CN111747973A - Binuclear zinc complex and preparation method and application thereof - Google Patents

Binuclear zinc complex and preparation method and application thereof Download PDF

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CN111747973A
CN111747973A CN202010625894.9A CN202010625894A CN111747973A CN 111747973 A CN111747973 A CN 111747973A CN 202010625894 A CN202010625894 A CN 202010625894A CN 111747973 A CN111747973 A CN 111747973A
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李昶红
李薇
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Abstract

The binuclear zinc complex disclosed by the invention takes p-chlorobenzoate ions and 1, 10-phenanthroline as ligands, has a binuclear structure, is good in stability of the molecular structure, has good luminous performance, can be widely applied to preparation of a light-emitting device as a luminous material, widens the selection range of the luminous material, and particularly has good antibacterial performance and particularly has good inhibition effect on staphylococcus aureus and escherichia coli. The method for preparing the binuclear zinc complex has the advantages of simple operation, mild reaction conditions, high yield and uniform crystal particles.

Description

Binuclear zinc complex and preparation method and application thereof
Technical Field
The invention relates to the technical field of novel multifunctional materials, and particularly relates to a binuclear zinc complex and a preparation method and application thereof.
Background
Zinc is an important vital element, participates in metabolic processes in organisms in various forms, including synthesis and degradation of carbohydrates, lipids, proteins and nucleic acids, and has special biological activity and catalytic action on a life system.
The simulation synthesis of coordination polymers with zinc, copper and the like as central ions and the research on the structure of the coordination polymers provide important information for people to know life phenomena related to the metal ions in a life system. During previous studies, the vast majority of the research has focused on their fluorescent probes [ Liu, x.et al.cn201010569190; yang, l.y.et al.cn201310273704, adsorption [ Lu, j.f.et al.cn201810734170 ], biosensing [ Li, s.d.et al.cn201810304829], PVC heat stabilizer [ Liu, f.q.et al.cn201410404671 ] and anticancer drug [ Pan, r.k.et al.cn201710676562; gao, C.Y.et al.CN201310159465], but the research on antibiosis and bacteriostasis is less.
Disclosure of Invention
The invention aims to provide a binuclear zinc complex with good luminous performance and antibacterial effect.
In order to achieve the above object, the present invention provides a binuclear zinc complex, which has a structural formula:
Figure BDA0002566527780000021
wherein, the binuclear zinc complex has a crystal structure, and the crystallographic data thereof are as follows: the crystal belongs to a monoclinic system, and the space group is C2/C; unit cell parameters:
Figure BDA0002566527780000022
Figure BDA0002566527780000023
β＝121.0580(10)°,
Figure BDA0002566527780000024
Figure BDA0002566527780000025
Dc＝1.509g/cm3z is 4, F (000) is 2256.2.58 ≤ theta is 25.50 ≤, mu (MoKa) is 0.797, GooF is 1.035, and crystal size is 0.49mm × 0.40.40 mm × 0.27mm R1＝0.0396，wR2＝0.0922。
In addition, the invention also provides a preparation method for the binuclear zinc complex, which comprises the following steps: adding a proper amount of p-chlorobenzoic acid and zinc salt into a mixed solution of acetonitrile and water, ultrasonically vibrating for 2-10 min at room temperature, then adding a proper amount of phenanthroline, adjusting the pH value to 6-7, stirring and reacting for 10-16 h at the temperature of 70-80 ℃ to obtain a light yellow solution, cooling and filtering, rotationally evaporating the solvent, and recrystallizing with acetonitrile and a methanol solvent to obtain a light yellow crystal, namely the binuclear zinc complex.
Wherein the p-chlorobenzoic acid, the zinc salt and the o-phenanthroline are all reactants, and the mass ratio of the p-chlorobenzoic acid, the zinc salt and the o-phenanthroline is (1-2): 2-5): 2-4; acetonitrile and water are used as reaction solvents, and the volume ratio is (1-6) to (1-3).
Wherein the zinc salt is one or more of zinc nitrate, zinc chloride, zinc sulfate, zinc carbonate, zinc hydroxide, basic zinc carbonate and zinc acetate.
In the preparation process, the pH value is adjusted to 6-7 by using alkali, and the alkali used for adjusting the pH value is one or two of sodium carbonate, sodium hydroxide, sodium bicarbonate, ammonia water, triethylamine and potassium hydroxide.
In addition, the invention also provides an application mode of the binuclear zinc complex as a fluorescent material and in preparation of an antibacterial material.
Specifically, the present invention defines the inclusion of the above dinuclear zinc complex in a photoluminescent device.
In addition, the invention also limits the inclusion of the above binuclear zinc complex in an antibacterial agent for inhibiting Staphylococcus aureus and Escherichia coli.
The invention has the following beneficial effects: 1. the binuclear zinc complex has a binuclear structure by taking p-chlorobenzoate ions and 1, 10-phenanthroline as ligands, and has good stability of the molecular structure. 2. The binuclear zinc complex has good luminescence performance, can be widely applied to preparation of luminescent devices as a luminescent material, and widens the selection range of the luminescent material. 3. The binuclear zinc complex also has good antibacterial performance, and particularly has good inhibition effect on staphylococcus aureus and escherichia coli. 4. The preparation method of the binuclear zinc complex has the advantages of simple operation, mild reaction conditions, high yield of the obtained product and uniform crystal particles.
Description of the drawings:
FIG. 1 is a schematic crystal structure of a binuclear zinc complex prepared in an example;
FIG. 2 is a fluorescent emission spectrum of a binuclear zinc complex;
FIG. 3 is a graph showing the thermal stability analysis of a binuclear zinc complex.
Detailed Description
In order to facilitate the understanding of those skilled in the art, the present invention will be further described with reference to the following examples, which are not intended to limit the present invention. It should be noted that the following examples are carried out in the laboratory, and it should be understood by those skilled in the art that the amounts of the components given in the examples are merely representative of the proportioning relationship between the components, and are not specifically limited.
1. Binuclear zinc complex-Zn2(p-C7H4O2Cl)4(C12H8N2)2·H2And (4) preparing O.
Adding 0.4mmol (62.5mg) of p-chlorobenzoic acid and 0.4mmol (about 39.76mg) of zinc hydroxide into a mixed solution of 20mL of acetonitrile and water (volume ratio is 4:1), ultrasonically vibrating for 5min at room temperature, adding 0.2mmol 1, 10-phenanthroline (36.0mg), adjusting pH value to 6-7 with sodium carbonate, continuously heating and stirring, controlling temperature to be 70-75 ℃, reacting for 10-16 hours (generally 13 hours), obtaining a light yellow solution, cooling, filtering, rotationally evaporating a solvent, recrystallizing with acetonitrile and a methanol solvent, obtaining a light yellow crystal, namely a binuclear zinc complex, wherein the size of the crystal is basically about 0.49mm × 0.40mm × 0.27mm, the yield is about 50.26%, and the melting point: 226 to 228 ℃. It should be noted that, in the above process for preparing the binuclear zinc complex, p-chlorobenzoic acid, zinc salt and o-phenanthroline are all reactants, and the mass ratio of the p-chlorobenzoic acid, the zinc salt and the o-phenanthroline can be (1-2): (2-5): (2-4); acetonitrile and water are used as reaction solvents, the volume ratio of the acetonitrile to the water can be (1-6) to (1-3), and the change of the ratio in the range has a slight influence on the yield. In addition, the zinc salt can be replaced by zinc nitrate, zinc chloride, zinc sulfate, zinc carbonate, basic zinc carbonate and zinc acetate besides zinc hydroxide. Or sodium carbonate can be replaced by sodium hydroxide, sodium bicarbonate, ammonia water, triethylamine and potassium hydroxide to adjust the pH value to 6-7.
The structural formula of the product is as follows:
Figure BDA0002566527780000051
in the above-mentioned Zn, Zn is2(p-C7H4O2Cl)4(C12H8N2)2·H2In O, p-C7H4O2The structural formula of Cl is:
Figure BDA0002566527780000052
C12H8N2the structural formula of (A) is:
Figure BDA0002566527780000053
elemental analysis (C)52H34Cl4Zn2N4O9) Theoretical (%) C, 55.01; h, 5.15; n, 4.97; measured value (%): C, 55.16; h, 3.03; and N, 4.95.
The IR major absorption peaks are: 3347(w),2924(s),1611(vs),1483(m),1427(vs),1346(vs),1281(m),1242(w),1065(m),851(m),729(m),685(w),557(w), 472 (w).
13C NMR(100Hz，CDCl3)(ppm)：31.7(Ar–COO)，127.7，128.6，131.0(C–Cl)，146.8(–COO)。
The binuclear zinc complex has a crystal structure, and the crystallographic data of the binuclear zinc complex are as follows: the crystal belongs to a monoclinic system, and the space group is C2/C; unit cell parameters:
Figure BDA0002566527780000054
Figure BDA0002566527780000055
β＝121.0580(10)°,
Figure BDA0002566527780000056
Dc＝1.509g/cm3z is 4, F (000) is 2256.2.58 ≤ theta is 25.50, mu (MoKa) is 0.797, GooF is 1.035, crystal size is 0.49mm × 0.40.40 mm × 0.27mm, R is 0.49mm 3532.40 mm 3926.27 mm1＝0.0396，wR2＝0.0922。
2. And (4) determining the crystal structure of the binuclear zinc complex.
The single crystals with a size of about 0.49mm × 0.40.40 mm × 0.27.27 mm were selected under a microscope, and subjected to diffraction experiments on a Bruker APEX-II CCD single crystal diffractometer using MoK α radiation (λ 0.071073nm) at 296(2) K to obtain a single crystal with a size of about 0.49mm 8978.40 mm 3532.27 mm
Figure BDA0002566527780000061
The scanning mode collects 18391 diffraction points and 4546 independent diffraction points [ R ] in the range of 2.58-25.05 DEGint＝0.0466,Rsigma＝0.0545]3342 observable diffraction points [ I>2σ(I)]For structural analysis and structural correction. All data were corrected for Lp factor and empirical absorption. The crystal structure is solved by a direct method by adopting an SHELXS-97 program, the structure refinement adopts a SHELXL-97 program, and the hydrogen atoms and the non-hydrogen atoms are respectively corrected by adopting isotropic and anisotropic temperature factors by a full matrix least square method. The final deviation factor R is 0.0457,
Figure BDA0002566527780000062
Figure BDA0002566527780000065
(Δ/σ)max＝0.00,S＝1.035,(Δρ)max0.476 and
Figure BDA0002566527780000063
Figure BDA0002566527780000064
the molecular structure of the complex is shown in FIG. 1, and the main bond lengths and bond angles are shown in Table 1. As can be seen from the crystal structure diagram 1, the title complex molecule is composed of 2 zinc (II) ions, 4 p-chlorobenzoic acid molecules, 2 o-phenanthroline molecules and 1 coordinated water molecule. The zinc (II) ion coordinates with 3 oxygen atoms, 2 nitrogen atoms and 1 water molecular oxygen atom from 3 p-chlorobenzoic acid molecules to form ZnN2O4A distorted octahedral structure. Different from other complexes (J.C.Cao, et al.CN106588961A; S.D.Li, et al.CN108395541A) in the same class, the structure of the complex is that two bridging molecules are provided, wherein one of the bridging molecules is bridged by an oxygen atom in a water molecule to form Zn-O-Zn effect, and the other one is bridged by two p-chlorobenzoic acid molecules to form two adjacent Zn-Zn; and carboxylic acid and central ion in the complex are coordinated in a monodentate and bidentate bridging mode. A Zn-Zn distance of
Figure BDA0002566527780000071
Slightly shorter than the same compounds
Figure BDA0002566527780000072
Figure BDA0002566527780000073
[W.Li,etal.Chem.J.Chin.Universities.29(2008)449],
Figure BDA0002566527780000074
[X.L.You,et al.Chin.J.Struct.Chem.33(2014)1007],
Figure BDA0002566527780000075
Figure BDA0002566527780000076
[F.F.Chang,etal.Eur.J.Inorg.Chem.(2017)546]}, but slightly longer than the same class of compounds
Figure BDA0002566527780000077
Figure BDA0002566527780000078
[F.F.Chang,et al.Eur.J.Inorg.Chem.(2017)540]. The bond angle range of each atomic bond connected with zinc is O/N-Zn-N/O84.02 (6) -174.21 (7) ° and the complex has the function of hydrogen bond and is mainly reflected between coordinated water molecules and oxygen atoms of paraoxybenzoic acid
Figure BDA0002566527780000079
Hydrogen bonding contributes to the stability of the complex.
TABLE 1 major bond length of the complexes
Figure BDA00025665277800000710
Angle of and key (°)
Figure BDA00025665277800000711
3. And (3) measuring the spectral performance of the binuclear zinc complex.
The infrared spectrum of the binuclear zinc complex is measured, and the result shows that: (1)3347cm-1The characteristic OH absorption peak of water appears; (2)1611, 1483cm–1And 1611, 1346cm–1Is p-chlorobenzoic acid vas(coo–)And vs(coo–)Absorption peak Δ ν (ν)as(C＝O)-υs(C＝O)) 128 and 293cm, respectively-1Two coordination modes of monodentate and bidentate bridging exist; (3)1427cm-1、851cm-1And 729cm-1A phenanthroline characteristic absorption peak appears; (4)557cm-1And 472cm-1The characteristic absorption peak of zinc nitrogen and zinc oxygen appears.
The fluorescence property of the binuclear zinc complex is measured, and the result shows that: (1) at room temperature, the solid fluorescence spectrum of the complex is measured, and under the excitation of ultraviolet light of 420-600 nm, the solid fluorescence emission spectrum of the material is shown in figure 2, wherein A: an emission spectrum; b: excitation spectrum. (2) As can be seen from FIG. 2, the emission spectrum of the complex was 418nm (. lamda.) (λ)ex390nm), this fluorescence emission spectrum is due to transitions between pi-pi, and 380nm (lambda) of the free ligand p-chlorobenzoic acid emission spectrumex＝300nm) compared with each other, the complex is red-shifted by 38nm, and is attributed to the interaction between the ligand and the metal ion in the complex, and compared with other complexes [ Li, W.et al, Chin.J.Inorg.chem.27(2011)1921]The fluorescence performance is enhanced; (3) the emission enhancement is a better fluorescent material due to the transfer of charges from the ligand to the metal ion, which is formed due to the high stability and poor solubility of the complex, which can be used in a photoluminescent device.
4. And (3) analyzing the thermal stability of the binuclear zinc complex.
FIG. 3 is a thermal stability analysis of the title complex: in an air atmosphere, the weight loss is almost 0 below 100 ℃, namely the complex has good thermal stability below 100 ℃. The weight loss in the range of 100 ℃ to 600 ℃ is carried out in three stages. 140-160 ℃ is the first stage, the weight loss rate is about 1.55%, and the corresponding lost product is probably 1 water molecule (the theoretical value is 1.59%); the temperature of 160-258 ℃ is the second stage, the weight loss rate is about 33.03%, and the corresponding lost product may be 2 o-phenanthroline (the theoretical value is 33.85%); at the third stage of 258-450 ℃, the weight loss rate is accumulated to about 52.18 percent, and the corresponding lost product is probably 4 p-chlorobenzoic acid (the accumulated theoretical value is 51.32 percent); since the final product is zinc oxide in an air atmosphere, the final residue retention is about 14.10% (theoretical 14.38%).
5. And (3) determining the antibacterial activity of the binuclear zinc complex.
The experimental method comprises the following steps: the antibacterial performance test of the experiment adopts a culture medium diffusion method and a nutrient broth dilution method for testing, the antibacterial capacity is large, and the results are listed in table 2 in the form of antibacterial diameter and minimum antibacterial concentration.
Wherein the result measured by the medium diffusion method is represented by the diameter of the inhibition zone; the result of the dilution method by the nutrient broth is expressed as the Minimum Inhibitory Concentration (MIC) of the complex, and generally, when the MIC of the sample is less than 800mg/L, the sample is considered to have an inhibitory effect. The results of the bacteriostatic experiments show that: (1) wherein, the bacteriostatic action of the p-chlorobenzoic acid on escherichia coli and staphylococcus aureus is poor; 1, 10-phenanthroline bacteriostatic diameter fraction on escherichia coli and staphylococcus aureusRespectively 23mm and 13mm, and the corresponding minimum inhibitory concentration is 80mg/L-1And 350mg/L-1Fully indicates that 1, 10-phenanthroline has an antibacterial effect on escherichia coli, but only has a medium-intensity antibacterial effect on staphylococcus aureus; (2) the binuclear zinc complex has a good inhibition effect on escherichia coli and staphylococcus aureus, and the diameter of an inhibition zone is larger than 20 mm. The minimum bacteriostatic concentration is less than 100mg/L-1The complex has strong bacteriostatic action on escherichia coli and staphylococcus aureus and can be used as an antibacterial agent.
TABLE 2 inhibitory diameters and minimum inhibitory concentrations of binuclear zinc complexes and other control substances
Figure BDA0002566527780000091
In summary, in the above embodiments, the binuclear zinc complex has a binuclear structure with p-chlorobenzoate ions and 1, 10-phenanthroline as ligands, and the stability of the molecular structure of the complex is good. The binuclear zinc complex has good luminescence performance, can be widely applied to preparation of luminescent devices as a luminescent material, widens the selection range of the luminescent material, and particularly has good antibacterial performance, and particularly has good inhibition effect on staphylococcus aureus and escherichia coli. As can be seen from the preparation process of the binuclear zinc complex, the preparation process is simple to operate, the reaction conditions are mild, the yield of the obtained product is high, and the crystal particles are uniform.
The above embodiments are preferred implementations of the present invention, and the present invention can be implemented in other ways without departing from the spirit of the present invention.
Finally, it should be emphasized that some of the descriptions of the present invention have been simplified to facilitate the understanding of the improvements of the present invention over the prior art by those of ordinary skill in the art, and that other elements have been omitted from this document for the sake of clarity, and those skilled in the art will recognize that these omitted elements may also constitute the content of the present invention.

Claims (10)

1. A binuclear zinc complex, characterized in that it has a repeating structural unit of the following structure:
Figure FDA0002566527770000011
2. the dinuclear zinc complex according to claim 1, wherein: the binuclear zinc complex has a crystal structure, and the crystallographic data of the binuclear zinc complex are as follows: the crystal belongs to a monoclinic system, and the space group is C2/C; unit cell parameters:
Figure FDA0002566527770000012
Figure FDA0002566527770000013
β＝121.0580(10)°,
Figure FDA0002566527770000014
Dc＝1.509g/cm3z is 4, F (000) is 2256.2.58 ≤ theta is 25.50 ≤, mu (MoKa) is 0.797, GooF is 1.035, and crystal size is 0.49mm × 0.40.40 mm × 0.27mm R1＝0.0396，wR2＝0.0922。
3. The method for preparing the dinuclear zinc complex according to claim 1, comprising the steps of: adding a proper amount of p-chlorobenzoic acid and zinc salt into a mixed solution of acetonitrile and water, ultrasonically vibrating for 2-10 min at room temperature, then adding a proper amount of phenanthroline, adjusting the pH value to 6-7, stirring and reacting for 10-16 h at the temperature of 70-80 ℃ to obtain a light yellow solution, cooling and filtering, rotationally evaporating the solvent, and recrystallizing with acetonitrile and a methanol solvent to obtain a light yellow crystal, namely the binuclear zinc complex.
4. The production method according to claim 3, characterized in that: wherein p-chlorobenzoic acid, zinc salt and o-phenanthroline are all reactants, and the mass ratio of p-chlorobenzoic acid, zinc salt and o-phenanthroline is (1-2): 2-5): 2-4; acetonitrile and water are used as reaction solvents, and the volume ratio is (1-6) to (1-3).
5. The method of claim 4, wherein: the zinc salt is one or more of zinc nitrate, zinc chloride, zinc sulfate, zinc carbonate, zinc hydroxide, basic zinc carbonate and zinc acetate.
6. The production method according to any one of claims 3 to 5, characterized in that: and adjusting the pH value to 6-7 by using alkali, wherein the alkali used for adjusting the pH value is one or two of sodium carbonate, sodium hydroxide, sodium bicarbonate, ammonia water, triethylamine and potassium hydroxide.
7. Use of the dinuclear zinc complex according to claim 1 or 2 as a fluorescent material.
8. Use of the dinuclear zinc complex according to claim 1 or 2 for the preparation of an antibacterial material.
9. A photoluminescent device, characterized by: comprising the dinuclear zinc complex according to claim 1 or 2.
10. An antibacterial agent for inhibiting staphylococcus aureus and escherichia coli, characterized by: comprising the dinuclear zinc complex according to claim 1 or 2.
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CN112300405A (en) * 2020-11-04 2021-02-02 湖南工学院 Copper coordination polymer and preparation method, crystal and application thereof

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