阅读说明：本技术 一种三维镉配合物合成及作为荧光探针的应用 (Synthesis of three-dimensional cadmium complex and application of three-dimensional cadmium complex as fluorescent probe ) 是由 王俊 张晨 陈宁宁 贾立永 陶建清 张康峰 岳煜菲 贾海瑞 梁良 俞梦娇 于 2019-04-25 设计创作，主要内容包括：本发明提供一种镉金属配合物,制备方法及其在三价铁离子(Fe<Sup>3+</Sup>)、碳酸根离子(CO<Sub>3</Sub><Sup>2-</Sup>)检测方面的应用。所述配合物的化学式为[Cd(L)(1,10-Phen)]<Sub>n</Sub>,其中,H<Sub>2</Sub>L＝3,3’-(1H,1’H-2,2’-联咪唑-1,1’-二亚甲基)苯甲酸,1,10-Phen＝1,10-菲罗啉；所述镉金属配合物为镉离子通过与L<Sup>2-</Sup>和1,10-Phen配体自组装而成三维结构。实验结果表明：该镉配合物具有很好的荧光性质,可高效检测水中铁离子和碳酸根离子,结构稳定,可重复使用,在环境污染检测领域具有潜在的应用价值。该配合物合成工艺简单,反应条件温和,使用方便,为环境中有害物质的检测提供了一种新的手段。(The invention provides a cadmium metal complex, a preparation method and application thereof in ferric ion (Fe) 3+ ) Carbonate ion (CO) 3 2‑ ) And (3) application in detection. The chemical formula of the complex is [ Cd (L) (1, 10-Phen)] n Wherein H is 2 L ═ 3, 3 '- (1H, 1' H-2, 2 '-biimidazole-1, 1' -dimethylene) benzoic acid, 1, 10-Phen ═ 1, 10-phenanthroline; the cadmium metal complex is formed by the passing of cadmium ions and L 2‑ And 1, 10-Phen ligand self-assemble to form a three-dimensional structure. The experimental results show that: the cadmium complex has good fluorescence property, can efficiently detect iron ions and carbonate ions in water, has a stable structure, can be repeatedly used, and has potential application value in the field of environmental pollution detection. The complex has simple synthesis process and reaction conditionsMild, convenient to use, provides a new means for the detection of harmful substances in the environment.)

1. A ferric ion (Fe)³⁺) Carbonate ion (CO)₃ ^2-) The cadmium complex of the fluorescent probe is characterized in that the chemical formula is [ Cd (L) (1, 10-Phen)]_nWherein H is₂L ═ 3, 3 '- (1H, 1' H-2, 2 '-biimidazole-1, 1' -dimethylene) benzoic acid, 1, 10-Phen ═ 1, 10-phenanthroline; the above-mentionedThe crystal of the cadmium complex belongs to a monoclinic system, the space group is C2/C, and the unit cell parameter isα is 90 °, β is 95.41(2 °), γ is 90 °; the Cd atom at the center of the complex is in a hexa-coordinated octahedral configuration, and two nitrogen atoms and four nitrogen atoms are from two L atoms in a 1, 10-Phen ligand^2-The oxygen atoms in the ligand coordinate to form a three-dimensional framework structure.

2. A method of preparing a cadmium complex according to claim 1, characterized by the steps of: the cadmium complex is obtained by the organic ligand 3, 3 '- (1H, 1' H-2, 2 '-biimidazole-1, 1' -dimethylene) benzoic acid, 1, 10-phenanthroline and cadmium nitrate tetrahydrate in a mixed solution of water and N, N-dimethylformamide through a solvothermal method.

3. The method of claim 2, wherein: the molar ratio of 3, 3 '- (1H, 1' H-2, 2 '-biimidazole-1, 1' -dimethylene) benzoic acid to 1, 10-phenanthroline to cadmium nitrate tetrahydrate is 1: 1, and each 0.05mmol of cadmium nitrate tetrahydrate corresponds to a mixed solution of 1mL of deionized water and 2mL of N, N-dimethylformamide at the temperature of 100 ℃ for 48 hours.

Technical Field

The invention belongs to the technical field of organic synthesis and metal organic chemistry, and particularly relates to preparation of a three-dimensional cadmium complex taking 3, 3 '- (1H, 1' H-2, 2 '-biimidazole-1, 1' -dimethylene) benzoic acid and 1, 10-phenanthroline as ligands and application of the three-dimensional cadmium complex as ferric ion (Fe) ³⁺) Carbonate ion (CO)₃ ^2-) Application of fluorescent probe.

Background

Compared with the traditional luminescent materials, the complex fluorescent material attracts much attention because of having high chemical stability of inorganic materials and high quantum yield of organic materials. The fluorescence property of the complex is influenced by factors such as the electronic configuration and energy level of metal ions, the coordination configuration and coordination environment, the ligand and external conditions such as solvent (solution fluorescence), temperature and the like. Particularly, the complexes have pore channels, bare metal sites and active organic groups with Lewis acids or basic sites in the structure, can effectively perform host-guest interaction with guest molecules (including anions, metal cations and organic small molecules), and directly reflect the action result in the fluorescence change of the substance, so that the complexes have good application values in the aspects of organic matter detection, metal ion detection, temperature probes, pH probes, active probes and the like. A series of fluorescent probe complexes have been reported, but there are fewer fluorescent probe complexes capable of simultaneously detecting multiple guests.

The presence of metal ions is closely related to the life of modern human beings: on one hand, with the rapid development of modern industry, the environmental pollution problems such as mining, industrial waste gas and waste water discharge become more serious, and heavy metal ions enter into organisms to cause chronic poisoning of the organisms. On the other hand, metal ions are also indispensable constituent elements for living beings and the human body. Therefore, it is very important to detect metal ions quickly, conveniently and accurately.

Iron is a trace transition metal element in organisms, participates in a plurality of enzymes and components of an immune system in a human body, and is also a main component of hemoglobin, and a plurality of diseases are caused by insufficient or excessive iron element in the body, so that the health of the human body is influenced. However, if the iron content in the human body is excessive, the structure of the human organ is changed, and the disease is caused; such as hepatic fibrosis, serious patients can be life-threatening. Carbonate plays an important role in regulating acid-base balance of a human body and maintaining homeostasis of the human body. The acid buffer agent formed by mixing sodium carbonate and sodium bicarbonate can maintain the relatively stable pH of the stomach of a human body; sodium bicarbonate is a weakly alkaline substance, and when gastric acid (mainly hydrochloric acid) is excessive, sodium carbonate reacts with hydrochloric acid to generate sodium bicarbonate, so that the pH can be increased; when the gastric acid is less and the pH value of the gastric environment is higher, the sodium bicarbonate can react with the strongly alkaline substance to generate sodium carbonate, and the sodium carbonate is weakly alkaline, so that the pH value of the gastric environment can be reduced, a bidirectional adjustment effect is achieved, and the pH value of the gastric environment is kept relatively stable. Therefore, it is very important to detect ferric ions and carbonate ions quickly, conveniently and accurately.

3, 3 '- (1H, 1' H-2, 2 '-biimidazole-1, 1' -dimethylene) benzoic acid is a bridging ligand with stronger coordination capacity: two carboxylic acid groups are arranged at two ends of the ligand, and two benzene rings are connected through biimidazole, so that the synthesis of the complex is facilitated; it can be partially or completely deprotonated, allows different coordination models with metal ions, and facilitates the synthesis of metal complexes with different dimensions, which is a crucial step in the completion of device formation.

The invention belongs to the technical field of organic synthesis and metal organic chemistry, and relates to synthesis of a three-dimensional cadmium metal fluorescent complex, in particular to synthesis of a cadmium coordination polymer taking 3, 3 '- (1H, 1' H-2, 2 '-biimidazole-1, 1' -dimethylene) benzoic acid as a ligand and application of the cadmium coordination polymer as a fluorescent probe. The cadmium fluorescent complex with the three-dimensional structure shows obvious fluorescent quenching effect on ferric ions and carbonate ions, can be applied to ion detection and analysis research as a fluorescent probe material, and has a wide application prospect.

In summary, there are many reports on complexes with fluorescent probe properties, respectively, but they can simultaneously have Fe³⁺、CO₃ ^2-Very few reports have been reported for all responsive complexes. In the invention, the synthesized metal complex has the advantages of low cost, high efficiency, good reproducibility, sensitive detection, easy separation and high yield, and Fe is used as a metal complex³⁺、CO₃ ^2-The detection method has a wide application prospect.

Disclosure of Invention

The invention aims to provide a three-dimensional cadmium complex used as a ferric ion and carbonate ion fluorescent probe and a preparation method thereof. The invention selects organic ligand 3, 3 '- (1H, 1' H-2, 2 '-biimidazole-1, 1' -dimethylene) benzoic acid, 1, 10-phenanthroline and tetrahydrate cadmium nitrate to construct a complex with a three-dimensional structure. The compound has a fluorescent recognition function on ferric ions and carbonate ions, and can detect trace ferric ions and carbonate ions in an aqueous solution. The compound has the advantages of simple synthesis process, low cost, high efficiency, good reproducibility, sensitive detection, easy separation and high yield, can be applied to industrial production, and has potential application prospects in the fields of environmental monitoring and life science.

The chemical formula of the cadmium complex used as the ferric ion and carbonate ion fluorescent probe is as follows: [ Cd (L) (1, 10-Phen)]_nWherein H is₂L ═ 3, 3 '- (1H, 1' H-2, 2 '-biimidazole-1, 1' -dimethylene) benzoic acid, 1, 10-Phen ═ 1, 10-phenanthroline. H₂The structural formula of L, 1, 10-Phen is as follows:

the structure of the three-dimensional cadmium complex used as the ferric ion and carbonate ion fluorescent probe is shown in figure 1(a), and the basic structure parameters are as follows: the crystal of the cadmium complex belongs to a monoclinic system, the space group is C2/C, the unit cell parameter is α is 90 °, β is 95.41(2 °), γ is 90 °; the Cd atom at the center of the complex is in a hexa-coordinated octahedral configuration, and two nitrogen atoms and four nitrogen atoms are from two L atoms in a 1, 10-Phen ligand^2-The oxygen atoms in the ligands coordinate to form a three-dimensional framework structure, as shown in FIG. 1 (b).

The preparation method of the cadmium complex comprises the following steps:

(1) the preparation method comprises the following steps: adding N, N-dimethylformamide (2mL) and deionized water (1mL) into 3, 3 '- (1H, 1' H-2, 2 '-biimidazole-1, 1' -dimethylene) benzoic acid to 1, 10-phenanthroline and tetrahydrate cadmium nitrate in a ratio of 1: 1, uniformly mixing by ultrasonic oscillation for 5 minutes, and putting the mixture into a polytetrafluoroethylene inner container of a hydrothermal reaction kettle to obtain a mixed solution;

(2) drying the mixed solution at 100 ℃ for 48 hours, taking out the product, and separating the solid;

(3) by H₂O the solid was washed three times to give colorless transparent bulk crystals.

Further, the invention provides an application of the cadmium complex as a ferric ion and carbonate ion fluorescent probe, which is used for monitoring ferric ions and carbonate ions in environment and organisms.

The invention has the advantages that: the preparation method has the advantages of simple process, high yield, easy separation, good reproducibility, high sensitivity and high yield, can obtain a single crystal form and high-purity crystal material, and is easy for industrial production; the product has a fluorescent recognition function on ferric ions and carbonate ions, can be used for trace ferric ions and carbonate ions in an aqueous solution, and has the advantages of qualitative, rapidness, sensitivity, high efficiency, simple and convenient operation and the like compared with the traditional detection method.

Brief description of the drawings

FIG. 1(a) is a diagram of the coordination environment of a cadmium complex of the present invention; FIG. 1(b) is a three-dimensional structural diagram of a cadmium complex of the present invention.

FIG. 2 is a thermogram of a cadmium complex of the present invention.

FIG. 3 is a solid fluorescence image of a cadmium complex of the present invention.

FIG. 4(a) a graph of the cationic response of a cadmium complex of the present invention; FIG. 4(b) is a graph of the anionic response of the cadmium complex of the present invention.

Detailed Description

In order to better understand the invention, the following description is further provided in connection with the examples, but the invention is not limited to the following examples.