阅读说明：本技术 一种含甲基侧链的吡啶二甲酸与1,10-菲罗啉构筑的铽配位聚合物及制备方法 (Methyl side chain-containing dipicolinic acid and 1, 10-phenanthroline-constructed terbium coordination polymer and preparation method thereof ) 是由 刘峥 王胜 王小燕 李伟 曹磊 彭静 孔翔飞 于 2021-10-11 设计创作，主要内容包括：本发明公开了一种含甲基侧链的吡啶二甲酸与1,10-菲罗啉(1,10-phen)构筑的铽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,与六水合硝酸铽反应,获得了化学式为{[Tb(L-(1))-(3)(1,10-phen)]·5H-(2)O}-(n)的铽配合物。该配合物采用氧原子和氮原子与Tb～(3+)离子螯合的配位模式,单核的铽离子通过配体的连接无限延伸形成一维链状的晶体结构。该铽配合物属于三斜晶系,空间群为Pī,晶胞参数为α＝94.5806(10)°,β＝105.4522(10)°,γ＝118.4654(12)°,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{[Tb(L-(1))-(3)(1,10-phen)]·5H-(2)O}-(n),为制备多元羧酸稀土金属配位聚合物提供一条新的途径。(The invention discloses a terbium coordination polymer constructed by pyridine dicarboxylic acid containing a methyl 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 terbium nitrate hexahydrate in a mixed solvent of N, N-Dimethylformamide (DMF) and water to obtain { [ Tb (L) with a chemical formula 1 ) 3 (1,10‑phen)]·5H 2 O} n Terbium complex of (1). The complex adopts oxygen atom and nitrogen atom and Tb 3+ In the coordination mode of ion chelation, mononuclear terbium ions extend infinitely through the connection of ligands to form a one-dimensional chain crystal structure. The terbium complex belongs to a triclinic crystal system, the space group is P ī, and the unit cell parameter is α＝94.5806(10)°，β＝105.4522(10)°，γ＝118.4654(12)°， 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 { [ Tb (L) { [ L ] 1 ) 3 (1,10‑phen)]·5H 2 O} n Provides a new way for preparing polycarboxylic acid rare earth metal coordination polymer.)

1. Terbium coordination polymer { [ Tb (L) constructed by pyridinedicarboxylic acid containing methyl side chain and 1, 10-phenanthroline (1,10-phen)₁)₃(1,10-phen)]·5H₂O}_nCharacterized in that the molecular formula is C₅₁H₃₇N₇O₁₂Tb₂·5(H₂O), relative molecular mass of 1347.82, and the complex is prepared from oxygen atom and nitrogen atom and Tb³⁺Coordination mode of ion chelation, monoThe terbium ion of the nucleus is infinitely extended through the connection of ligands to form a one-dimensional chain crystal structure, the terbium complex belongs to a triclinic crystal system, the space group is P ī, and the unit cell parameter isα＝94.5806(10)°，β＝105.4522(10)°，γ＝118.4654(12)°，Z is 2, the crystallographic data is shown in Table 1, the part and the bond angle are shown in Table 2,

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

TABLE 2 [ ZnL (4, 4' -bipy) (H)₂O)]_nPartial bond length ofAngle of harmony key (°)

The terbium 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) weigh 0.1306g Tb (NO)₃)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 terbium coordination polymer constructed by 1, 10-phenanthroline.

Technical Field

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

Background

The metal functional complex is an inorganic-organic hybrid material which takes metal ions as central ions and is formed by the self-assembly property of the metal ions, organic ligands, inorganic anions and neutral heterocyclic ligands. The coordination polymer has different structures and properties due to the diversity of self-assembly forms, so that the coordination polymer has respective applications in the fields of light, electricity, magnetism, biological carriers, molecular recognition, adsorption, desorption and the like.

Among the organic ligands, carboxylic acid ligands have strong space coordination capability and multiple coordination modes, because two oxygen atoms on carboxyl can react with metal ions, and the coordination modes are complex and changeable and have good bridging capability. After the carboxyl is coordinated, negative charges are carried due to proton loss, and the carboxyl can be combined with central metal ions with positive charges, so that the electric effect between ions is relieved, the neutrality is kept, and a complex with a stable structure is formed. Meanwhile, oxygen atoms on the carboxyl groups can generate certain hydrogen bond acting force, and the stability of the structural framework of the complex is better facilitated.

The coordination polymer prepared based on the dicarboxylpyridine organic ligand combines the pi-pi stacking effect between ligands with excellent coordination performance of carboxyl, so that the designed and synthesized coordination polymer has molecular framework stability and pore size adjustability, and the superiority of the nitrogen-containing heterocyclic ligand promotes the development of the coordination polymer.

This patent provides a process for the preparation of a compound of 2, 6-dimethyl-3,5-Pyridinedicarboxylic acid (H)₂L₁) 1, 10-phenanthroline (1,10-phen) and the rare earth metal terbium salt (Tb (NO)₃)₃·6H₂O) is used as a raw material, and the chemical formula { [ Tb (L) is obtained by a solvothermal method₁)₃(1,10-phen)]·5H₂O}_nA structure of terbium coordination polymer and a preparation method thereof.

Disclosure of Invention

The purpose of the invention is as follows: provides a methyl side chain-containing pyridinedicarboxylic acid and 1, 10-phenanthroline constructed terbium coordination polymer 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-pyridine dicarboxylic acid is used as a main ligand, 1, 10-phenanthroline is used as an auxiliary ligand, and oxygen atoms of carboxylic acid, nitrogen atoms of 1, 10-phenanthroline and Tb are utilized³⁺Ion chelation and coordination to form an infinitely extended one-dimensional chain structure.

The methyl side chain-containing pyridinedicarboxylic acid and the 1, 10-phenanthroline-constructed terbium complex have the structural characteristics that: belongs to the triclinic system, the space group is P ī, the cell parameter is α＝94.5806(10)°，β＝105.4522(10)°，γ＝118.4654(12)°，The crystallographic data are shown in table 1, and the part and bond angle are shown in table 2.{ [ Tb (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 { [ Tb (L)₁)₃(1,10-phen)]·5H₂O}_nCrystallographic data of

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

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

(1) weigh 0.1306g Tb (NO)₃)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 a yellow transparent needle crystal, namely the methyl side chain-containing pyridinedicarboxylic acid and the terbium complex 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 { [ Tb (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 a chemical formula { [ Tb (L) according to the present invention₁)₃(1,10-phen)]·5H₂O}_nTerbium complexThe molecular structure of the substance is an ellipsoid diagram.

FIG. 2 shows a chemical formula { [ Tb (L) according to the present invention₁)₃(1,10-phen)]·5H₂O}_nPolyhedral diagram of terbium complex.

FIG. 3 shows a chemical formula { [ Tb (L) according to the present invention₁)₃(1,10-phen)]·5H₂O}_nOne-dimensional stacking diagram of terbium complex.

Detailed Description

Example 1:

(1) weigh 0.1306g Tb (NO)₃)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 a yellow transparent needle crystal, namely the methyl side chain-containing pyridinedicarboxylic acid and the terbium complex constructed by 1, 10-phenanthroline. The yield was 57.24%.

(3) Structural analysis of methyl side chain-containing pyridinedicarboxylic acid and 1, 10-phenanthroline-constructed terbium complex: theoretical value of elemental analysis as C₅₁H₃₇N₇O₁₂Tb₂·5(H₂O) calculation (%): c, 45.45; n, 7.31; h, 2.77. Found (%): c, 45.48; n, 7.35; h, 2.78.

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＝94.5806(10)°，β＝105.4522(10)°，γ＝118.4654(12)°，Z＝2。

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

As shown in the attached figure 2, in the complex, a central metal ion Tb (III) is respectively 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 +1, -z, (iii) -x +2, -y +2, -z +1, and (iv) x +1, y +1, z + 1). The sum of the bond angles formed by the 4 coordinating atoms N4, N5, O9 and O10 is 359.83 degrees and is close to the ideal 360 degrees, which indicates that the 4 coordinating atoms form a plane and have better planarity. The metal Tb is positioned at the center of a distorted triangular prism consisting of O3, O4ii, N4, N5, O9 and O10, the coordination atoms O5 and O6ii are positioned at the periphery of the triangular prism, and the coordination atoms O5 and O6ii and 6 atoms constituting the triangular prism form a distorted double-cap triangular prism.

As can be seen from Table 2, the Tb-O bond length of the coordination bond is inTb-N bond length is inThe bond angle O-Tb-X (X ═ O, N) is in the normal range from 53.52(8) to 149.82(8) °.

As can be seen from the stacking diagram of the complex (FIG. 3 in the drawing), the complex is Tb³⁺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.