CN111747973B - Binuclear zinc complex and preparation method and application thereof - Google Patents
Binuclear zinc complex and preparation method and application thereof Download PDFInfo
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- CN111747973B CN111747973B CN202010625894.9A CN202010625894A CN111747973B CN 111747973 B CN111747973 B CN 111747973B CN 202010625894 A CN202010625894 A CN 202010625894A CN 111747973 B CN111747973 B CN 111747973B
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- 239000011701 zinc Substances 0.000 title claims abstract description 48
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims description 11
- 238000010668 complexation reaction Methods 0.000 title description 2
- 239000013078 crystal Substances 0.000 claims abstract description 21
- 230000000844 anti-bacterial effect Effects 0.000 claims abstract description 18
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 241000588724 Escherichia coli Species 0.000 claims abstract description 10
- 241000191967 Staphylococcus aureus Species 0.000 claims abstract description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 30
- XRHGYUZYPHTUJZ-UHFFFAOYSA-N 4-chlorobenzoic acid Chemical compound OC(=O)C1=CC=C(Cl)C=C1 XRHGYUZYPHTUJZ-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 6
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 6
- 229940007718 zinc hydroxide Drugs 0.000 claims description 6
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 6
- 230000002401 inhibitory effect Effects 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 235000017550 sodium carbonate Nutrition 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000003242 anti bacterial agent Substances 0.000 claims description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000002447 crystallographic data Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 3
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 3
- 239000000243 solution Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims 1
- 239000003446 ligand Substances 0.000 abstract description 6
- -1 p-chlorobenzoate ions Chemical class 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000005764 inhibitory process Effects 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 239000002245 particle Substances 0.000 abstract description 3
- 238000004020 luminiscence type Methods 0.000 abstract description 2
- 150000003751 zinc Chemical class 0.000 description 11
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 230000004580 weight loss Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 4
- 238000002189 fluorescence spectrum Methods 0.000 description 4
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000000295 emission spectrum Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 235000000621 Bidens tripartita Nutrition 0.000 description 2
- 240000004082 Bidens tripartita Species 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 230000003385 bacteriostatic effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000002815 broth microdilution Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 208000006637 fused teeth Diseases 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 235000015097 nutrients Nutrition 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- 239000011667 zinc carbonate Substances 0.000 description 2
- 235000004416 zinc carbonate Nutrition 0.000 description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 description 2
- 239000011592 zinc chloride Substances 0.000 description 2
- 235000005074 zinc chloride Nutrition 0.000 description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 2
- 229960001763 zinc sulfate Drugs 0.000 description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 description 2
- 125000006414 CCl Chemical group ClC* 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- UHIJLWIHCPPKOP-UHFFFAOYSA-N [N].[Zn] Chemical compound [N].[Zn] UHIJLWIHCPPKOP-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000002246 antineoplastic agent Substances 0.000 description 1
- 229940041181 antineoplastic drug Drugs 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 235000014633 carbohydrates Nutrition 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000000695 excitation spectrum Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 239000012760 heat stabilizer Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002632 lipids Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 150000007523 nucleic acids Chemical class 0.000 description 1
- 102000039446 nucleic acids Human genes 0.000 description 1
- 108020004707 nucleic acids Proteins 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000012916 structural analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229940043825 zinc carbonate Drugs 0.000 description 1
- 229960001939 zinc chloride Drugs 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- PCHQDTOLHOFHHK-UHFFFAOYSA-L zinc;hydrogen carbonate Chemical group [Zn+2].OC([O-])=O.OC([O-])=O PCHQDTOLHOFHHK-UHFFFAOYSA-L 0.000 description 1
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- 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
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
- A01N37/10—Aromatic or araliphatic carboxylic acids, or thio analogues thereof; Derivatives thereof
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Abstract
The binuclear zinc complex takes p-chlorobenzoate ions and 1, 10-phenanthroline as ligands, has a binuclear structure, has good molecular structure stability, has good luminescence property, can be widely used as a luminescent material for preparing luminescent devices, widens the selection range of the luminescent material, and particularly has good antibacterial property, 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
Technical Field
The invention relates to the technical field of multifunctional new materials, in particular to a binuclear zinc complex and a preparation method and application thereof.
Background
Zinc is an important vital element and 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 vital system.
The simulation of synthesis of coordination polymers with zinc, copper, etc. as central ions and the study of their structure will provide important information for people to recognize life phenomena related to these metal ions in life systems. In the past research process, most of the fluorescent probes are focused on [ Liu, X.et al CN201010569190; yang, l.y.et al, cn201310273704], adsorption [ Lu, j.f.et al, cn20181073417 ], biosensing [ Li, s.d.et al, cn201810304829], PVC heat stabilizer [ Liu, f.q.et al, cn2014104046 71], anticancer drug [ Pan, r.k.et al, cn201710676562; gao, C.Y.et al CN201310159565 ], but has little research on antibiosis and bacteriostasis.
Disclosure of Invention
The invention aims at providing 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 the structural formula:
wherein, the binuclear zinc complex is in 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:
β＝121.0580(10)°,/>
Dc＝1.509g/cm 3 z= 4,F (000) = 2256.2.58 +.θ+.25.50 μ (MoKa) =0.797, goof=1.035, crystal size: 0.49mm by 0.40mm by 0.27mm R 1 ＝0.0396，wR 2 ＝0.0922。
In addition, the invention also provides a preparation method for the binuclear zinc complex, which comprises the following steps: adding proper amount of p-chlorobenzoic acid and zinc salt into a mixed solution of acetonitrile and water, carrying out ultrasonic vibration at room temperature for 2-10 min, then adding proper amount of o-phenanthroline, regulating the pH value to 6-7, stirring and reacting for 10-16 h at 70-80 ℃ to obtain a pale yellow solution, cooling and filtering, rotationally evaporating the solvent, and recrystallizing with acetonitrile and methanol solvent to obtain pale yellow crystals, namely the binuclear zinc complex.
Wherein, p-chlorobenzoic acid, zinc salt and phenanthroline are reactants, and the mass ratio 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.
Wherein, in the preparation process, the pH value is regulated to 6-7 by alkali, and the alkali used for regulating 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 serving as a fluorescent material in preparation of antibacterial materials.
In particular, the present invention defines the inclusion of the above dinuclear zinc complexes in a photoluminescent device.
The present invention also provides an antibacterial agent for inhibiting Staphylococcus aureus and Escherichia coli, which comprises the binuclear zinc complex.
The beneficial effects of the invention are mainly as follows: 1. the binuclear zinc complex takes p-chlorobenzoate ions and 1, 10-phenanthroline as ligands, has a binuclear structure, and has good molecular structure stability. 2. The binuclear zinc complex has good luminescence property, can be widely used as a luminescent material for preparing luminescent devices, and widens the selection range of the luminescent material. 3. The binuclear zinc complex provided by the invention 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 diagram of the crystal structure of a binuclear zinc complex prepared in the examples;
FIG. 2 is a graph of fluorescence emission spectra of binuclear zinc complexes;
FIG. 3 is a graph of thermal stability analysis of binuclear zinc complexes.
Detailed Description
The present invention is further illustrated below in conjunction with examples, which are not intended to limit the scope of the invention, in order to facilitate understanding of those skilled in the art. It should be noted in advance that the following examples are carried out in a laboratory, and it should be understood by those skilled in the art that the amounts of the components given in the examples merely represent the ratio relationship between the components, and are not particularly limited.
1. Binuclear zinc complex-Zn 2 (p-C 7 H 4 O 2 Cl) 4 (C 12 H 8 N 2 ) 2 ·H 2 And (3) preparation of O.
Adding 0.4mmol (62.5 mg) of p-chlorobenzoic acid and 0.4mmol (about 39.76 mg) 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 of 1, 10-phenanthroline (36.0 mg), regulating pH value to 6-7 by sodium carbonate, continuously heating and stirring, controlling the temperature to 70-75 ℃ for 10-16 hours (generally 13 hours), obtaining a pale yellow solution, cooling, filtering, rotationally evaporating the solvent, recrystallizing by acetonitrile and methanol solvent to obtain pale yellow crystals, namely the binuclear zinc complex, wherein the crystal size is basically about 0.49mm multiplied by 0.40mm multiplied by 0.27mm, the yield is about 50.26%, and the melting point is as follows: 226-228 ℃. It should be noted that in the process of 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 to the zinc salt to the o-phenanthroline can be (1-2): 2-5): 2-4; acetonitrile and water are reaction solvents, the volume ratio of the acetonitrile to the water can be (1-6): (1-3), and the change of the proportion in the range has little influence on the yield. In addition, zinc salts other than zinc hydroxide may be replaced with zinc nitrate, zinc chloride, zinc sulfate, zinc carbonate, basic zinc carbonate, or zinc acetate. Sodium hydroxide, sodium bicarbonate, ammonia water, triethylamine and potassium hydroxide can be used for replacing sodium carbonate to adjust the pH value to 6-7.
The structural formula of the product is as follows:
the above Zn 2 (p-C 7 H 4 O 2 Cl) 4 (C 12 H 8 N 2 ) 2 ·H 2 In O, p-C 7 H 4 O 2 The structural formula of Cl is: />
C 12 H 8 N 2 The structural formula is as follows:
elemental analysis (C) 52 H 34 Cl 4 Zn 2 N 4 O 9 ) Theoretical values (%) C,55.01; h,5.15; n,4.97; measurement (%) C,55.16; h,3.03; n,4.95.
The IR main absorption peaks were: 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).
13 C NMR(100Hz，CDCl 3 )δ(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 has crystallographic data: the crystal belongs to a monoclinic system, and the space group is C2/C; unit cell parameters:
β＝121.0580(10)°,
Dc＝1.509g/cm 3 z= 4,F (000) = 2256.2.58 +.θ+.25.50 μ (MoKa) =0.797, goof=1.035, crystal size: 0.49mm by 0.40mm by 0.27mm, R 1 ＝0.0396，wR 2 ＝0.0922。
2. And (5) measuring the crystal structure of the binuclear zinc complex.
Single crystals of about 0.49mm by 0.40mm by 0.27mm in size were selected under a microscope and subjected to diffraction experiments on an a Bruker APEX-II CCD single crystal diffractometer using MoK alpha rays (λ= 0.071073 nm) at 296 (2) K to
The scanning mode is to collect 18391 diffraction points in total within the range of theta being more than or equal to 2.58 and less than or equal to 25.05 degrees, wherein, the 4546 diffraction points are independent int ＝0.0466,R sigma ＝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 through a SHELXS-97 procedure, the structure is refined through the SHELXL-97 procedure, and the hydrogen atoms and the non-hydrogen atoms are respectively corrected through a full matrix least square method through isotropic and anisotropic temperature factors. The final deviation factor r=0.0457,
(Δ/σ) max ＝0.00,S＝1.035,(Δρ) max =0.476 and->
The molecular structure of the complex is shown in FIG. 1, and the main bond lengths and bond angles are shown in Table 1. From the crystal structure diagram 1, the title complex molecule consists of 2 zinc (II) ions, 4 p-chlorobenzoic acid molecules, 2 phenanthroline molecules and 1 coordination water molecule. Zinc (II) ions with 3 oxygen atoms, 2 nitrogen atoms from 3 p-chlorobenzoic acid moleculesAnd 1 water molecule oxygen atom coordinates to form ZnN 2 O 4 Is a deformed octahedral structure. Unlike other complexes of the same class (J.C.Cao, et al CN106588961A; S.D.Li, et al CN108395541A), there are two bridging molecules, one of which forms a Zn-O-Zn action by bridging oxygen atoms in water molecules, and the other of which bridges two adjacent Zn-Zn molecules by two p-chlorobenzoic acid molecules; and the carboxylic acid and the central ion in the complex are coordinated through two modes of single-tooth bridging and double-tooth bridging. Zn-Zn distance is
Slightly shorter than the similar compound->
[W.Li,et al.Chem.J.Chin.Universities.29(2008)449],/>
[X.L.You,et al.Chin.J.Struct.Chem.33(2014)1007],/>
[F.F.Chang,et al.Eur.J.Inorg.Chem.(2017)546]But slightly longer than the same class of compounds +.>
[F.F.Chang,et al.Eur.J.Inorg.Chem.(2017)540]. The bond angle range of each atom connected with zinc is O/N-Zn-N/O84.02 (6) to 174.21 (7) °, and in addition, the complex has the function of hydrogen bond, which is mainly reflected between coordinated water molecules and oxygen atoms of paraoxybenzoic acid
The hydrogen bonding is beneficial to the stability of the complex.
TABLE 1 major bond lengths of the complexes
Bond angle (°)
3. Spectral properties of binuclear zinc complexes were determined.
The infrared spectrum of the binuclear zinc complex is measured, and the result shows that: (1) 3347cm -1 An OH characteristic absorption peak of water appears; (2) 1611, 1483cm –1 And 1611, 1346cm –1 Is p-chlorobenzoic acid v as(coo–) And v s(coo–) Absorption peak of Deltav (v) as(C＝O) -υ s(C＝O) ) 128 and 293cm respectively -1 Two coordination modes of single-tooth and double-tooth bridging are illustrated; (3) 1427cm -1 、851cm -1 And 729cm -1 O-phenanthroline characteristic absorption peaks appear at the positions; (4) 557cm -1 And 472cm -1 There appears a characteristic absorption peak of zinc nitrogen and zinc oxygen.
The fluorescent properties of the binuclear zinc complex are measured, and the results show 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 418nm (lambda ex =390 nm), this fluorescence emission spectrum is due to the transition between pi-pi, and the free ligand p-chlorobenzoic acid emission spectrum is 380nm (λ ex =300 nm) the complex is red shifted by 38nm, ascribed to the interaction between the ligand and the metal ion in the complex, compared to other complexes [ Li, w.et al, chip.j. Inorg. Chem.27 (2011) 1921]The fluorescence performance is enhanced; (3) The enhancement of the emitted light is due to the transfer of charges from the ligand to the metal ion, which is a better fluorescent material due to the high stability and poor solubility of the complex, the double pairThe core zinc complex can be used on photoluminescent devices.
4. Analysis of the thermal stability properties of binuclear zinc complexes.
FIG. 3 is a thermal stability analysis of the title complex: the weight loss is almost 0 below 100 ℃ in the air atmosphere, 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. The weight loss rate is about 1.55% in the first stage at 140-160 ℃, and the corresponding lost product is probably 1 water molecule (theoretical value is 1.59%); 160-258 ℃ is the second stage, the weight loss rate is about 33.03%, and 2 phenanthroline (theoretical value is 33.85%) are corresponding to the lost product; 258-450 ℃ is the third stage, the weight loss rate is accumulated by about 52.18%, and the corresponding lost product is possibly 4 p-chlorobenzoic acid (the accumulated theoretical value is 51.32%); since the final product was zinc oxide in an air atmosphere, the final residue retention was about 14.10% (theoretical 14.38%).
5. And (3) measuring the antibacterial activity of the binuclear zinc complex.
The experimental method comprises the following steps: the antibacterial performance test of the experiment is carried out by adopting two methods of a culture medium diffusion method and a nutrient broth dilution method, and the antibacterial capacity is measured, and the results are shown in table 2 in the form of antibacterial diameter and minimum antibacterial concentration.
Wherein the result measured by the culture medium diffusion method is represented by the diameter of the bacteriostasis ring; the results of the nutrient broth dilution are expressed as the Minimum Inhibitory Concentration (MIC) of the complex, and the sample is generally considered to have an inhibitory effect when the MIC of the sample is less than 800 mg/L. The antibacterial experiment result shows that: (1) Wherein, the antibacterial effect of the p-chlorobenzoic acid on escherichia coli and staphylococcus aureus is poor; the antibacterial diameters of 1, 10-phenanthroline on escherichia coli and staphylococcus aureus are 23mm and 13mm respectively, and the corresponding minimum antibacterial concentration is 80mg/L -1 And 350mg/L -1 Fully shows that the 1, 10-phenanthroline has antibacterial effect on escherichia coli, and has only moderate-intensity antibacterial effect on staphylococcus aureus; (2) The binuclear zinc complex has good inhibition effect on escherichia coli and staphylococcus aureus, and the diameter of a bacteriostasis zone is larger than 20mm. The minimum inhibitory concentration is smaller than100mg/L -1 The complex has strong antibacterial effect on escherichia coli and staphylococcus aureus, and can be used as an antibacterial agent.
TABLE 2 bacteriostatic diameter and minimum bacteriostatic concentration of binuclear zinc complex and other controls
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 molecular structure of the complex has good stability. The binuclear zinc complex has good luminous performance, can be widely used as a luminous material for preparing luminous devices, 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 preparation process of the binuclear zinc complex has the advantages of simple operation, mild reaction conditions, high yield of the obtained product and uniform crystal particles.
The foregoing embodiments are preferred embodiments of the present invention, and in addition, the present invention may be implemented in other ways, and any obvious substitution is within the scope of the present invention without departing from the concept of the present invention.
Finally, it should be emphasized that some descriptions of the present invention have been simplified and some other elements have been omitted for clarity in order to make it easier for a person of ordinary skill in the art to understand the improvements of the present invention over the prior art, and those omitted elements will be recognized by those skilled in the art to make up the present invention.
Claims (8)
1. A dinuclear zinc complex, characterized in that it has a repeating structural unit of the structure:
the crystallographic data are: the crystal belongs to monoclinic system, and the space group isC2/cThe method comprises the steps of carrying out a first treatment on the surface of the Unit cell parameters:a = 23.413(3) Å，b = 15.6066(17) Å，c = 15.6156(17) Å， β= 121.0580(10) º, V = 4888.0(9) Å 3 ，Dc = 1.509 g/cm 3 ，Z = 4，F(000) = 2256. 2.58≤θ≤25.50，μ(MoKa) = 0.797, GooF=1.035, crystal size: 0.49mm by 0.40mm by 0.27mmR 1 = 0.0396，wR 2 = 0.0922。
2. The method for preparing the binuclear zinc complex according to claim 1, which comprises the following steps: adding proper amount of p-chlorobenzoic acid and zinc hydroxide into a mixed solution of acetonitrile and water, performing ultrasonic vibration at room temperature for 2-10 min, then adding proper amount of o-phenanthroline, adjusting the pH value to 6-7, stirring and reacting at 70-80 ℃ for 10 h-16 h to obtain a pale yellow solution, cooling and filtering, performing rotary evaporation on the solvent, and recrystallizing with acetonitrile and methanol solvent to obtain pale yellow crystals, namely the dinuclear zinc complex.
3. The preparation method according to claim 2, characterized in that: wherein p-chlorobenzoic acid, zinc hydroxide and phenanthroline are reactants, and the mass ratio of the p-chlorobenzoic acid to the zinc hydroxide to the 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).
4. A method of preparation according to claim 2 or 3, characterized in that: and (3) 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.
5. Use of the binuclear zinc complex according to claim 1 as fluorescent material.
6. Use of the binuclear zinc complex of claim 1 for preparing antibacterial material.
7. A photoluminescent device, characterized by: comprising the binuclear zinc complex according to claim 1.
8. An antibacterial agent for inhibiting staphylococcus aureus and escherichia coli, characterized by: comprising the binuclear zinc complex according to claim 1.
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