
In summary, in the embodiment of the invention, under hydrothermal conditions, adding deionized water into soluble zinc salt, 4-bipyridine, 3,5-dinitrobenzoic acid and inorganic base, stirring for 60 minutes at room temperature, adding into a stainless steel reaction kettle with a polytetrafluoroethylene lining, placing the reaction kettle into a forced air drying oven, heating to 130-150 ℃, reacting for 72-96 hours, closing the oven, naturally cooling the reaction kettle to room temperature to obtain colorless needle-like large crystals, filtering, washing with deionized water for several times, and drying at room temperature to obtain a non-core zinc complex [ Zn (3,5-DNB)2(4,4-bipy)]n。
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (5)
1. A noncardiac zinc complex characterized by: the complex is formed by carrying out hydrothermal reaction on soluble zinc salt, 4-bipyridine, 3,5-dinitrobenzoic acid and inorganic base, and has a chemical formula as follows: [ Zn (3,5-DNB)2(4,4-bipy)]n3,5-DNB is 3, 5-dinitrobenzoate anion, 4,4-bipy is 4,4-bipyridine, and n is the degree of polymerization. The non-core zinc complex belongs to an orthorhombic system, namely Pca21Space group, the specific unit cell parameters are as follows:
α＝β＝γ＝90°。
2. a noncardiac zinc complex as claimed in claim 1 wherein: the basic structure of the complex is a one-dimensional chain spiral structure, a basic unit contains a central zinc ion, two 3, 5-dinitrobenzoate groups and a 4,4-bipyridine molecule, the central zinc ion is in a tetrahedron configuration in a four-coordination mode, two oxygen atoms in four coordination atoms are respectively from carboxylic acid group oxygen atoms in the two 3, 5-dinitrobenzoate groups, and the other two nitrogen atoms are respectively from the two 4,4-bipyridine molecules.
3. The method of claim 1, wherein the method comprises the steps of: the method comprises the following steps:
s1, selecting soluble zinc salt, 4-bipyridine, 3,5-dinitrobenzoic acid and inorganic base, wherein the soluble zinc salt, the 4,4-bipyridine, the 3,5-dinitrobenzoic acid and the inorganic base are selected according to a molar ratio of 1:1: 1-2;
s2, dissolving the selected soluble zinc salt, 4-bipyridine, 3,5-dinitrobenzoic acid and inorganic base in 1000 parts of deionized water, and stirring for 60 minutes at room temperature to obtain a white suspension;
s3, adding the white suspension obtained in the step S2 into a stainless steel reaction kettle with a polytetrafluoroethylene lining;
s4, slowly heating the reaction kettle to 130-150 ℃ in a blast drying oven, maintaining the temperature for 72-96 hours, closing the drying oven, naturally cooling the reaction kettle to room temperature to obtain colorless needle-like large crystals, filtering, washing with deionized water for several times, and drying at room temperature to obtain the non-core zinc complex.
4. A process for preparing a noncardiac zinc complex as claimed in claim 3, wherein: the soluble zinc salt is one or a combination of zinc sulfate heptahydrate, zinc nitrate hexahydrate and zinc dichloride.
5. A process for preparing a noncardiac zinc complex as claimed in claim 3, wherein: and the inorganic alkali in the step S2 is sodium hydroxide or potassium hydroxide.
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