CN114685807B - Cadmium coordination polymer based on pyrazole carboxylic acid ligand and preparation method thereof - Google Patents
Cadmium coordination polymer based on pyrazole carboxylic acid ligand and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a cadmium coordination polymer based on a pyrazole carboxylic acid ligand, which has a chemical formula as follows: [ Cd (Hppza) ‑ )(H 2 O)I] n (ii) a Wherein H 2 ppza is 5- (4-pyridine) -1H-pyrazole-3-carboxylic acid. The invention also discloses a preparation method of the cadmium coordination polymer, cadmium iodide is dissolved in distilled water to obtain a cadmium iodide aqueous solution; h is to be 2 ppza was dissolved in acetonitrile to give H 2 ppza acetonitrile solution; mixing aqueous solution of cadmium iodide with H 2 Mixing ppza acetonitrile solutions, placing the mixture at a high temperature for reaction, and cooling the mixture to room temperature at a rate of 5 ℃ per half hour after the reaction to obtain yellow massive crystals; and filtering, washing and drying the obtained product to obtain the target product. The complex with the crystal structure has good thermal stability and excellent fluorescence property, and is expected to become a potential candidate material of a photochemical sensor; in addition, the synthesis method is simple, easy to operate and high in yield.
Description
Technical Field
The invention relates to a cadmium coordination polymer based on a pyrazole carboxylic acid ligand and a preparation method of the cadmium coordination polymer.
Background
CPs material (coordination polymer material) is a novel crystal material formed by self-assembling metal ions or metal clusters and multifunctional organic ligands under proper conditions, and has great application potential in the fields of fluorescence sensing, catalysis, magnetism, gas adsorption, electrochemistry and the like.
Disclosure of Invention
The invention aims to: the invention aims to provide a cadmium coordination polymer based on pyrazole carboxylic acid ligand with a one-dimensional structure, and the invention also aims to provide a preparation method of the cadmium coordination polymer.
The technical scheme is as follows: the cadmium coordination polymer based on the pyrazole carboxylic acid ligand has the chemical formula as follows: [ Cd (Hppza) - )(H 2 O)I] n (ii) a Wherein H 2 ppza is 5- (4-pyridine) -1H-pyrazole-3-carboxylic acid.
Wherein the basic structural unit of the cadmium coordination polymer is as follows: cd (II) ion as central metal ion, oxygen atom coordinating with water, I - And one incompletely deprotonated Hppza - Coordinating the ligand; wherein, pyrazole ring nitrogen atom, carboxylic acid oxygen atom and central metal ion Cd in the ligand 2+ And (4) coordination.
The pyrazole group of the 5- (4-pyridine) -1H-pyrazole-3-carboxylic acid ligand contains a proton on the N atom and a proton on the carboxyl oxygen atom, both of which may be deprotonated during the reaction, which is called deprotonation. According to the single crystal test result, the ligand in the complex is deprotonated only by carboxyl, and the proton on pyrazole is still remained, so that the complex is not completely deprotonated, and is completely deprotonated if both protons are deprotonated.
Wherein the pyridine nitrogen atom in each basic structural unit is connected to another metal central ion Cd 2+ Extended into a one-dimensional chain structure, and a carboxyl oxygen atom is simultaneously connected with another metal central ion Cd 2+ Forming a double-chain structure, and growing to obtain the one-dimensional double-chain polymer.
Wherein, the coordination polymer has a one-dimensional double-chain structure, belongs to a triclinic system, has a space group of P-1, and has the following unit cell parameters:
α＝100.353(2)°，β＝106.301(2)°，γ＝112.195(2)°，
Z＝2。
the preparation method of the cadmium coordination polymer comprises the following steps:
(1) Dissolving cadmium iodide in distilled water to obtain a cadmium iodide aqueous solution;
(2) H is to be 2 ppza dissolved in acetonitrile to give H 2 ppza acetonitrile solution;
(3) Mixing aqueous solution of cadmium iodide with H 2 Mixing ppza acetonitrile solutions, placing the mixture at a high temperature for reaction, and cooling the mixture to room temperature at a rate of 5 ℃ per half hour after the reaction to obtain yellow massive crystals;
(4) And filtering, washing and drying the obtained product.
Wherein, in the step (3), the cadmium iodide aqueous solution and H 2 Cadmium iodide and H in mixed solution obtained by mixing ppza acetonitrile solution 2 The molar ratio of ppza was 1:1.
wherein, in the step (3), the reaction temperature is 120 ℃, and the reaction time is three days.
Cd (II) and H 2 The complex obtained after the ppza self-assembly has excellent fluorescence performance, on one hand, the used 5- (4-pyridine) -1H-pyrazole-3-formic acid ligand has a large conjugated pi-electron system, which is beneficial to the transmission of electrons in the complex and further obtains a material with good optical performance; on the other hand because of 3d 10 The Cd (II) ions in the configuration do not have d-d electron transition, and energy is not consumed, so that the quantization efficiency of the organic ligand is improved, and the cadmium complex obtained by the method can show stronger fluorescence. The complex obtained by self-assembling Cd (II) and a 5- (4-pyridine) -1H-pyrazole-3-formic acid ligand has good thermal stability, and on one hand, the overall structural stability is stronger because a new five-membered ring structure is formed after coordination; on the other hand, the complex has a large number of coordination bonds, hydrogen bonds and pi \8230, and pi stacking effects, so that the rigidity of the whole complex is enhanced, the structure is firmer, the thermal stability of the complex is effectively improved, and the structure is stable at high temperature.
Has the advantages that: the complex with the crystal structure has good thermal stability and excellent fluorescence property, and is expected to become a potential candidate material of a photochemical sensor; in addition, the synthesis method is simple, easy to operate and high in yield.
Drawings
FIG. 1 is a schematic diagram of an asymmetric unit of a Cd (II) coordination polymer;
FIG. 2 shows Cd (II) coordination polymer Cd 2+ Schematic diagram of the coordination environment of (a);
FIG. 3 is a schematic diagram of one-dimensional double-strand of a Cd (II) coordination polymer along the a-axis direction;
FIG. 4 is a three-dimensional supramolecular stacking diagram of a Cd (II) coordination polymer along the a-axis direction;
FIG. 5 shows [ Cd (Hppza) - )(H 2 O)I] n A PXRD pattern of the complex;
FIG. 6 shows [ Cd (Hppza) - )(H 2 O)I] n TG plot of the complex;
FIG. 7 shows [ Cd (Hppza) - )(H 2 O)I] n And (3) solid-state fluorescence emission diagram of the complex.
Detailed Description
The technical solution of the present invention is further described with reference to the following specific embodiments.
Example 1
The chemical formula of the Cd (II) coordination polymer is as follows: [ Cd (Hppza) - )(H 2 O)I] n (ii) a Wherein H 2 ppza is 5- (4-pyridine) -1H-pyrazole-3-carboxylic acid.
The Cd (II) coordination polymer is prepared by the following method: mixing CdI 2 (0.3 mmol, 0.1098g) was dissolved in 15mL of distilled water to obtain an aqueous solution of cadmium iodide; will H 2 ppza (0.3 mmol, 0.0567g) was dissolved in 15mL acetonitrile to give H 2 ppza in acetonitrile; mixing aqueous solution of cadmium iodide with H 2 Mixing ppza acetonitrile solution, placing the mixture into a sealed reaction kettle, heating the mixture in a blast drying oven at 120 ℃ for three days, cooling the mixture to room temperature at a rate of 5 ℃ per half hour after heating, and separating out yellow massive crystals in the kettle; the obtained product is filtered, washed and dried at room temperature to obtain the target product, wherein the yield is 58%.
The infrared absorption peaks of the obtained Cd (II) coordination polymer comprise: 3442 (s), 1623 (m), 1383 (w), 1306 (w), 1108 (m), 813 (w), 714 (w), 622 (w), 516 (w), 495 (w). The elemental analysis data were: c,39.22; h,3.35; n,18.54 (theoretical); c,39.12; h,3.41; n,18.55 (experimental values). The crystallographic data of the complex are as follows: triclinic, P-1 space group,
α＝100.353(2)°，β＝106.301(2)°，γ＝112.195(2)°，
Z＝2。
as shown in FIG. 1, asymmetric unit package of the complex of the present inventionContaining one Cd (II) ion, one Hppza which is not completely deprotonated - Ligand anion, one iodide ion and one coordinating water molecule. As shown in FIG. 2, each Cd (II) center is located in the N2O2 coordination environment of the ligand (each Cd is 2+ The metal center is hexacoordinated, i.e. coordinated to six atoms, four of which are derived from the ligand, O2B, N1A, N3, two carboxylic acid oxygen atoms (O2, O2B), one pyridine nitrogen atom (N1A), one pyrazole nitrogen atom (N3), one oxygen atom coordinating water (O3) and one I of three asymmetric ligands - Coordination; thus, the resulting CdN2O3I polyhedral geometry can be considered as a distorted octahedron, where the equatorial position is occupied by N1A, O2B, N3, O3 atoms and the axial position is occupied by I1, O2 atoms (symmetric opcode: A =1+ x,1+ y,1+ z B =2-x,3-y, 2-z), and with the normal Cd-O (2.3664 (19) } x
) Cd-N (2.307 (2)) and
)、Cd–I
the bond length. As shown in FIG. 3, the deprotonated ligand links Cd (II) into a one-dimensional double-stranded structure. As shown in FIG. 4, adjacent one-dimensional chains are connected into a two-dimensional layered structure through hydrogen bonds formed between oxygen atoms of coordinated water molecules and iodide ions, and the layers are stacked into a three-dimensional supramolecular structure through hydrogen bonds formed between oxygen atoms of coordinated water molecules and carboxylic acid oxygen atoms of ligands. As shown in FIG. 5, the powder diffraction pattern of the solid was determined and [ Cd (Hppza) - )(H 2 O)I] n The simulation patterns of the single crystal structure analysis are basically consistent, which indicates that the complex is crystallized in a pure phase.
The x-ray diffraction data of the Cd (II) coordination polymer is collected by a Bruker Smart Apex CCD single crystal diffractometer, and graphite is adopted for monochromeChemical Mo-K alpha ray
Diffraction point data were collected at low temperature by means of a ω -scan technique. And (3) analyzing the crystal structure by using SHELXS-97 software through a direct method, and refining by using a full matrix least square method to perform anisotropic displacement parameter refining on all non-hydrogen atoms. The crystallographic parameters of the complex are shown in table 1:
TABLE 1 is a table of crystallographic parameters for Cd (II) coordination polymers
Thermal stability test of Cd (II) coordination polymer prepared in example 1:
in N 2 The sample (Cd (II) coordination polymer prepared in example 1) was heated in an alumina crucible at a rate of 10 ℃/min in an atmosphere in the range of 30 to 800 ℃. As shown in FIG. 6, the complex maintains its structure at 273 ℃ or lower, and the complex begins to lose weight rapidly (removal of coordinated water) by further heating, and the skeleton completely collapses at 900 ℃ in response to the decomposition of the organic ligand.
Fluorescence performance test of Cd (II) coordination polymer prepared in example 1:
free ligand H was tested at room temperature 2 Solid state fluorescence emission spectra of ppza and the complex. As shown in FIG. 7, H at 324nm excitation 2 The ppza ligand showed weak luminescence with a maximum emission wavelength of 351nm, probably due to the semi-rigid ligand π - π * Due to electron migration. The maximum emission wavelength of the complex under 317nm excitation is 347nm. The maximum emission peak of the complex is slightly blue-shifted compared to the ligand. This is due to d 10 The Cd (II) ion in the configuration is difficult to oxidize or reduce, so the fluorescence emission of the complex is the result of charge transfer between ligands. In addition, the fluorescence intensity of the complex is farIs larger than a free ligand, especially a Cd (II) complex, on one hand, the introduction of the transition metal can effectively enhance the rigidity of the ligand so as to be beneficial to the migration of electrons, further reduce the energy loss caused by non-radiative decay and enhance the luminous intensity, and on the other hand, the introduction of the transition metal is d 10 The configured metal ions are good luminescent centers.
Claims (5)
1. A cadmium coordination polymer based on a pyrazole carboxylic acid ligand is characterized in that the chemical formula of the cadmium coordination polymer is as follows: [ Cd (Hppza) − )(H 2 O)I] n ；H 2 ppza is 5- (4-pyridine) -1H-pyrazole-3-carboxylic acid;
the coordination polymer has a one-dimensional double-chain structure, belongs to a triclinic system, and has a space group ofP-1The unit cell parameters are:a＝7.0227(3)Å，b＝9.1109(4) Å，c＝10.5042(4) Å，α＝100.353(2)°，β＝106.301(2)°，γ＝112.195(2)°，V＝565.56(4) Å 3 ，Z＝2。
2. the cadmium coordination polymer based on pyrazole carboxylic acid ligand according to claim 1, characterized in that the basic structural unit of the cadmium coordination polymer is: cd (II) ion as central metal ion, oxygen atom of coordinated water, I − And Hppza − Coordinating the ligand; wherein, pyrazole ring nitrogen atom, carboxylic acid oxygen atom and central metal ion Cd in the ligand 2+ And (4) coordination.
3. The pyrazole carboxylic acid ligand-based cadmium coordination polymer according to claim 2, wherein: the pyridine nitrogen atom in each basic structural unit is connected to a metal central ion Cd 2+ Extended into a one-dimensional chain structure, and a carboxyl oxygen atom is simultaneously connected with another metal central ion Cd 2+ Forming a double-chain structure, and growing to obtain the one-dimensional double-chain polymer.
4. The method of preparing a cadmium coordination polymer according to claim 1, comprising the steps of:
(1) Dissolving cadmium iodide in distilled water to obtain a cadmium iodide aqueous solution;
(2) H is to be 2 ppza dissolved in acetonitrile to give H 2 ppza acetonitrile solution; h 2 ppza is 5- (4-pyridine) -1H-pyrazole-3-carboxylic acid;
(3) Mixing aqueous solution of cadmium iodide with H 2 Mixing ppza acetonitrile solutions, placing the mixture at a high temperature for reaction, and cooling the mixture to room temperature at a rate of 5 ℃ per half hour after the reaction to obtain yellow massive crystals; aqueous cadmium iodide solution and H 2 Cadmium iodide and H in mixed solution obtained by mixing ppza acetonitrile solution 2 The molar ratio of ppza was 1:1;
(4) And filtering, washing and drying the obtained product to obtain the target product.
5. The method of claim 4, wherein the cadmium coordination polymer is prepared by: in the step (3), the reaction temperature is 120 ℃ and the reaction time is three days.
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| CN101798319A (en) * | 2009-12-10 | 2010-08-11 | 郑州轻工业学院 | 2, 3, 4, 5-tetrahydrofuran tetracarboxylic acid and 3-(2-pyridyl) pyrazol-mixed cadmium composition, as well as preparation method and application thereof |
| CN103554083A (en) * | 2013-11-11 | 2014-02-05 | 吉林化工学院 | Monocrystal structure of cadmium coordination compound with blue light performance and preparation method thereof |
| WO2014114948A1 (en) * | 2013-01-24 | 2014-07-31 | Johnson Matthey Public Limited Company | Method of manufacture |
| CN105585586A (en) * | 2016-01-21 | 2016-05-18 | 山西大学 | Benzimidazole type cadimium complexes with fluorescence as well as preparation method and application of cadimium complexes |
| CN111875809A (en) * | 2020-08-07 | 2020-11-03 | 江苏师范大学 | Cationic cadmium-based metal-organic framework crystalline material and preparation method and application thereof |
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| CN101798319A (en) * | 2009-12-10 | 2010-08-11 | 郑州轻工业学院 | 2, 3, 4, 5-tetrahydrofuran tetracarboxylic acid and 3-(2-pyridyl) pyrazol-mixed cadmium composition, as well as preparation method and application thereof |
| WO2014114948A1 (en) * | 2013-01-24 | 2014-07-31 | Johnson Matthey Public Limited Company | Method of manufacture |
| CN103554083A (en) * | 2013-11-11 | 2014-02-05 | 吉林化工学院 | Monocrystal structure of cadmium coordination compound with blue light performance and preparation method thereof |
| CN105585586A (en) * | 2016-01-21 | 2016-05-18 | 山西大学 | Benzimidazole type cadimium complexes with fluorescence as well as preparation method and application of cadimium complexes |
| CN111875809A (en) * | 2020-08-07 | 2020-11-03 | 江苏师范大学 | Cationic cadmium-based metal-organic framework crystalline material and preparation method and application thereof |
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