CN115490870B - Silver coordination polymer based on pyrazine and phenyl dicarboxylic acid and preparation method thereof - Google Patents
Silver coordination polymer based on pyrazine and phenyl dicarboxylic acid and preparation method thereof Download PDFInfo
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- KYQCOXFCLRTKLS-UHFFFAOYSA-N Pyrazine Chemical compound C1=CN=CC=N1 KYQCOXFCLRTKLS-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000013256 coordination polymer Substances 0.000 title claims abstract description 68
- 229920001795 coordination polymer Polymers 0.000 title claims abstract description 68
- PCNDJXKNXGMECE-UHFFFAOYSA-N Phenazine Natural products C1=CC=CC2=NC3=CC=CC=C3N=C21 PCNDJXKNXGMECE-UHFFFAOYSA-N 0.000 title claims abstract description 35
- -1 phenyl dicarboxylic acid Chemical compound 0.000 title claims abstract description 24
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 24
- 239000004332 silver Substances 0.000 title claims abstract description 22
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 13
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 7
- 239000000725 suspension Substances 0.000 claims abstract description 7
- 239000012046 mixed solvent Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims abstract description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 45
- WWYDYZMNFQIYPT-UHFFFAOYSA-N ru78191 Chemical compound OC(=O)C(C(O)=O)C1=CC=CC=C1 WWYDYZMNFQIYPT-UHFFFAOYSA-N 0.000 claims description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 2
- 239000011787 zinc oxide Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 239000013110 organic ligand Substances 0.000 abstract description 4
- 238000005556 structure-activity relationship Methods 0.000 abstract description 3
- 239000003446 ligand Substances 0.000 description 45
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 6
- 125000004430 oxygen atom Chemical group O* 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000003993 interaction Effects 0.000 description 5
- 229910021645 metal ion Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 208000016261 weight loss Diseases 0.000 description 5
- 230000004580 weight loss Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 150000003378 silver Chemical class 0.000 description 4
- 235000000621 Bidens tripartita Nutrition 0.000 description 3
- 240000004082 Bidens tripartita Species 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical class OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 3
- 208000006637 fused teeth Diseases 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 238000005424 photoluminescence Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 150000003216 pyrazines Chemical class 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000000844 transformation Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- FQCRIFDLUQGBHF-UHFFFAOYSA-N 3-oxo-3-phenoxypropanoic acid Chemical compound OC(=O)CC(=O)OC1=CC=CC=C1 FQCRIFDLUQGBHF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 238000006114 decarboxylation reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000005232 molecular self-assembly Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
Abstract
The invention discloses a silver coordination polymer based on pyrazine and phenyl dicarboxylic acid and a preparation method thereof, belonging to the technical field of coordination polymer preparation, and comprising the following steps: and respectively adding silver salt, pyrazine and phenyl dicarboxylic acid into a mixed solvent of methanol and dichloromethane to obtain a suspension, dropwise adding ammonia water while ultrasonic treatment to clarify the suspension, continuing ultrasonic treatment after the ammonia water is dropwise added to obtain a mixed solution, filtering, volatilizing the solvent under a light-shielding condition to obtain colorless crystals, and thus obtaining the silver coordination polymer. The invention synthesizes two coordination polymers with the same structural unit but different supermolecular structures by using an ultrasonic method, and provides an ideal model for researching the structure-activity relationship between the formation influence of an organic ligand coordination mode on the supermolecular structure and the structural performance.
Description
Technical Field
The invention relates to the technical field of coordination polymer preparation, in particular to a silver coordination polymer based on pyrazine and phenyl dicarboxylic acid and a preparation method thereof.
Background
Ag-based coordination compounds are classified into discrete silver clusters and infinite coordination compounds, wherein infinite coordination polymers have attracted extensive attention by researchers due to their novel topology and various functional properties, such as potential applications in catalysis, gas storage, molecular recognition, and magnetic materials. The synthesis of coordination compounds is in fact a molecular self-assembly process, and the design and assembly of coordination compounds with the desired structural and functional properties has been a challenge, and many scientists have been studying discrete silver clusters and infinite coordination polymers based on trial and error results. This is mainly due to numerous factors affecting the final solid state structure during assembly, such as the kind of ligand, the changeable coordination mode, the size of the ligand functional group affecting steric hindrance, the changeable coordination number of the central metal ion and various factors affecting the reaction kinetics including reaction temperature, solvent kind, solution ph, the ratio of central metal ion and ligand, etc. Among these factors, the influence of each factor may lead to different differences in the synthesized structure, so that it is more difficult to synthesize supramolecular structures with the same composition but different coordination modes, understanding the structural characteristics of coordination polymers helps to achieve ideal and rational design of new materials with more predictable solid structures, and designing complex structures with comparable lines is key to understanding the structural characteristics; on the other hand, although there are complex compounds based on pyrazines and aromatic carboxylic acids in the prior art, polymers using pyrazines with phthalic acid and phenylmalonic acid as mixed ligands are rare.
Disclosure of Invention
In view of the above problems, the present invention provides a silver coordination polymer based on pyrazine and phenyl dicarboxylic acid and a preparation method thereof.
The aim of the invention is realized by adopting the following technical scheme:
a method for preparing a silver coordination polymer based on pyrazine and phenyl dicarboxylic acid, comprising the following steps:
respectively adding silver salt, pyrazine and phenyl dicarboxylic acid into a mixed solvent of methanol and dichloromethane to obtain a suspension, dropwise adding ammonia water while ultrasonic treatment to clarify the suspension, continuing ultrasonic treatment after the ammonia water is dropwise added to obtain a mixed solution, filtering, volatilizing the solvent under a light-shielding condition to obtain colorless crystals, and preparing the silver coordination polymer;
wherein the phenyl dicarboxylic acid is phthalic acid or phenylmalonic acid; the molar ratio of the silver salt to the pyrazine and phenyl dicarboxylic acid is 1:1:1, a step of; the volume ratio of the methanol to the dichloromethane in the mixed solvent is 1:1.
preferably, the power of the ultrasonic treatment is 160W, and the ultrasonic frequency is 40kHz.
Preferably, the ultrasonic treatment time is 30min after the completion of the ammonia water dropwise addition.
Another object of the present invention is to provide a silver coordination polymer based on pyrazine and phenyl dicarboxylic acid, having the formula [ Ag (pz) (pta) ]] n Or [ Ag ] 2 (pz)(phma)] n Is a repeating unit of (2); wherein pz is a pyrazine ligand, pta is a phthalic acid ligand, and phma is a phenylmalonic acid ligand.
The beneficial effects of the invention are as follows:
because of numerous factors influencing the final solid structure in the assembly process, such as the types of ligands, changeable coordination modes, the influence of the sizes of ligand functional groups on steric hindrance, changeable coordination numbers of central metal ions, various factors influencing reaction kinetics including reaction temperature, solvent types, solution pH value, the ratio of central metal ions to ligands and the like, the influence of each factor can possibly lead to different days of the synthesized structure, and the supermolecular polymer with structural comparability is difficult to synthesize; the invention synthesizes two coordination polymers with similar structural units but different supermolecular structures by using an ultrasonic method, and provides an ideal model for researching the structure-activity relationship between the formation influence of an organic ligand coordination mode on the supermolecular structure and the structural performance; the polymer prepared by taking pyrazine, phthalic acid and phenylmalonic acid as mixed ligands further perfects the research of pyrazine and aromatic carboxylic acid complexes, and simultaneously, the photoluminescence property of the coordination polymer prepared by the invention also shows that the coordination polymer has good application prospect in optical materials.
Drawings
The invention will be further described with reference to the accompanying drawings, in which embodiments do not constitute any limitation of the invention, and other drawings can be obtained by one of ordinary skill in the art without inventive effort from the following drawings.
FIG. 1 is a schematic view of a club model of the coordination environment of monovalent silver ions in the center of coordination polymer 1 according to an embodiment of the present invention; wherein the hydrogen atoms on the coordination polymer are omitted; ellipsoids are plotted with 50% probability; symmetric operation code: 1 ：3/2-X，3/2-Y，1-Z； 2 ：+X，1-Y，-1/2+Z；
FIG. 2 is a one-dimensional chain structure formed by connecting a pyrazine ligand with a silver atom in the coordination polymer 1 according to the embodiment of the invention; wherein the hydrogen atoms on the coordination polymer are omitted; ellipsoids are plotted with 50% probability;
FIG. 3 is a schematic view of a club model of a coordination polymer 1 phthalic acid ligand coordination mode according to an embodiment of the invention; wherein the hydrogen atoms on the coordination polymer are omitted; ellipsoids are plotted with 50% probability;
FIG. 4 is a two-dimensional view of a wave-like structure of a coordination polymer 1 of the embodiment of the present invention formed of pyrazine ligands and Ag atoms; wherein, the left side is an a-axis direction view, and the right side is a c-axis direction view; the hydrogen atoms on the coordination polymer are omitted;
FIG. 5 is a schematic view of a club model of the coordination environment of monovalent silver ions in the center of coordination polymer 2 according to an embodiment of the present invention; wherein the hydrogen atoms on the coordination polymer are omitted; ellipsoids are plotted with 50% probability; symmetric operation code: 1 ：1-X，2-Y，1-Z； 2 ：-X，2-Y，1-Z； 3 ：-X，3-Y，1-Z；
FIG. 6 is a schematic view of a club model of a coordination polymer 2 phthalic acid ligand coordination mode according to an embodiment of the invention; wherein the hydrogen atoms and pyrazine ligands on the coordination polymer are omitted; ellipsoids are plotted with 50% probability;
FIG. 7 is a three-dimensional structure diagram of a coordination polymer 2 formed by connecting two-dimensional surfaces with pyrazine ligands according to an embodiment of the invention; wherein, the left side is an a-axis direction view, and the right side is a c-axis direction view; the hydrogen atoms on the coordination polymer are omitted;
FIG. 8 is a three-dimensional structure unit cell stacking diagram of a coordination polymer 2 according to an embodiment of the present invention; wherein the hydrogen atoms on the coordination polymer are omitted;
FIG. 9 is a DSC-TGA curve of coordination polymer 1 of the present invention;
FIG. 10 is a DSC-TGA curve of coordination polymer 2 of an embodiment of the present invention;
FIG. 11 is a photoluminescence spectrum of the coordination polymer 1, 2 of the embodiment of the invention.
Detailed Description
The invention will be further described with reference to the following examples; all reagents and solvents used in the following examples were obtained directly commercially without further purification.
Examples
The silver coordination polymer based on pyrazine and phenyl dicarboxylic acid provided by the embodiment of the invention comprises the following steps:
silver nitrate (17.1 mg,0.1 mmol), pyrazine ligand (8.1 mg,0.1 mmol) and phthalic acid (16.6 mg,0.1 mmol) are respectively added into a mixed solvent of methanol and dichloromethane, ultrasonic treatment (160W, 40HKz,30 min) is carried out, the ultrasonic temperature is 40 ℃, ammonia water is dropwise added in the ultrasonic process until the suspension becomes clear, ultrasonic is continued for 30min, the mixed solution is filtered and then slowly volatilized in dark environment in dark place, colorless crystals are obtained within one week, and the colorless crystals are recorded as coordination polymer 1; yield based on silver was 67%;
the molecular formula of the product is C 12 H 9 AgN 2 O 4 Molecular weight 353.08, wherein C:40.79%; n:7.93%; h:2.55%; o:18.13%.
Substitution of the phthalic acid with equimolar phenylmalonic acid, producing colorless crystals, noted coordination polymer 2, with a yield of 63% based on silver;
the molecular formula of the product is C 13 H 10 Ag 2 N 2 O 4 Molecular weight 473.96, wherein C:40.79%; n:7.93%; h:2.55%; o:18.13%.
Analyzing the monocrystal structure of two coordination polymers, and using monocrystal X-ray diffraction intensity data to adopt monochromatic MoK alpha radiation with graphiteIs collected at 173k using a Bruker APEX-II CCD diffractometer. Data were reduced using the program Bruker SAINT and empirical absorption correction based on the multiscan method. The structure of the complex was solved on F2 using the SHELXS-14 procedure and the SHELxsl-18 procedure, respectively, using the full matrix least squares method and the direct method.
Single crystal x-ray diffraction results show that coordination polymer 1 crystallizes in the space group of monoclinic C2/C, and that asymmetric units comprise one independent monovalent silver ion, one phthalic acid ligand and one pyrazine ligand, two nitrogen atoms from two different pyrazine ligands and two oxygen atoms from two different ortho-xylene ligands enclose the crystal independent monovalent silver ion in a distorted tetrahedron in a bridged coordination manner, as shown in fig. 1, the distorted tetrahedron can be denoted as { AgN2O2}. The distortion parameter t4 of the distorted tetrahedral AgN2O2 geometry with the central monovalent silver ion is 0.71, the value of the distortion parameter t represents the geometrical distortion degree of the tetrahedral coordinate metal system, and the value is expressed as perfect four from 1The face geometry to 0 is represented as a full planar geometry. Wherein the Ag-N distance is distributed inWithin the range; ag-O distance distributionThe bond lengths and angles around the central metal silver ion are included in table 1, within the range, comparable to the monovalent silver bond lengths of other monovalent silver coordination polymers.
TABLE 1 determination of bond lengths around coordination Polymer 1 Metal center by x-ray diffractionAnd key angle (°)
| Ag1-Ag1 1 | 3.3626(8) | Ag1-O3 1 | 2.584(2) |
| Ag1-O3 | 2.502(3) | Ag1-N1 | 2.200(3) |
| Ag1-N2 2 | 2.205(3) | ||
| O3Ag1O3 1 | 97.24(8) | N1Ag1O3 | 102.92(11) |
| N1Ag1O3 1 | 92.33(10) | N1Ag1N2 2 | 156.60(14) |
| N2 2 Ag1O3 1 | 91.74(10) | N2 2 Ag1O3 1 | 99.41(11) |
Note that: symmetric transformations for generating equivalent atoms: 1 ：3/2-X，3/2-Y，1-Z； 2 ：+X，1-Y，-1/2+Z。
both the pyrazine ligand and the phthalic acid ligand coordinate with the central metal ion in a double-tooth bridging mode. The pyrazine ligand connects silver ions through a mu 2-N:N' coordination mode to form a one-dimensional infinite chain structure, as shown in figure 2, the chains are connected into a two-dimensional structure through Ag-Ag bonds and Ag-O bonds between the oxygen ions on phthalic acid and the Ag ions, and the Ag-Ag distance isComparable to twice the van der Waals radius, no significant silverphilic interactions were found. The phthalic acid ligand adopts a coordination mode of mu 2-kappa 2:kappa 0:kappa 0 to consolidate the two-dimensional structure, as shown in figure 3, but due to the steric hindrance of phthalic acid, the phthalic acid groups are staggered, so that the final two-dimensional structure is wavy, as shown in figure 4, the phthalic acid ligand is packaged at two sides of the wavy two-dimensional structureNo other supramolecular forces were found, preventing the structure from reaching higher dimensions.
Single crystal x-ray diffraction results show that coordination polymer 2 crystallizes in a triclinic P-1 space group, the asymmetric unit comprising two central monovalent silver ions, one phenylmalonic acid ligand and one pyrazine ligand, wherein half of the pyrazine molecules are generated by a symmetrical operation of (1-x, 1-y, -z), both central silver ions are four-coordinated distorted tetrahedral structures surrounded by oxygen atoms on three different O-phenylmalonic acid ligands and N atoms on one pyrazine ligand, the tetrahedral structures can be represented as { AgO3N1}, as shown in fig. 5, the distortion parameter t4 of the distorted tetrahedral AgO3N1 geometry in which the central monovalent silver ions are located is 0.77, the ag—o distance distribution of which is distributedWithin the range and Ag-N distance of +.>The bond length and angle of the central metallic silver ion around coordination polymer 2 are included in table 2.
TABLE 2 determination of bond lengths around coordination Polymer 2 Metal center by x-ray diffractionAnd key angle (°)
| Ag1-Ag1 2 | 2.8812(5) | Ag1-O1 2 | 2.270(2) |
| Ag1-O2 1 | 2.465(2) | Ag1-O2 | 2.304(2) |
| Ag1-N1 | 2.341(3) | ||
| O1 1 Ag1O2 2 | 113.20(8) | O1 1 Ag1O2 | 137.53(9) |
| O1 1 Ag1N1 | 106.03(9) | O2Ag1O2 2 | 93.47(8) |
| O2Ag1N1 | 107.39(9) | N1Ag1O2 2 | 87.98(9) |
Note that: symmetric transformations for generating equivalent atoms: 1 ：-X，2-Y，1-Z； 2 ：1-X，2-Y，1-Z。
in the coordination polymer 2, the ligand of phenylmalonic acid adopts a coordination mode of mu 6-kappa 1:kappa 2:kappa 1 to connect Ag ions into a two-dimensional structure, as shown in figure 6, but due to the influence of phenyl steric hindrance on phenylmalonic acid, phenyl groups are alternately arranged in opposite directions on the two-dimensional surface, which is importantThe point is that on the two-dimensional surface, the minimum units are connected by Ag-Ag bond and Ag-O bond, the bond length ranges are respectivelyAnd->The average length of Ag-Ag bond is +.>Two times less than Van der Waals radius ++>The presence of significant silver-philic interactions, which are often used to construct supramolecular entities, results in a more stable two-dimensional structure of the connection, the two-dimensional surface being further bridged by pyrazine ligands using a μ2-N: N' coordination mode to form a three-dimensional structure, as shown in FIG. 7.
It should be noted that the coordination polymer 1 and the coordination polymer 2 have the same minimum structural unit and ligand composition, but have such great difference in the final solid structural composition, and the inventor analyzes the reason for this difference, mainly because of the difference between two carboxylic acid coordination modes, in the coordination polymer 1, one oxygen atom of phthalic acid is connected with a central silver atom in a double-tooth coordination manner, and the other three oxygen atoms are not involved in structural coordination, so that only the two-dimensional structure of the coordination polymer is consolidated, and meanwhile, three oxygen atoms which are not coordinated only have O-H … O hydrogen bonds in a single phthalic acid ligand, but also have no other weak interactions to form a three-dimensional structure. In contrast, the four oxygen atoms of the coordination polymer 2 phthalic acid all participate in coordination, and the next smallest structural unit is connected on a two-dimensional surface, so that a critical effect is played on the formation of the two-dimensional surface, and the three-dimensional structure is further bridged by pyrazine double-tooth, as shown in fig. 8.
Thermogravimetric analysis of two coordination polymers was performed and measured at N 2 Thermal stability in the environment, from room temperature to 800 ℃. Warm temperatureThe degree of rise was 10 ℃/min, and referring to fig. 9, it can be seen from the thermogravimetric curve of the coordination polymer 1 that the weight loss was 9.67% from 136.33 ℃ to 199.70 ℃, two water molecules were lost (calculated value was 10.19%, error rate was 5.10%) per structural unit, and from the solid structure of the coordination polymer 1, it can be understood that since the phthalic acid ligand was exposed on the upper and lower sides of the two-dimensional structure and the phthalic acid was monodentate bridged on the two-dimensional surface, the intramolecular dehydration of carboxyl group easily occurred under heating conditions, and that the weight loss was 30.22% from 287.33 ℃ to 316.75 ℃ and the total loss was 39.89% as seen from the endothermic peak corresponding to 168.77 ℃ on DSC differential scanning calorimetric analysis, which can be attributed to the continuous incomplete decomposition of one phthalic acid ligand (calculated value was 47.06%, error rate was 15.23%), while the exothermic peak corresponding to 293.19 ℃ on DSC was continuously heated to 800 ℃ after 315.75 ℃, and the weight loss was 4.24%, which was a result of continuous volatilization of the solid residue.
Referring to fig. 10, coordination polymer 2 was heated from room temperature to 127.05 c with a weight loss of 3.08% (calculated 3.77%), which is caused by the loss of one molecule of water by decarboxylation of the phenylmalonic acid ligand, from 127.05 c to 370.23 c, accompanied by complete decomposition of the phenyldicarboxylic acid ligand and partial decomposition of the pyrazine ligand, resulting in a weight loss of 46.29% (calculated 47.06%, error rate of 1.63%), with a collapse of the three-dimensional framework, which was shown on the thermogravimetric curve by two different decomposition rates, from 370.23 c with continued heating to 800 c with complete loss of weight of the molecule to form a stable product, which was found by calculation and analysis to coincide with the theoretical percentage of elemental silver (calculated 45.57%, practical value of 46.81%).
The photoluminescence behavior of two coordination polymers was studied at room temperature and the emission spectra of the organic ligand pyrazine and two aromatic carboxylic acid ligands could be attributed to the n-pi or pi-pi transition of the ligands. As shown in FIG. 11, the maximum emission wavelength of the coordination polymer 1 at the excitation wavelength of 340nm was 460nm, and two maximum emission waves were observed at 460nm and 525nm at the excitation wavelength of 390nm for the coordination polymer 2. The main emission peaks of coordination polymers 1 and 2 are red shifted not only because of coordination of the metal center and the ligand, effectively enhancing the rigidity of the ligand, reducing energy loss caused by non-radiative decay, but also because of charge transfer of the ligand-metal (LMCT). Furthermore, the difference in Ag-Ag interactions may also have a significant impact on the photoluminescent properties of such complexes. The appearance of two maximum emission peaks for coordination polymer 2 may be that coordination polymer 2 has a stronger silver-philic interaction than 1. The results show that the coordination polymer provided by the invention may have good application prospects in optical materials.
In the embodiment of the invention, two coordination polymers with similar structural units but different supramolecular structures are synthesized by using an ultrasonic method, and an ideal model is provided for researching the structure-activity relationship between the formation influence of an organic ligand coordination mode on the supramolecular structure and the structural performance; the polymer prepared by taking pyrazine, phthalic acid and phenylmalonic acid as mixed ligands further perfects the research of pyrazine and aromatic carboxylic acid complexes, and simultaneously, the photoluminescence property of the coordination polymer prepared by the invention also shows that the coordination polymer has good application prospect in optical materials.
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (1)
1. A method for preparing a silver coordination polymer based on pyrazine and phenyl dicarboxylic acid, characterized by comprising the following steps:
respectively adding silver salt, pyrazine and phenyl dicarboxylic acid into a mixed solvent of methanol and dichloromethane to obtain a suspension, dropwise adding ammonia water while ultrasonic treatment to clarify the suspension, continuing ultrasonic treatment after the ammonia water is dropwise added to obtain a mixed solution, filtering, volatilizing the solvent under a light-shielding condition to obtain colorless crystals, and preparing the silver-doped zinc oxide film;
wherein the phenyl dicarboxylic acid is phthalic acid or phenylmalonic acid; the molar ratio of the silver salt to the pyrazine and phenyl dicarboxylic acid is 1:1:1, a step of; the volume ratio of the methanol to the dichloromethane in the mixed solvent is 1:1, a step of;
the power of the ultrasonic treatment is 160W, and the ultrasonic frequency is 40kHz;
and continuing ultrasonic treatment for 30min after the ammonia water is added dropwise.
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| Synthesis, crystal structures and photocatalytic properties of four silver(I) coordination polymers based on nitroterephthalic acid;Yuan-Yuan Yang et al.;Polyhedron;第148卷;161-170 * |
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