阅读说明：本技术 一种含甲基侧链的吡啶二甲酸与1,10-菲罗啉构筑的铕配位聚合物及制备方法 (Methyl side chain-containing pyridinedicarboxylic acid and 1, 10-phenanthroline-constructed europium coordination polymer and preparation method thereof ) 是由 刘峥 王胜 鲁明峻 李伟 彭静 曹磊 唐富顺 于 2021-10-11 设计创作，主要内容包括：本发明公开了一种含双甲基侧链的吡啶二甲酸与1,10-菲罗啉(1,10-phen)构筑的铕配位聚合物及制备方法。所述方法是以2,6-二甲基-3,5-吡啶二甲酸为主配体,1,10-菲罗啉为辅助配体,在N,N-二甲基甲酰胺(DMF)和水的混合溶剂中,与六水合硝酸铕反应,获得了化学式为{[Eu(L-(1))-(3)(1,10-phen)]·5H-(2)O}-(n)的铕配合物。该配合物采用氧原子和氮原子与Eu～(3+)离子螯合的配位模式,单核的铕离子通过配体的连接无限延伸形成一维链状的晶体结构。该铕配合物属于三斜晶系,空间群为Pī,晶胞参数为α＝94.7181(17)°,β＝105.3618(18)°,γ＝118.335(2)°,Z＝2。本发明的所述制备方法具有工艺简单、重复性好、绿色环保且产率较高等优点。本发明成功制备{[Eu(L-(1))-(3)(1,10-phen)]·5H-(2)O}-(n),为制备多元羧酸稀土金属配合物提供一条新的途径。(The invention discloses a europium coordination polymer constructed by pyridinedicarboxylic acid containing a dimethyl side chain and 1, 10-phenanthroline (1,10-phen) and a preparation method thereof. The method takes 2, 6-dimethyl-3, 5-pyridinedicarboxylic acid as a main ligand and 1, 10-phenanthroline as an auxiliary ligand to react with europium nitrate hexahydrate in a mixed solvent of N, N-Dimethylformamide (DMF) and water to obtain { [ Eu (L) 1 ) 3 (1,10‑phen)]·5H 2 O} n The europium complex of (1). The coordination compound adopts oxygen atoms and nitrogen atoms and Eu 3+ The coordination mode of ion chelation is that mononuclear europium ions extend infinitely through the connection of ligands to form a one-dimensional chain crystal structure. The europium complex belongs to a triclinic system, the space group is P ī, and the unit cell parameter is α＝94.7181(17)°，β＝105.3618(18)°，γ＝118.335(2)°， And Z is 2. The preparation method disclosed by the invention has the advantages of simple process, good repeatability, environmental friendliness, higher yield and the like. The invention successfully prepares { [ Eu (L) ] 1 ) 3 (1,10‑phen)]·5H 2 O} n Provides a new way for preparing the polycarboxylic acid rare earth metal complex.)

1. Europium coordination polymer { [ Eu (L) constructed by pyridinedicarboxylic acid containing methyl side chain and 1, 10-phenanthroline₁)₃(1,10-phen)]·5H₂O}_nCharacterized in that the molecular formula is C₅₁H₃₆Eu₂N₇O₁₂·5(H₂O), relative molecular mass of 1332.89, the coordination polymer is derived from oxygen atoms and nitrogen atoms and Eu³⁺The coordination mode of ion chelation is that mononuclear europium ions are infinitely extended through the connection of ligands to form a one-dimensional chain-shaped crystal structure, the europium complex belongs to a triclinic system, the space group is P ī, and the unit cell parameter isα＝94.7181(17)°，β＝105.3618(18)°，γ＝118.335(2)°，Z is 2, the crystallographic data is shown in Table 1, the part and the bond angle are shown in Table 2,

TABLE 1 { [ Eu (L)₁)₃(1,10-phen)]·5H₂O}_nCrystallographic data of

TABLE 2 { [ Eu (L)₁)₃(1,10-phen)]·5H₂O}_nPartial bond length ofAngle of harmony key (°)

The europium coordination polymer constructed by the picolinic acid containing the methyl side chain and the 1, 10-phenanthroline is characterized by comprising the following specific steps:

(1) 0.0892g Eu (NO) were weighed out₃)₃·6H₂Dissolving O, 0.0390g of 2, 6-dimethyl-3, 5-pyridinedicarboxylic acid and 0.0360g of 1, 10-phenanthroline in a beaker containing 6mL of N, N-dimethylformamide and 4mL of distilled water, and stirring for 30min by using a magnetic stirrer at room temperature to prepare a mixed solution;

(2) transferring the mixed solution prepared in the step (1) into a 25mL reaction kettle with a polytetrafluoroethylene bottle, putting the reaction kettle into an oven, heating the reaction kettle to 90 DEG CAfter 72 hours of reaction, the reaction was carried out at 10 ℃ h^-1Cooling to 60 ℃, keeping the temperature for 2 hours, closing the oven, cooling to room temperature in a natural state, taking out the reaction kettle, and generating yellow transparent needle crystals, namely the methyl side chain-containing pyridinedicarboxylic acid and the europium coordination polymer constructed by 1, 10-phenanthroline.

Technical Field

The invention belongs to the technical field of metal organic coordination polymer preparation, and particularly relates to a europium coordination polymer constructed by picolinic acid containing a methyl side chain and 1, 10-phenanthroline and a preparation method thereof.

Background

Coordination polymers are supramolecular compounds with 1D, 2D and 3D structures constructed by metal ions and organic ligands. Metal ions are easy to coordinate and combine with non-metal atoms such as N, O, S and the like, so that some coordination polymers with novel topological structures are constructed by using ligand coordination reaction containing the atoms in a designability way and through self-assembly molecules.

Coordination polymers not only contain the properties of organic and inorganic moieties, but may even have some new properties. Due to the diversity of properties caused by the diversity of the coordination polymer structure, the coordination polymer has great application value in many fields such as catalysis, anti-cancer drugs, sensors, photoelectric materials, adsorption and separation and the like. Will have a more significant application potential.

The ligand contains pyridine ring and double carboxyl structure rich in pi electrons, so that the pyridine carboxylic acid coordination polymer designed and synthesized has higher porosity and specific surface area, and the synthesized coordination polymer has more significant application potential.

The patent provides a method for preparing a compound with 2, 6-dimethyl-3, 5-pyridinedicarboxylic acid (H)₂L₁) 1, 10-phenanthroline (1,10-phen) and rare earth europium salt (Eu (NO)₃)₃·6H₂O) is taken as a raw material, and a chemical formula is obtained by a solvothermal methodIs { [ Eu (L)₁)₃(1,10-phen)]·5H₂O}_nA structure of europium coordination polymer and a preparation method thereof.

Disclosure of Invention

The purpose of the invention is as follows: provides a europium coordination polymer constructed by pyridine dicarboxylic acid containing methyl side chain and 1, 10-phenanthroline and a preparation method thereof.

The idea of the invention is as follows: based on the excellent properties of the pyridine polycarboxylic acid ligand, 2, 6-dimethyl-3, 5-pyridinedicarboxylic acid is adopted as a main ligand, 1, 10-phenanthroline is adopted as an auxiliary ligand, and the Eu is reacted through a carboxylic acid oxygen atom, a 1, 10-phenanthroline nitrogen atom and the Eu³⁺Ion chelation and coordination to form an infinitely extended one-dimensional chain structure.

The europium complex constructed by the picolinic acid containing methyl side chain and 1, 10-phenanthroline has the structural characteristics that: belongs to the triclinic system, the space group is P ī, the cell parameter is α＝94.7181(17)°，β＝105.3618(18)°，γ＝118.335(2)°，The crystallographic data are shown in table 1, and the part and bond angle are shown in table 2.{ [ Eu (L)₁)₃(1,10-phen)]·5H₂O}_nThe ellipsoid diagram of the molecular structure of the complex is shown in figure 1, the polyhedral diagram of the complex is shown in figure 2, and the one-dimensional stacking diagram of the complex is shown in figure 3.

TABLE 1 { [ Eu (L)₁)₃(1,10-phen)]·5H₂O}_nCrystallographic data of

TABLE 2 { [ Eu (L)₁)₃(1,10-phen)]·5H₂O}_nPartial bond length ofAngle of harmony key (°)

{[Eu(L₁)₃(1,10-phen)]·5H₂O}_nThe preparation method comprises the following steps:

(1) 0.0892g Eu (NO) were weighed out₃)₃·6H₂O, 0.0390g of 2, 6-dimethyl-3, 5-pyridinedicarboxylic acid, 0.0360g of 1, 10-phenanthroline were dissolved in a beaker containing 6mL of N, N-dimethylformamide and 4mL of distilled water; and (3) stirring the mixed solution obtained in the step (1) for 30min by using a magnetic stirrer at room temperature to obtain a mixed solution.

(2) Transferring the mixed solution prepared in the step (1) into a 25mL reaction kettle with a polytetrafluoroethylene bottle, putting the reaction kettle into an oven, heating the reaction kettle to 90 ℃, reacting for 72 hours, and reacting at 10 ℃ for h^-1Cooling to 60 ℃, keeping the temperature for 2 hours, closing the oven, cooling to room temperature in a natural state, taking out the reaction kettle, and generating yellow transparent needle crystals, namely the methyl side chain-containing pyridinedicarboxylic acid and the europium coordination polymer constructed by 1, 10-phenanthroline.

The preparation method provided by the invention has the advantages of easy operation, good reproducibility, environmental protection, no pollution and the like, and the obtained { [ Eu (L)₁)₃(1,10-phen)]·5H₂O}_nThe purity is high, and the preparation method provides a new way for the polycarboxylic acid rare earth metal complex.

Drawings

FIG. 1 shows the chemical formula { [ Eu (L)₁)₃(1,10-phen)]·5H₂O}_nThe molecular structure of the europium complex is an ellipsoid diagram.

FIG. 2 shows the chemical formula { [ Eu (L)₁)₃(1,10-phen)]·5H₂O}_nPolyhedrons of europium complexesFigure (a).

FIG. 3 shows the chemical formula { [ Eu (L)₁)₃(1,10-phen)]·5H₂O}_nOne-dimensional stacking diagram of europium complex.

Detailed Description

Example 1:

(1) 0.0892g Eu (NO) were weighed out₃)₃·6H₂O, 0.0390g of 2, 6-dimethyl-3, 5-pyridinedicarboxylic acid, 0.0360g of 1, 10-phenanthroline were dissolved in a beaker containing 6mL of N, N-dimethylformamide and 4mL of distilled water; stirring with magnetic stirrer for 30min to obtain mixed solution;

(2) transferring the mixed solution prepared in the step (1) into a 25mL reaction kettle with a polytetrafluoroethylene bottle, putting the reaction kettle into an oven, heating the reaction kettle to 90 ℃, reacting for 72 hours, and reacting at 10 ℃ for h^-1Cooling to 60 ℃, keeping the temperature for 2 hours, closing the oven, cooling to room temperature in a natural state, taking out the reaction kettle, and generating yellow transparent needle crystals, namely the methyl side chain-containing pyridinedicarboxylic acid and the europium complex constructed by 1, 10-phenanthroline. The yield was 52.64%.

(3) Structural analysis of a europium complex constructed by picolinic acid containing a methyl side chain and 1, 10-phenanthroline: theoretical value of elemental analysis as C₅₁H₃₆Eu₂N₇O₁₂·5(H₂O) calculation (%): c, 49.96; n, 7.36; h, 2.72. Found (%): c, 49.93; n, 7.38; h, 2.76.

As can be seen from the crystallographic data in Table 1, the complex belongs to the triclinic system, space group is P ī, and unit cell parameters areα＝94.7181(17)°，β＝105.3618(18)°，γ＝118.335(2)°，Z＝2；

As can be seen from the attached figure 1, the basic unit of the complex comprises 1 Eu (III) central ion, 3 main ligands, 2, 6-dimethyl-3, 5-pyridinedicarboxylic acid and 1 auxiliary ligand, 1, 10-phenanthroline;

as shown in the attached figure 2, in the complex, a central metal ion Eu (III) is coordinated with 6 carboxyl oxygen atoms of a ligand 2, 6-dimethyl-3, 5-pyridine dicarboxylic acid and 2 nitrogen atoms of 1, 10-phenanthroline to form an eight-coordination structure (symmetrical codes of (i) x-1, y-1, z-1, (ii) -x +1, -y, -z, (iii) x +1, y +1, z +1, (iv) -x +2, -y +1, -z + 1.). Among atoms participating in coordination, the sum of bond angles formed by four atoms of O5ii, O9ii, O6 and O10 is 359.93 degrees and is close to an ideal 360 degrees, which indicates that the 4 coordination atoms form a plane and have better planarity. Metal Eu is positioned at the center of a distorted triangular prism composed of O5ii, O9ii, O6, O10, O3, O5, O4, N4 on the ligand are positioned at the periphery of the triangular prism, and form a distorted double-capped triangular prism with 6 atoms constituting the triangular prism.

As can be seen from Table 2, the Eu-O bond length of the coordination bond is inWith Eu-N bond length inThe bond angle O — Eu — X (X ═ O, N) is in the normal range of 46.59(8) ° to 148.99(9) °.

As can be seen from the stacking diagram of the complex (FIG. 3 in the figure), the complex is Eu³⁺Is a metal node, L₁ ^2-And 1,10-phen as a connecting body are connected with each other to form an infinitely extending one-dimensional chain structure.