CN111732614B - Synthesis method of novel eutectic cobalt complex - Google Patents
Synthesis method of novel eutectic cobalt complex Download PDFInfo
- Publication number
- CN111732614B CN111732614B CN202010648610.8A CN202010648610A CN111732614B CN 111732614 B CN111732614 B CN 111732614B CN 202010648610 A CN202010648610 A CN 202010648610A CN 111732614 B CN111732614 B CN 111732614B
- Authority
- CN
- China
- Prior art keywords
- reaction kettle
- eutectic
- cobalt
- phenanthroline
- complex
- 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
- 230000005496 eutectics Effects 0.000 title claims abstract description 31
- 150000004700 cobalt complex Chemical class 0.000 title claims abstract description 28
- 238000001308 synthesis method Methods 0.000 title description 4
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 8
- 229940011182 cobalt acetate Drugs 0.000 claims abstract description 7
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims abstract description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims abstract description 6
- 239000000706 filtrate Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000001914 filtration Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract 18
- 239000013078 crystal Substances 0.000 claims description 18
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- SBBQDUFLZGOASY-OWOJBTEDSA-N 4-[(e)-2-(4-carboxyphenyl)ethenyl]benzoic acid Chemical compound C1=CC(C(=O)O)=CC=C1\C=C\C1=CC=C(C(O)=O)C=C1 SBBQDUFLZGOASY-OWOJBTEDSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 6
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims 4
- 150000001868 cobalt Chemical class 0.000 claims 3
- 239000000376 reactant Substances 0.000 claims 2
- 238000005303 weighing Methods 0.000 claims 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 5
- 238000011160 research Methods 0.000 abstract description 4
- 238000010791 quenching Methods 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 238000005424 photoluminescence Methods 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract 1
- 239000003446 ligand Substances 0.000 description 17
- 230000015572 biosynthetic process Effects 0.000 description 5
- OONPLQJHBJXVBP-UHFFFAOYSA-N 3-(2-phenylethenyl)phthalic acid Chemical class OC(=O)C1=CC=CC(C=CC=2C=CC=CC=2)=C1C(O)=O OONPLQJHBJXVBP-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910020647 Co-O Inorganic materials 0.000 description 3
- 229910020704 Co—O Inorganic materials 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 125000004430 oxygen atom Chemical group O* 0.000 description 3
- 229910020676 Co—N Inorganic materials 0.000 description 2
- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 229910001429 cobalt ion Inorganic materials 0.000 description 2
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 238000012844 infrared spectroscopy analysis Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000000474 nursing effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/06—Cobalt compounds
- C07F15/065—Cobalt compounds without a metal-carbon linkage
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C63/00—Compounds having carboxyl groups bound to a carbon atoms of six-membered aromatic rings
- C07C63/66—Polycyclic acids with unsaturation outside the aromatic rings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1007—Non-condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1003—Carbocyclic compounds
- C09K2211/1011—Condensed systems
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/187—Metal complexes of the iron group metals, i.e. Fe, Co or Ni
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- Nitrogen Condensed Heterocyclic Rings (AREA)
Abstract
A novel eutectic cobalt complex belongs to a triclinic system and P ī space group, and the chemical formula of the novel eutectic cobalt complex is [ Co (1, 10-phen) 2(AcO)]·H2SDA·11H2 O. Putting 1, 10-phenanthroline, 4' -diphenylethylene dicarboxylic acid and sodium hydroxide solid into a polytetrafluoroethylene substrate hydrothermal reaction kettle with the volume of 30mL, adding dimethylformamide and water, stirring, adding cobalt acetate, adjusting the pH value, and then putting into the reaction kettle for constant-temperature reaction. And taking out the reaction kettle, naturally cooling the reaction kettle at room temperature, filtering the reaction kettle, and standing the filtrate. And under the room temperature condition, carrying out natural volatilization crystallization for three days. The research result of fluorescence properties shows that the eutectic cobalt complex has certain fluorescence intensity at low concentration, has good photoluminescence performance, and the fluorescence intensity gradually weakens or even quenches along with the increase of the concentration of the solution, so that the fluorescence concentration self-quenching effect exists.
Description
Technical Field
The invention relates to a complex and a synthesis method thereof, in particular to a synthesis method of a novel eutectic cobalt complex [ Co (1, 10-phen) 2(AcO)]·H2SDA·11H2 O.
Background
In recent years, the design and synthesis of functional complexes has been widely studied and focused due to their unique framework and topology and potential applications in the fields of catalysis, magnetism, luminescence, and gas absorption. In the synthesis of functional complexes, many factors, such as the structural characteristics of the organic ligand, the coordination environment of the metal ion, the counter anion, the solvent system, the reaction temperature, and the pH of the system, affect the final structure of the complex. Therefore, even after many years of research, the structure of the functional complex is difficult to predict accurately. Among them, the choice of metal ions and the structure of the organic ligand are particularly important, and can directly influence the structure and properties of the complex. Compared with other ligands, the aromatic carboxylic acid ligand not only has the characteristic of diversified coordination modes of the carboxylic acid ligand, but also has the characteristics that the special skeleton aromatic ring structure is easy to produce pi.pi.pi.stack, and oxygen atoms in the carboxylic acid are easy to form hydrogen bonds by hydrogen ions in the structure, so that the structure and the performance of the synthesized metal-aromatic carboxyl complex are influenced to a certain extent. The stilbene dicarboxylic acid derivative is used as an organic ligand, and after the carboxyl of the stilbene dicarboxylic acid derivative is coordinated, the stilbene dicarboxylic acid derivative still has hydrogen bonding capability as a proton acceptor, a benzene ring is a potential pi-pi action site, and the interaction information is stored in a generated complex structure, so that the formation of a stacking structure can be guided. Besides aromatic carboxylic acid, the framework structure of the conventional rigid ligands is fixed, the nitrogen heterocycle rigid ligands are not easy to deform during coordination, the structure is easy to control, and the nitrogen heterocycle rigid ligands are widely applied to the synthesis of functional complexes by scientific researchers.
Disclosure of Invention
Aiming at the defects of the prior art, the invention adopts a solvothermal method, takes 4,4 '-stilbene dicarboxylic acid and 1, 10-phenanthroline as ligands, constructs a novel eutectic cobalt complex [ Co (1, 10-phen) 2(AcO)]·H2SDA·11H2 O,1, 10-phen=1, 10-phenanthroline, and H 2 SDA=4, 4' -stilbene dicarboxylic acid by regulating and controlling reaction conditions, and researches the crystal structure and fluorescence of the eutectic cobalt complex.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
A novel Co-crystal cobalt complex having the chemical formula of [ Co (1, 10-phen) 2(AcO)]·H2SDA·11H2 O, wherein 1, 10-phen=1, 10-phenanthroline, H 2 sda=4, 4' -stilbene dicarboxylic acid, the crystallographic parameters of the novel Co-crystal cobalt complex are shown in table 1, the partial bond lengths and bond angles of the novel Co-crystal cobalt complex are shown in table 2, and the bond lengths and bond angles of hydrogen bonds of the novel Co-crystal cobalt complex are shown in table 3.
Compared with the prior art, the invention has the following beneficial effects:
By adopting a solvothermal method, 4' -diphenylethylene dicarboxylic acid and 1, 10-phenanthroline are used as directional ligands, and the novel eutectic cobalt complex [ Co (1, 10-phen) 2(AcO)]·H2SDA·11H2 O is successfully constructed by adjusting the conditions of raw material molar ratio, reaction solvent, pH value, reaction time, reaction temperature and the like. And the structure of the complex is characterized by IR, elemental analysis and other methods, and the single crystal structure is obtained by X-ray single crystal diffraction measurement. The monocrystal structure of the eutectic cobalt complex comprises an independent mononuclear cobalt complex formed by coordination of 1, 10-phenanthroline and cobalt acetate, an independent 4,4' -stilbene dicarboxylic acid and 11 free water molecules. The research result of the fluorescence property of the cobalt eutectic compound shows that the cobalt eutectic compound has certain fluorescence intensity at low concentration, has good photoluminescence performance, gradually weakens or even quenches along with the increase of the concentration of the solution, and has the fluorescence concentration self-quenching effect.
Drawings
FIG. 1 shows the crystal structure of the complex.
FIG. 2 is a three-dimensional stacking diagram of the complex.
FIG. 3 is an infrared absorption spectrum of the complex and ligand.
FIG. 4 is a thermogravimetric plot of the complex.
FIG. 5 is a fluorescence spectrum of the complex.
Detailed Description
The technical scheme of the invention is further described below through examples.
Example 1
1 Experimental part
1.1 Instruments and reagents
AgilentG8910ACCD single crystal diffractometer; a Perkin-Elmer240Q elemental analyzer; brukerVector22FT-IR type IR spectrometer; RF-5301PC type fluorescence spectrometer. All reagents were analytically pure and were purchased from the company of the chemical industry, inc. The safety temperature of the polytetrafluoroethylene substrate hydrothermal reaction kettle is 220 ℃, the highest pressure is 3Mpa, the polytetrafluoroethylene substrate hydrothermal reaction kettle is formed by adopting high-quality nonmagnetic 0Cr18Ni9Ti stainless steel for finish machining, and the polytetrafluoroethylene substrate hydrothermal reaction kettle is internally provided with a polytetrafluoroethylene lining, is double-layer for nursing, and can resist acid, alkali and the like. The English name of the 1,10-phenanthroline is 1,10-phenanthroline, which is called phenanthroline, phenanthroline and phenanthroline for short, and the English name of the 1,10-phenanthroline is 1,10-phenanthroline, 1,10-phenanthroline and the like.
1.2 Synthesis of eutectic complexes
1, 10-Phenanthroline (0.0991 g,0.5 mmol) and 4,4' -stilbenedicarboxylic acid (0.0671 g,0.25 mmol) are put into a polytetrafluoroethylene substrate hydrothermal reaction kettle with a volume of 30mL, 7mL of Dimethylformamide (DMF) and 8mL of water are added, cobalt acetate (0.0443 g,0.25 mmol) is added after stirring for 1 hour by a magnetic stirrer, the pH value is regulated to about 10 after stirring for half an hour, and the mixture is put into the reaction kettle after stirring for 30 minutes, and is put into an electrothermal blowing drying oven with 160 ℃ for constant temperature reaction for 3 days. And taking out the reaction kettle, naturally cooling the reaction kettle at room temperature for 12 hours, filtering the reaction kettle, and standing the filtrate. Under the condition of room temperature, red crystals [ Co (1, 10-phen) 2(AcO)]·H2SDA·11H2 O can be obtained from the filtrate through three days of natural volatilization crystallization.
Yield 37.0mg, 78.4% (calculated on 1,10-phen basis).
IRν：3435(O-H),1610(C＝C),1426(C＝C),1367(C-O),1226(C-O),826(C-H),779(C-H),716(C-H),526(Co-O),477(Co-N)cm-1.Anal.calcdforC42H53N4O17Co:C,53.39;H,5.65;N,5.93;foundC,50.42;H,5.63;N,5.90.
1.3 Resolution of Crystal Structure
The test sample (0.13 mm. Times.0.12 mm. Times.0.10 mm) was placed on AGILENTCCD single crystal diffractometer and irradiated with MoK. AlphaCollecting data in an omega-2 theta scanning mode at room temperature, wherein the theta value range is 3.78-27.28 degrees (1), correcting Lp factors and absorbing and correcting by using SADABS program, determining the position of metal ions by using the Petersen method, obtaining the hydrogen atom coordinates by using the hydrogenation theory, and correcting all structural data by using the least square method. The calculation was performed using the SHELXS-97 and SHLEXL-97 and Olex procedure.
2 Results and discussion
2.1 Crystal Structure description
Table 1 shows the crystallographic parameters of the complexes
TABLE 2 partial bond lengths and bond angles for complexes
TABLE 3 bond length and bond angle of Complex hydrogen bonds
The eutectic cobalt complex belongs to a triclinic system, and P ī space group, and crystallographic parameters, partial bond length and bond angles and hydrogen bond parameters are shown in tables 1, 2 and 3 respectively. From the crystal structure diagram 1 of the eutectic cobalt complex [ Co (1, 10-phen) 2(AcO)]·H2SDA·11H2 O (1, 10-phen=1, 10-phenanthroline, H 2 SDA=4, 4 '-stilbene dicarboxylic acid), it can be seen that the structure contains a single independent mononuclear cobalt complex, a single independent 4,4' -stilbene dicarboxylic acid and 11 water molecules. This eutectic compound contains 1 mononuclear cobalt complex, 14, 4' -stilbenedicarboxylic acid and 11 free water molecules. Because the free 11 solvent water molecules in the structure have no strong bonding effect with the main structure, the structure is in a disordered state, and the wR 2 value in the crystal parameters is larger. In the independent mononuclear cobalt complex structure, the valence of cobalt ions can be obtained to be +2 based on the bond length of conventional Co-O and Co-N bonds and the principle of molecular electroneutrality. Co (II) is in a hexacoordinated environment with four nitrogen atoms from two 1, 10-phenanthroline rings, respectively With two oxygen atoms per acetic acid ] Coordination is performed. N (1), N (3), N (4), O (1) form the equatorial plane of the octahedron, 0.4828x-0.3718y-0.7929 z= -6.0645 is the best square plane equation, four atoms on the equatorial plane deviate equally/>O (2) and N (2) are two vertices of an octahedron, and the distances to the plane are/>, respectivelyCo (II) is offset from the plane by a distance/>Forming it into a twisted CoN 4O2 octahedral configuration. In the eutectic structure, O-H.O hydrogen bonding effect exists between water molecules and between solvent water molecules and oxygen atoms of the stilbene dicarboxylic acid ligand, as shown in a structural diagram, and specific hydrogen bonding parameters are shown in table 3. The three-dimensional stacking diagram is shown in figure 3, in the complex, one-dimensional chains of the complex 1 are stacked through pi.pi.pi.action of intermolecular 1, 10-phenanthrene Luo Linhuan to form a two-dimensional plane structure, chains of adjacent layers are parallel, and the two-dimensional structure is further stacked through inter-molecular pi.pi.action of another 1, 10-phenanthroline ring in the structure to form a three-dimensional structure, as shown in figure 2.
2.2 Infrared spectroscopic analysis of complexes
As shown in FIG. 3, the infrared absorption spectrum of the complex is 3435cm – 1, 1610cm – 1、1426cm– 1, 1367cm – 1 and 1226cm – 1, 826cm – 1, 779cm -1 and 716cm – 1, and the pyridine ring is C-H external bending vibration peak. 526cm – 1 and 477cm – 1 are the telescopic vibrational peaks of Co-O, co-N, respectively, indicating that cobalt ions are involved in coordination.
2.3 Thermal stability
The thermogravimetric TGA profile of the complex is shown in figure 4, the analysis being carried out under nitrogen, with a temperature rise rate of in particular 10 ℃/min. Thermogravimetric analysis showed that the title complex lost weight at 45-220 ℃ of 19.8% and lost 11 free solvent water molecules in the crystal structure; as the temperature increases, the complex continues to lose weight, the loss rate is 25% between 225 and 410 ℃, and eutectic H 2 SDA ligand is lost. When the temperature is higher than 410 ℃, the framework structure of the complex is unstable, decomposition starts, the weight loss rate is 21% between 410 and 600 ℃, one 1, 10-phenanthroline ligand participating in coordination is lost, the weight loss rate is 28% between 600 and 700 ℃, and the complex framework continues to decompose, and the other coordinated 1, 10-phenanthroline ligand and acetate are lost successively. The final residue may be the metal oxide CoO.
2.4 Fluorescence Properties
Under 365nm ultraviolet lamp irradiation, a certain concentration of complex DMF solution (1X 10-5 mol/L) emits certain fluorescence, which shows that the target complex has certain luminescence property, and the fluorescence intensity is stronger than that of the ligand 1, 10-phenanthroline and 4,4' -stilbenedicarboxylic acid. This luminescence mode of the ligand and the complex is attributed to pi→pi-electron transitions within the ligand. The complex has a higher luminescence intensity because the ligand has an enhanced structural rigidity after coordination and the proportion of energy consumed by relaxation by vibration after excitation is reduced. Meanwhile, the fluorescence spectra of the eutectic complex DMF solution with the concentration of 5X10 -5mol/L、1×10-5mol/L、5×10-6mol/L、1×10-6mol/L、5×10-7 mol/L are respectively measured, and the influence of the concentration on the fluorescence intensity is explored. As shown in fig. 5, the fluorescence intensity of the eutectic compound significantly decreased with increasing concentration of the solution, indicating that it had a fluorescence self-quenching effect.
Claims (5)
1. A eutectic cobalt complex is characterized in that the chemical formula of the eutectic cobalt complex is [ Co (1, 10-phen) 2(AcO)]·H2SDA·11H2 O, wherein 1, 10-phen=1, 10-phenanthroline, H 2 SDA=4, 4' -stilbenedicarboxylic acid belongs to a triclinic system and P ī space group, the crystallographic parameters of the eutectic cobalt complex are shown in table 1, the partial bond lengths and bond angles of the eutectic cobalt complex are shown in table 2, the bond lengths and bond angles of hydrogen bonds of the eutectic cobalt complex are shown in table 3,
Table 1 shows the crystallographic parameters of the eutectic cobalt complexes
Table 2 shows partial bond lengths and bond angles for eutectic cobalt complexes
Table 3 shows bond lengths and bond angles of hydrogen bonds of eutectic cobalt complexes
2. A method for synthesizing a eutectic cobalt complex [ Co (1, 10-phen) 2(AcO)]·H2SDA·11H2 O is characterized in that,
Reagents and amounts thereof required for the reaction
1, 10-Phenanthroline, 4' -diphenylethylene dicarboxylic acid, sodium hydroxide and cobalt acetate are used as reactants,
The mass ratio of the 1, 10-phenanthroline, 4' -stilbene dicarboxylic acid, sodium hydroxide and cobalt acetate is 1.8-2.2:0.8-1.2:1.8-2.2:0.8-1.2;
DMF and water are used as solvents,
The DMF consumption is calculated by adding 6.5-7.5 mL of DMF per 0.5mmol of 1, 10-phenanthroline,
The water consumption is calculated by adding 7.5-8.5 mL of water into each 0.5mmol of 1, 10-phenanthroline;
(II) operation procedure of Synthesis reaction
(1) Weighing each reactant according to the proportion in the step (A) for standby, and weighing the solvent according to the proportion in the step (A) for standby;
(2) Placing the 1, 10-phenanthroline, 4' -stilbene dicarboxylic acid and sodium hydroxide in the step (1) into a reaction kettle;
(3) Adding the DMF and water in the step (1) into a reaction kettle, and uniformly stirring;
(4) Adding the cobalt acetate obtained in the step (1) into a reaction kettle, and uniformly stirring;
(5) Regulating the pH value of the reaction system to 9.5-10.5, and uniformly stirring;
(6) Placing the reaction kettle in a drying oven at the temperature of 150-170 ℃ for constant-temperature reaction until the reaction is finished;
(7) Taking the reaction kettle out of the drying box, naturally cooling the reaction kettle at room temperature, and filtering to obtain filtrate;
(8) At room temperature, the filtrate naturally volatilizes and crystallizes to obtain crystals which are [ Co (1, 10-phen) 2(AcO)]·H2SDA·11H2 O.
3. The method for synthesizing the eutectic cobalt complex [ Co (1, 10-phen) 2(AcO)]·H2SDA·11H2 O according to claim 2, wherein the reaction kettle is a polytetrafluoroethylene substrate hydrothermal reaction kettle.
4. The method for synthesizing a cobalt eutectic complex [ Co (1, 10-phen) 2(AcO)]·H2SDA·11H2 O according to claim 2, wherein the pH value is adjusted by sodium hydroxide solution in step (5).
5. The method for synthesizing a Co-crystal cobalt complex [ Co (1, 10-phen) 2(AcO)]·H2SDA·11H2 O according to claim 2, wherein the mass ratio of 1, 10-phenanthroline, 4' -stilbenedicarboxylic acid, sodium hydroxide and cobalt acetate is 2:1:2:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010648610.8A CN111732614B (en) | 2020-07-07 | 2020-07-07 | Synthesis method of novel eutectic cobalt complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010648610.8A CN111732614B (en) | 2020-07-07 | 2020-07-07 | Synthesis method of novel eutectic cobalt complex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111732614A CN111732614A (en) | 2020-10-02 |
| CN111732614B true CN111732614B (en) | 2024-05-03 |
Family
ID=72655517
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010648610.8A Active CN111732614B (en) | 2020-07-07 | 2020-07-07 | Synthesis method of novel eutectic cobalt complex |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111732614B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112321650B (en) * | 2020-11-25 | 2022-06-24 | 广西民族师范学院 | Preparation method and application of novel cobalt complex with two-dimensional structure |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105524117A (en) * | 2014-09-28 | 2016-04-27 | 中国科学院大连化学物理研究所 | Preparation method for nanometer organic metal framework by ultrasonic atomization |
-
2020
- 2020-07-07 CN CN202010648610.8A patent/CN111732614B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105524117A (en) * | 2014-09-28 | 2016-04-27 | 中国科学院大连化学物理研究所 | Preparation method for nanometer organic metal framework by ultrasonic atomization |
Non-Patent Citations (4)
| Title |
|---|
| [Co(Phen)2(H2O)2](HL)NO3·3H2O的合成及晶体结构;陈延民 等;《化学研究》;20051231;第16卷(第3期);第28-31页 * |
| Huan-Yu Wang 等.catena-Poly[[diaqua(1,10-phenanthro-line-k2N,N’)cobalt(II)]-μ-trans-stilbene-4,4’-dicarboxylato-k2O:O’].《Acta Cryst.》.2007,第m3046–m3047页. * |
| 两个Co(II)配位超分子的合成、晶体结构及光谱;玉占君 等;《辽宁师范大学学报(自然科学版)》;20071231;第30卷(第3期);第332-335页 * |
| 黄秋萍 等.新型共晶配合物[Co(1,10-phen)2(AcO)]·H2SDA·11H2O的合成、晶体结构及性质.《合成化学》.2021,第29卷(第2期),第105-110页. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111732614A (en) | 2020-10-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Three-dimensional lanthanide polyoxometalate organic complexes: correlation of structure with properties | |
| Srinivasan et al. | Thermal and spectroscopic characterization of Mg (II) complexes of nitro-substituted benzoic acids | |
| Schmidt et al. | High-throughput and in situ EDXRD investigation on the formation of two new metal aminoethylphosphonates–Ca (O3PC2H4NH2) and Ca (OH)(O3PC2H4NH3)· 2H2O | |
| Zhang et al. | Assembly and tunable luminescence of lanthanide-organic frameworks constructed from 4-(3, 5-dicarboxyphenyl) pyridine-2, 6-dicarboxylate ligand | |
| CN111732614B (en) | Synthesis method of novel eutectic cobalt complex | |
| Hu et al. | Self-assembly of cuprous iodide cluster-based calix [4] resorcinarenes and photocatalytic properties | |
| Xu et al. | Comparative structural and spectral analyses for mononuclear and dinuclear metal complexes of 2-thiophen and 2-(5-bromothiophen) imidazo [4, 5-f][1, 10] phenanthroline | |
| CN106519255B (en) | Imidazole carboxylic acid complex, and synthesis method and application thereof | |
| Srinivasan et al. | Synthesis, X-ray structure and properties of a calcium (II) coordination polymer showing μ2-η1: η1 and μ3-η2: η1 coordination modes of 4-nitrobenzoate | |
| Guo et al. | Lanthanide metal–organic frameworks constructed by asymmetric 2-nitrobiphenyl-4, 4′-dicarboxylate ligand: syntheses, structures, luminescence and magnetic investigations | |
| Umamahesh et al. | A novel, facile, rapid, solvent free protocol for the one pot green synthesis of chromeno [2, 3-d] pyrimidines using reusable nano ZnAl 2 O 4–a NOSE approach and photophysical studies | |
| Głuchowska et al. | Effect of N, N′-dimethylformamide solvent on structure and thermal properties of lanthanide (III) complexes with flexible biphenyl-4, 4′-dioxydiacetic acid | |
| CN108610380B (en) | Tetrapyridyl porphyrin zinc-ruthenium complex and preparation and application thereof | |
| Wang et al. | Series of 3D lanthanide MOFs derived from saddle-like alicyclic tetracarboxylate ligands: synthesis, characterization and structure–photoluminescence correlations | |
| Wu et al. | Synthesis, Structure and Coordination Self‐Assembly of Azacalix [4‐n] pyridine [n] pyrazines (n= 1–3) | |
| Chen et al. | Five lanthanide supramolecular frameworks based on mixed 3-(4-hydroxyphenyl) propanoic acid and 1, 10-phenanthroline tectons: Crystal structures and luminescent properties | |
| CN111825727B (en) | Synthesis method of novel eutectic compound | |
| Li et al. | Hydrothermal in situ ligand reaction: copper (II)-mediated stepwise oxidation of 2, 3, 5-and 2, 4, 6-trimethylpyridine to pyridinecarboxylates | |
| Marjit Singh et al. | Iron (II) and Manganese (II) Complexes of 2-{2-(3-Carboxypyridin-2-yl) disulfanyl} pyridine-3-carboxylic acid Through C–S Bond Cleavage | |
| Liu et al. | Syntheses, structures, and properties of four coordination polymers based on 2, 7‐di (pyridin‐4‐yl)‐9H‐fluoren‐9‐one | |
| Sławińska et al. | Synthesis, crystal structure and selected properties of two new peroxidomolybdates | |
| Zhang et al. | Dielectric and optical properties of a new organic–inorganic hybrid phase transition material | |
| Švančárek et al. | Oxo Peroxo Glycolato Complexesof Vanadium (V). Crystal Structureof (NBu 4) 2 [V 2 O 2 (O 2) 2 (C 2 H 2 O 3) 2] ċH 2 O | |
| Jürgens et al. | Synthesis, Crystal Structure and Properties of Rubidium Dihydrogentricyanomelaminate Semihydrate Rb [H2C6N9]· 1/2 H2O | |
| Zima et al. | Alkaline-earth metal phosphonocarboxylates: synthesis, structures, chirality, and luminescence properties |
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 |