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
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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
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
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。
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