Phenanthroline ligand-containing Cd (II) complex and preparation method and application thereof
阅读说明：本技术 一种含邻菲罗啉配体的Cd(II)配合物及其制备方法和应用 (Phenanthroline ligand-containing Cd (II) complex and preparation method and application thereof ) 是由 冯勋 李荣芳 张甜 刘新芳 洪满洲 陈楠 于 2020-06-30 设计创作，主要内容包括：本发明涉及一种含邻菲罗啉配体的Cd(II)配合物及其制备方法和应用。配合物化学式为Cd(phen)<Sub>2</Sub>ASBA·H<Sub>2</Sub>O,其中ASBA为4-氨基-N-(5-甲基-1,2-硫代噻唑-3-基)苯磺酰胺,phen为1,10-邻菲罗啉,配合物晶体属于三斜晶系,空间群为P<Sub>-1</Sub>,晶胞参数为：<Image he="69" wi="337" file="DDA0002562320490000011.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image><Image he="62" wi="700" file="DDA0002562320490000012.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>α＝105.116(4)°,β＝97.181(3)°,γ＝98.744(4)°,<Image he="75" wi="399" file="DDA0002562320490000013.GIF" imgContent="drawing" imgFormat="GIF" orientation="portrait" inline="no"></Image>Z＝4。本发明的配合物材料晶体结晶性较好,无毒、无污染,热稳定性高,抑菌性能优良,原料成本低。(The invention relates to a phenanthroline ligand-containing Cd (II) complex and a preparation method and application thereof. The chemical formula of the complex is Cd (phen) 2 ASBA·H 2 O, wherein ASBA is 4-amino-N- (5-methyl-1, 2-thiothiazol-3-yl) benzenesulfonamide, phen is 1, 10-phenanthroline, the complex crystal belongs to a triclinic crystal system, and the space group is P ‑1 The unit cell parameters are: α＝105.116(4)°，β＝97.181(3)°，γ＝98.744(4)°， and Z is 4. The complex material crystal of the invention has the advantages of good crystallinity, no toxicity, no pollution, high thermal stability, excellent antibacterial performance and low cost of raw materials.)
1. A Cd (II) complex containing a phenanthroline ligand, which is characterized in that: chemical formula is Cd (phen)2ASBA·H2O, wherein ASBA is 4-amino-N- (5-methyl-1, 2-thiothiazol-3-yl) benzenesulfonamide, phen is 1, 10-phenanthroline, the complex crystal belongs to a triclinic crystal system, and the space group is P-1The unit cell parameters are:
2. the method for preparing a phenanthroline ligand-containing Cd (II) complex as claimed in claim 1, wherein: the method comprises the following steps:
(1) adding an organic ligand ASBA into a mixed solution of water and ethanol, and stirring and mixing to obtain a solution A;
(2) taking Cd (ClO)4)2·6H2O or Cd (CH)3COO)2·4H2Adding O into a mixed solution of water and an organic solvent, and stirring and mixing to obtain a solution B;
(3) adding the solution A into the solution B, stirring to obtain a turbid solution C, adding a ligand phen into the turbid solution C, adjusting the pH to 6.5-7.5, stirring to obtain a mixed solution D, and stirring the mixed solution D with a magnetic stirrer at normal temperature and normal pressure to obtain a precursor solution E;
(4) transferring the precursor solution E into a hydrothermal reaction kettle with polytetrafluoroethylene, sealing the reaction kettle, putting the reaction kettle into an oven, selecting a temperature control mode to carry out reaction, controlling the temperature to be 60-100 ℃ and reacting for 60-90h, controlling the reaction kettle to cool to room temperature at a cooling rate of 5 ℃/h after the reaction is finished, collecting colorless crystals appearing at the bottom in the reaction kettle, and washing and drying the collected crystals to obtain the colorless rhombus blocky crystal complex.
3. The method for preparing a phenanthroline ligand-containing Cd (II) complex as claimed in claim 2, wherein: the adding amount ratio of the organic ligand ASBA and the mixed solution in the step (1) is as follows: 0.1-0.5mmol of organic ligand is added to each 10ml of the mixed solution.
4. The method for preparing a phenanthroline ligand-containing Cd (II) complex as claimed in claim 2, wherein: the volume ratio of the water to the organic solvent in the step (2) is 0.5:1-3:1, and the organic solvent is methanol, ethanol, DMF or DMSO.
5. The method for preparing a phenanthroline ligand-containing Cd (II) complex as claimed in claim 1, wherein: cd (ClO) in the step (2)4)2·6H2O、Cd(CH3COO)2·4H2The adding amount ratio of O to the mixed solution is as follows: 0.1mmol Cd (ClO) per 10ml water and organic solvent mixture4)2·6H2O or Cd (CH)3COO)2·4H2O。
6. The method for preparing a phenanthroline ligand-containing Cd (II) complex as claimed in claim 1, wherein: the adding amount ratio of the solution B, the solution A and the ligand phen in the step (3) is as follows: 10-50ml of solution B and 0.1-0.2mmol of phen are added to every 10ml of solution A.
7. The method for preparing a phenanthroline ligand-containing Cd (II) complex as claimed in claim 1, wherein: and (3) adjusting the pH value of the solution by using dilute nitric acid and sodium hydroxide.
8. The method for preparing a phenanthroline ligand-containing Cd (II) complex as claimed in claim 1, wherein: the drying temperature of the vacuum drying oven in the step (5) is controlled to be 50-70 ℃.
9. The use of the phenanthroline ligand-containing Cd (II) complex of claim 1 for bacteriostasis.
10. The use of the phenanthroline ligand-containing Cd (II) complex as claimed in claim 1 in fluorescent luminescent materials.
Technical Field
The invention relates to the technical field of complex compounds, in particular to a Cd (II) complex containing phenanthroline ligands and a preparation method and application thereof.
Background
Having d10The electronic structure of Cd ions has unique spectroscopic characteristics that make them important in life sciences and luminescent material research. Over the last few years, the clinical success of cisplatin and its use have led to a wide interest in the search for new metal-based anticancer drugs, however, platinum anticancer drugs are extremely expensive, prone to serious side effects, and the selectivity of this class of compounds is limited, and in addition to their effectiveness, they have acquired resistance. Therefore, there is a need to develop new metal-based anti-cancer anti-inflammatory, bacteriostatic therapeutic agents with different mechanisms of action that overcome the above-mentioned disadvantages of platinum-based chemotherapeutic agents. In recent years, transition metal complexes based on amino acids have stable physicochemical properties, adjustable functions and wide application range, and have attracted extensive attention and research interest in bio-inorganic medical materials and potential applications thereof in many scientific fields. Applications are in many areas, such as gas storage, molecular recognition and separation, chemical catalysis, sensing, ion exchange and drug delivery. Has become a new direction for the research and development of new luminescent materials. Nitrogen-containing heterocyclic compounds are currently used for their broad range of biological activities, such as insecticidal, fungicidal, herbicidal, antiviral, and anticancer properties. Has attracted great interest in the field of modern supramolecular chemistry. Thiazole compounds are important components of nitrogen-containing heterocycles and are widely used in pesticides and pharmaceuticals due to their unique structures. Many of them are used as commercial insecticides, fungicides and weedsAnd (3) preparing. Efficient and simple synthesis methods the supramolecular functional compounds are largely dependent on the appropriate choice of carefully designed organic building blocks as terminal components or bridging groups as nodes.
The metal organic supermolecular chemistry is a novel scientific research subject related to multiple subjects such as inorganic chemistry, organic chemistry, coordination chemistry and the like, has attracted worldwide attention and is based on d10The metal organic framework compound with electronic configuration, heterocyclic compound such as azole and thiazole can be combined with amino acid ions especially necessary for life, such as glycine and glutamic acid to form protein, and have biological activity. Meanwhile, 1, 10-phenanthroline (abbreviated as phen) is generally used as a simple secondary N receptor building block, can coordinate the environment and stabilize the structure, and is also a common redox indicator. It is a bidentate heterocyclic compound ligand, and the introduction of the molecules increases the absorption of light often due to a conjugated structure. Because of the existence of aromatic ring, the beneficial formation of pi-pi stacking or hydrogen bond interaction, improvement can improve the stability of the compound, improve the structure of the compound. The metal organic framework compound has the advantages of modification and adjustable function, but most of the organic framework compounds of transition metal and rare earth metal have poor water solubility due to molecular polymerization, so that the biological bacteriostasis process is difficult to complete.
Disclosure of Invention
The invention aims to solve the technical problems and the defects, and provides a phenanthroline ligand-containing Cd (II) complex and a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the technical scheme that: a Cd (II) complex containing phenanthroline ligand, which has a chemical formula of Cd (phen)2ASBA·H2O, wherein ASBA is 4-amino-N- (5-methyl-1, 2-thiothiazol-3-yl) benzenesulfonamide, phen is 1, 10-phenanthroline, the complex crystal belongs to a triclinic system, the space group is P-1, and the unit cell parameters are as follows:
a preparation method of a phenanthroline ligand-containing Cd (II) complex comprises the following steps:
(1) adding an organic ligand ASBA into a mixed solution of water and ethanol, and stirring and mixing to obtain a solution A;
(2) taking Cd (ClO)4)2·6H2Adding O into a mixed solution of water and an organic solvent, and stirring and mixing to obtain a solution B;
(3) adding the solution A into the solution B, stirring to obtain a turbid solution C, adding a ligand phen into the turbid solution C, adjusting the pH to 6.5-7.5, stirring to obtain a mixed solution D, and stirring the mixed solution D with a magnetic stirrer at normal temperature and normal pressure to obtain a precursor solution E;
(4) transferring the precursor solution E into a hydrothermal reaction kettle with polytetrafluoroethylene, sealing the reaction kettle, putting the reaction kettle into an oven, selecting a temperature control mode to carry out reaction, controlling the temperature to be 60-100 ℃ and reacting for 60-90h, controlling the reaction kettle to cool to room temperature at a cooling rate of 5 ℃/h after the reaction is finished, collecting colorless crystals appearing at the bottom in the reaction kettle, and washing and drying the collected crystals to obtain the colorless rhombus blocky crystal complex.
The preparation method of the phenanthroline ligand-containing Cd (II) complex is further optimized as follows: the adding amount ratio of the organic ligand ASBA and the mixed solution in the step (1) is as follows: 0.1-0.5mmol of organic ligand is added to each 10ml of the mixed solution.
The preparation method of the phenanthroline ligand-containing Cd (II) complex is further optimized as follows: the volume ratio of the water to the organic solvent in the step (2) is 0.5:1-3:1, and the organic solvent is methanol, ethanol, DMF or DMSO.
The preparation method of the phenanthroline ligand-containing Cd (II) complex is further optimized as follows: cd (ClO) in the step (2)4)2·6H2The adding amount ratio of O to the mixed solution is as follows: every 10ml of water andadding 0.1mmol Cd (ClO) into the organic solvent mixture4)2·6H2O。
The preparation method of the phenanthroline ligand-containing Cd (II) complex is further optimized as follows: the adding amount ratio of the solution B, the solution A and the ligand phen in the step (3) is as follows: 10-50ml of solution B and 0.1-0.2mmol of phen are added to every 10ml of solution A.
The preparation method of the phenanthroline ligand-containing Cd (II) complex is further optimized as follows: and (3) adjusting the pH value of the solution by using dilute nitric acid and sodium hydroxide.
The preparation method of the phenanthroline ligand-containing Cd (II) complex is further optimized as follows: the drying temperature of the vacuum drying oven in the step (5) is controlled to be 50-70 ℃.
The application of Cd (II) complex containing phenanthroline ligand in bacteriostasis.
The application of Cd (II) complex containing phenanthroline ligand in fluorescent luminescent material.
The invention has the following beneficial effects:
the complex material crystal has the advantages of good crystallinity, no toxicity, no pollution, high thermal stability, excellent antibacterial performance and low raw material cost;
secondly, the complex material synthesis process equipment is simple, the method is simple and convenient, and the complex material is suitable for large-scale controllable production;
the complex material can meet the requirements of environmental disinfection, bacteriostasis and community and family antibacterial use, and has certain application in the aspect of photoluminescence materials.
Drawings
FIG. 1 is a comparison of a powder X-ray diffraction (PXRD) pattern of a product prepared in accordance with example 1 of the present invention and simulated XRD of single crystal diffraction data;
FIG. 2 is a Fourier transform infrared spectrum of the product produced in example 1 of the present invention;
FIG. 3 is a structural diagram of the molecular basic unit of the product produced in example 1 of the present invention;
FIG. 4 is a thermogravimetric analysis of the product produced in example 1 of the present invention;
FIG. 5 is a graph of excitation/emission fluorescence spectra in a solution of the product prepared in example 1 of the present invention;
FIG. 6 is a graph showing the bacteriostatic effect of the product (10% DMSO) prepared in example 1 of the present invention;
FIG. 7 is a graph showing the bacteriostatic effect of the product (15% DMSO) prepared in example 1 of the present invention;
FIG. 8 is a graph showing the bacteriostatic effect of the products (20% and 30% DMSO) prepared in example 1 of the present invention.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.