CN107629217B - Cu-Nd dissimilar metal coordination polymer and preparation method thereof - Google Patents
Cu-Nd dissimilar metal coordination polymer and preparation method thereof Download PDFInfo
- Publication number
- CN107629217B CN107629217B CN201710924741.2A CN201710924741A CN107629217B CN 107629217 B CN107629217 B CN 107629217B CN 201710924741 A CN201710924741 A CN 201710924741A CN 107629217 B CN107629217 B CN 107629217B
- Authority
- CN
- China
- Prior art keywords
- coordination polymer
- dissimilar metal
- metal coordination
- dicarboxylic acid
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Landscapes
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention discloses a Cu-Nd dissimilar metal coordination polymer and a preparation method thereof. The chemical formula of the Cu-Nd dissimilar metal coordination polymer is { [ Nd (L)1)2Cu(L2)(H2O)2]·3H2O}nThe molecular formula is: c15H15CuN6NdO15The molecular weight is: 727.10. (1) dissolving neodymium perchlorate hexahydrate and copper acetate in distilled water; (2) dissolving 3, 5-pyrazole dicarboxylic acid and 2-pyrazine carboxylic acid in DMF; (3) mixing the solutions prepared in the steps (1) and (2), adjusting the pH value with ethylenediamine, filtering and drying to obtain a Cu-Nd dissimilar metal coordination polymer L1Is represented by 3, 5-pyrazole dicarboxylic acid with two negative charges of two units after two carboxyl hydrogen atoms are removed; l is2Represents 2-pyrazine carboxylic acid without one carboxyl hydrogen atom. The invention has simple process and good repeatability.
Description
Technical Field
The invention relates to the field of Cu-Nd dissimilar metal coordination polymer preparation, in particular to a dissimilar metal coordination polymer and a preparation method thereof.
Background
In recent decades, with the continuous development of structural testing techniques and other related subjects, coordination polymer materials have emerged endlessly, and become one of the research hotspots in the material field. The coordination polymer material has various types, special topological structure, large specific surface area and adjustable pore size, and a novel structure can be constructed by selecting and designing different metal centers and organic ligands, so that certain contribution is made to the application field of the coordination polymer material. At present, no related reports are found on the heterometallic coordination polymer constructed by 3, 5-pyrazole dicarboxylic acid and 2-pyrazine formic acid.
Disclosure of Invention
The invention aims to provide a synthetic method of a Cu-Nd dissimilar metal coordination polymer.
The chemical formula of the Cu-Nd dissimilar metal coordination polymer related by the invention is { [ Nd (L)1)2Cu(L2)(H2O)2]·3H2O}nThe molecular formula is: c15H15CuN6NdO15The molecular weight is: 727.10, wherein L1Is represented by 3, 5-pyrazole dicarboxylic acid with two negative charges of two units after two carboxyl hydrogen atoms are removed; l is2Represents that 2-pyrazine carboxylic acid has one unit of negative charge after one carboxyl hydrogen atom is removed. The crystal structure data are shown in the table I, and the bond length and the bond angle are shown in the table II.
Cu-Nd heterometallic coordination polymer { [ Nd (L)1)2Cu(L2)(H2O)2]·3H2O}nThe infrared spectrum of the product is confirmed to be 3403.38cm-1A wide absorption peak is formed, and the peak is caused by the stretching vibration of O-H of water molecules; at 1688.96cm-1The absorption peak is caused by the stretching vibration of C ═ O; 1340.59cm-1The strong peak vibration is the stretching vibration of the carboxylic acid C-O; 1232.75cm-1The vibration of (b) is the vibration of C-N. The N-H stretching vibration peak, C ═ N stretching vibration absorption peak and O-H bending vibration peak of carboxyl group were not found in the figure, indicating that nitrogen and oxygen atoms of 3, 5-pyrazoledicarboxylic acid and 2-pyrazinecarboxylic acid were coordinated. The infrared test results are the same as the single crystal diffraction results.
In N2Under protection, the test range is 25-800 ℃, the temperature is increased at the speed of 10 ℃/min, and the Cu-Nd dissimilar metal coordination polymer { [ Nd (L) } is tested1)2Cu(L2)(H2O)2]·3H2O}nThe thermal properties of (a). The weight loss is about 8 percent between 82 ℃ and 145 ℃, the loss is three free water molecules in the pore canal of the complex, the three free water molecules are consistent with the theoretical calculation value of 7.76 percent, and the complex collapses at the skeleton about 290 ℃ along with the rise of the temperature. The temperature continues to rise, and the remainder is the mostFinally decomposing into metal oxide. The results show that the coordination polymer has better thermal stability.
Table one: { [ Nd (L)1)2Cu(L2)(H2O)2]·3H2O}nCrystal parameter (d)
aR1＝Σ||Fo|–|Fc||/Σ|Fo|.bwR2＝[Σw(|Fo 2|–|Fc 2|)2/Σw(|Fo 2|)2]1/2
Table two: { [ Nd (L)1)2Cu(L2)(H2O)2]·3H2O}nLength of the bond
Angle of harmony key (°)
Symmetry codes:(i)x+1/2,-y+1/2,z-1/2；(ii)x-1/2,-y+1/2,z-1/2；(iii)-x+1,-y,-z+1；(iv)x-1/2,-y+1/2,z+1/2；(v)x+1/2,-y+1/2,z+1/2.
The { [ Nd (L) { [ L ]1)2Cu(L2)(H2O)2]·3H2O}nThe synthesis method comprises the following specific steps:
(1) 0.1180g of NdCl3·6H2O and 0.05g Cu (OAC)2·H2Dissolving O in 10mL of distilled water, and uniformly stirring to prepare a mixed metal solution for later use.
(2) 0.172g of 3, 5-pyrazole dicarboxylic acid and 0.120g of 2-pyrazine carboxylic acid were dissolved in 10mL of analytically pure N, N-Dimethylformamide (DMF), and the mixture was stirred uniformly to prepare a mixed ligand solution.
(3) Dropwise adding the mixed metal solution obtained in the step (1) into the mixed ligand solution obtained in the step (2), uniformly stirring to obtain a blue turbid solution, then adjusting the pH value by using analytically pure ethylenediamine until the solution is just clear, wherein the pH value of the solution is about 5-6, stirring for 30 minutes, filtering, placing the filtrate into a beaker, sealing by using a preservative film, placing the beaker into a 70-80 ℃ incubator, reacting for 12 hours, and then forming a blue flaky transparent crystal, namely the Cu-Nd heterometallic coordination polymer { [ Nd (L)1)2Cu(L2)(H2O)2]·3H2O}n. Measurement of { [ Nd (L) by Single Crystal diffractometer1)2Cu(L2)(H2O)2]·3H2O}nThe crystal structure data is shown in table one, and the bond length and bond angle is shown in table two.
The method has the advantages of simple process, easy control of chemical components, good repeatability, high yield and the like.
Drawings
FIG. 1 shows a Cu-Nd heterometallic coordination polymer { [ Nd (L)1)2Cu(L2)(H2O)2]·3H2O}nThe structure of (1).
FIG. 2 shows a Cu-Nd heterometallic coordination polymer { [ Nd (L)1)2Cu(L2)(H2O)2]·3H2O}nThe infrared absorption spectrum of (1).
FIG. 3 shows a Cu-Nd heterometallic coordination polymer { [ Nd (L)1)2Cu(L2)(H2O)2]·3H2O}nThermal performance map of.
Detailed Description
Example (b):
the chemical formula of the Cu-Nd dissimilar metal coordination polymer constructed by 3, 5-pyrazole dicarboxylic acid and 2-pyrazine formic acid is as follows: { [ Nd (L)1)2Cu(L2)(H2O)2]·3H2O}nThe molecular weight is: 727.10, wherein L1Is represented by 3,5Pyrazole dicarboxylic acid is deprived of two carboxyl hydrogen atoms and has two units of negative charge; l is2Represents that 2-pyrazine carboxylic acid has one unit of negative charge after one carboxyl hydrogen atom is removed.
{[Nd(L1)2Cu(L2)(H2O)2]·3H2O}nThe synthesis method comprises the following specific steps:
(1) 0.1180g of NdCl3·6H2O and 0.05g Cu (OAC)2·H2Dissolving O in 10mL of distilled water, and uniformly stirring to obtain a mixed metal solution.
(2) 0.172g of 3, 5-pyrazole dicarboxylic acid and 0.120g of 2-pyrazine carboxylic acid were dissolved in 10mL of analytically pure N, N-Dimethylformamide (DMF), and the mixture was stirred uniformly to prepare a mixed ligand solution.
(3) Dropwise adding the mixed metal solution obtained in the step (1) into the mixed ligand solution obtained in the step (2), uniformly stirring to obtain a blue turbid solution, then adjusting the pH value by using analytically pure ethylenediamine until the solution is just clear, wherein the pH value of the solution is 5, stirring for 30 minutes, filtering, placing the filtrate in a beaker, sealing by using a preservative film, placing the beaker in a 70 ℃ incubator, reacting for 12 hours, and then forming a blue flaky transparent crystal, namely the Cu-Nd heterometallic coordination polymer { [ Nd (L)1)2Cu(L2)(H2O)2]·3H2O}n. Determination of Cu-Nd heterometallic Polymer { [ Nd (L) by Single Crystal diffractometer1)2Cu(L2)(H2O)2]·3H2O}nThe crystal structure data is shown in table one, and the bond length and bond angle is shown in table two.
Claims (1)
1. A synthetic method of a Cu-Nd dissimilar metal coordination polymer is characterized by comprising the following specific steps:
(1) 0.1180g of NdCl3·6H2O and 0.05g Cu (OAC)2·H2Dissolving O in 10mL of distilled water, and uniformly stirring to obtain a mixed metal salt solution;
(2) dissolving 0.172g of 3, 5-pyrazole dicarboxylic acid and 0.120g of 2-pyrazine carboxylic acid in 10mL of analytically pure N, N-dimethylformamide, and uniformly stirring to prepare a mixed ligand solution;
(3) dropwise adding the mixed metal salt solution obtained in the step (1) into the mixed ligand solution obtained in the step (2), uniformly stirring to obtain a blue turbid solution, then adjusting the pH value by using analytically pure ethylenediamine until the solution is just clear, wherein the pH value of the solution is 5-6, stirring for 30 minutes, filtering, placing the filtrate in a beaker, sealing by using a preservative film, placing in a 70-80 ℃ incubator, reacting for 12 hours, and then generating a blue flaky transparent crystal, namely a Cu-Nd dissimilar metal coordination polymer;
the chemical formula of the Cu-Nd dissimilar metal coordination polymer is { [ Nd (L)1)2Cu(L2)(H2O)2]·3H2O}nWherein L is1Represents that 3, 5-pyrazole dicarboxylic acid is deprived of two carboxyl hydrogen atoms and has two units of negative charges; l is2The compound is 2-pyrazine carboxylic acid with one unit of negative charge after one carboxyl hydrogen atom is removed, and the molecular formula is as follows: c15H15CuN6NdO15Belonging to the monoclinic system, space group is P21And/n, the molecular structure is as follows:
the basic structural unit of the Cu-Nd dissimilar metal coordination polymer comprises a neodymium ion, a copper ion, two 3, 5-pyrazole dicarboxylic acid anions, a 2-pyrazine carboxylic acid anion and two water molecules; the neodymium ion is nine-coordinate, and the copper ion is five-coordinate; one of the oxygen atoms of the carboxyl groups of the 3, 5-pyrazole dicarboxylic acid chelates neodymium ions with the adjacent nitrogen atom, and the other oxygen atom of the carboxyl groups chelates copper ions with the adjacent nitrogen atom; one oxygen atom of carboxyl in the 2-pyrazinecarboxylic acid and one nitrogen atom of a pyrazine group chelate neodymium ion, and the other nitrogen atom of the pyrazine group coordinates with copper ion; the crystal structure data is shown in a table I, and the bond length and the bond angle are shown in a table II;
table one: { [ Nd (L)1)2Cu(L2)(H2O)2]·3H2O}nCrystal parameter (d)
aR1＝∑||Fo|-|Fc||/∑|Fo|.bwR2＝[∑w(|Fo 2|-|Fc 2|)2/∑w(|Fo 2|)2]1/2
Table two: { [ Nd (L)1)2Cu(L2)(H2O)2]·3H2O}nLength of the bond
Angle of harmony key (°)
Symmetry codes：(i)x+1/2，-y+1/2，z-1/2；(ii)x-1/2，-y+1/2，z-1/2；(iii)-x+1，-y，-z+1；(iv)x-1/2，-y+1/2，z+1/2；(v)x+1/2，-y+1/2，z+1/2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710924741.2A CN107629217B (en) | 2017-10-01 | 2017-10-01 | Cu-Nd dissimilar metal coordination polymer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710924741.2A CN107629217B (en) | 2017-10-01 | 2017-10-01 | Cu-Nd dissimilar metal coordination polymer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107629217A CN107629217A (en) | 2018-01-26 |
| CN107629217B true CN107629217B (en) | 2021-01-05 |
Family
ID=61103752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710924741.2A Active CN107629217B (en) | 2017-10-01 | 2017-10-01 | Cu-Nd dissimilar metal coordination polymer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107629217B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108440769B (en) * | 2018-04-19 | 2021-03-26 | 同济大学 | Hydrogen-bonded porous copper coordination polymer and preparation method thereof |
| CN112029109B (en) * | 2020-09-11 | 2022-02-25 | 陕西师范大学 | Metal organic framework material with copper-pyrazine ligand regulating pore size, preparation method thereof and application of metal organic framework material in methane purification |
| CN115530233B (en) * | 2022-10-25 | 2023-11-14 | 嘉应学院 | Fresh-keeping composition and method for delaying lignification of grapefruit pulp |
| CN117143350B (en) * | 2023-08-29 | 2024-03-12 | 广东工业大学 | Dissimilar metal organic molecular cage material, preparation method and application thereof, and preparation method for oxidizing thioether into sulfone |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659852A (en) * | 2012-05-16 | 2012-09-12 | 北京化工大学 | Metal-organic coordination polymer containing neodymium and copper and preparation method |
| WO2015183813A2 (en) * | 2014-05-26 | 2015-12-03 | King Abdullah University Of Science And Technology | Design, synthesis and characterization of metal organic frameworks |
| CN106866986A (en) * | 2017-01-10 | 2017-06-20 | 沈阳化工大学 | Pd/Ln different metal organic frames and preparation method and application |
-
2017
- 2017-10-01 CN CN201710924741.2A patent/CN107629217B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102659852A (en) * | 2012-05-16 | 2012-09-12 | 北京化工大学 | Metal-organic coordination polymer containing neodymium and copper and preparation method |
| WO2015183813A2 (en) * | 2014-05-26 | 2015-12-03 | King Abdullah University Of Science And Technology | Design, synthesis and characterization of metal organic frameworks |
| CN106866986A (en) * | 2017-01-10 | 2017-06-20 | 沈阳化工大学 | Pd/Ln different metal organic frames and preparation method and application |
Non-Patent Citations (4)
| Title |
|---|
| "一系列基于吡啶-2， 3-二羧酸的铜-稀土异金属配位聚合物";刘颖等;《黑龙江大学工程学报》;黑龙江大学;20170331;第8卷(第1期);第34-41页 * |
| "稀土有机框架材料（Ln-MOFs）的合成及应用";董飘平等;《有色金属科学与工程》;20160630;第7卷(第3期);第137-150页 * |
| "系列双核异金属型MOFs材料的合成及性质";丁伟刚等;《2017年中西部地区无机化学化工学术研究会论文集》;中国化学会;20170428;第200页 * |
| "系列双核异金属型MOFs材料的合成及性质研究";丁伟刚等;《2017年中西部地区无机化学化工学术研究会论文集》;20170428;第200页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107629217A (en) | 2018-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107629217B (en) | Cu-Nd dissimilar metal coordination polymer and preparation method thereof | |
| Wisser et al. | Chiral Coordination Polymers with Amino Acids: \rm^2_∞Cu_2(μ-L-tryptophanato)_2(μ-4,4′-bipyridine)(H_2O)_2(NO_3)_2 | |
| Hou et al. | Synthesis, crystal structure, photoluminescence property and photoelectronic behavior of two uranyl-organic frameworks constructed from 1, 2, 4, 5-benzenetetracarboxylic acid as ligand | |
| CN103787875A (en) | Method of preparing metal organic frame compound by using ultrasonic waves | |
| CN107746465B (en) | Nd-MOF material constructed by taking 3, 5-pyrazole dicarboxylic acid as ligand and preparation method thereof | |
| Qin et al. | Two dinuclear copper (II) complexes based on 5, 6-dimethylbenzimidazole ligands: synthesis, crystal structures, and catalytic properties | |
| CN115254189B (en) | Iron tailing sand MOF composite photocatalyst and preparation method and application thereof | |
| CN105001246A (en) | 8-aminoquinoline Schiff base zinc azide metal complex and preparation method thereof | |
| CN109096314A (en) | (-) -4,5- firpene-bipy 2,2' bipyridyl copper nitrate monokaryon chiral coordination compound and preparation method thereof | |
| CN104341456B (en) | (R, R)-1,2-diphenyl ethylene diamine nitrine nickel complex and preparation method thereof | |
| CN110862404A (en) | Metal organic framework crystal material based on cyclohexane hexacarboxylic acid and bipyridyl and preparation method thereof | |
| CN103086916A (en) | Schiff base functionalized Gemini ionic liquid and preparation method thereof | |
| CN106832326B (en) | A kind of high-thermal-stability cerium coordination polymer and its preparation method and application | |
| Majid et al. | Synthesis, characterization and coordinating behaviour of aminoalcohol complexes with transition metals | |
| CN104829637A (en) | Zinc complex containing bistriazole butane and pyrazine diacid and preparation method of zinc complex | |
| CN107840967B (en) | Cu-Sm dissimilar metal coordination polymer and preparation method thereof | |
| CN113980286A (en) | Synthesis method and application of Ni-based coordination polymer | |
| Paolucci et al. | Compartmental ligands: Synthesis and characterization of polynuclear uranyl complexes | |
| CN111116932A (en) | Metal organic coordination polymer based on hexanuclear cobalt (II) and preparation method thereof | |
| Yu et al. | Synthesis and NMR studies of silver complexes with octaaza Schiff-base cryptands and the structure of a polymeric silver cryptate | |
| Snavely et al. | Magnetic behavior of metal derivatives of substituted phenylazo-5-pyrazolones | |
| Masoud et al. | Synthesis and stereochemistry of new cobalt azo-nitroso complexes | |
| Ding et al. | Synthesis, Structure and Properties of an Unusual 2D Network Zinc Coordination Polymer Based on Pentanuclear Zinc Cluster | |
| CN108912180B (en) | (-) -2- (4 ', 5 ' -pinene pyridyl-2 ') pyrazine azide cobalt (III) complex and preparation method thereof | |
| WO2020184336A1 (en) | Liquid metal complex having oxygen-absorbing ability |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20180126 Assignee: Guilin Qi Hong Technology Co.,Ltd. Assignor: GUILIN University OF TECHNOLOGY Contract record no.: X2022450000122 Denomination of invention: A Cu Nd Heterometal Coordination Polymer and Its Preparation Method Granted publication date: 20210105 License type: Common License Record date: 20221123 |
|
| EE01 | Entry into force of recordation of patent licensing contract |