CN111592523A - Layered structure sym-triazine imine zinc complex - Google Patents
Layered structure sym-triazine imine zinc complex Download PDFInfo
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- CN111592523A CN111592523A CN202010379583.9A CN202010379583A CN111592523A CN 111592523 A CN111592523 A CN 111592523A CN 202010379583 A CN202010379583 A CN 202010379583A CN 111592523 A CN111592523 A CN 111592523A
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- triazine
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- JIHQDMXYYFUGFV-UHFFFAOYSA-N 1,3,5-triazine Chemical compound C1=NC=NC=N1 JIHQDMXYYFUGFV-UHFFFAOYSA-N 0.000 title claims abstract description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 8
- 150000002466 imines Chemical class 0.000 title claims abstract description 8
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 8
- 239000011701 zinc Substances 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 claims abstract description 8
- CSDSSGBPEUDDEE-UHFFFAOYSA-N 2-formylpyridine Chemical compound O=CC1=CC=CC=N1 CSDSSGBPEUDDEE-UHFFFAOYSA-N 0.000 claims abstract description 4
- PADPILQDYPIHQQ-UHFFFAOYSA-L zinc;diperchlorate;hexahydrate Chemical compound O.O.O.O.O.O.[Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O PADPILQDYPIHQQ-UHFFFAOYSA-L 0.000 claims abstract description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 238000001338 self-assembly Methods 0.000 claims description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- WEVYAHXRMPXWCK-FIBGUPNXSA-N acetonitrile-d3 Chemical compound [2H]C([2H])([2H])C#N WEVYAHXRMPXWCK-FIBGUPNXSA-N 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- -1 nitrophenoxy-s-triazine Chemical compound 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RTZZCYNQPHTPPL-UHFFFAOYSA-N 3-nitrophenol Chemical compound OC1=CC=CC([N+]([O-])=O)=C1 RTZZCYNQPHTPPL-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000000706 filtrate Substances 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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- 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
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- 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
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- 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
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1059—Heterocyclic compounds characterised by ligands containing three nitrogen atoms as heteroatoms
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- 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
- C09K2211/188—Metal complexes of other metals not provided for in one of the previous groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
A layered structure sym-triazine imine zinc complex (I) has the following chemical formula:
Description
Technical Field
The invention relates to an organic metal coordination supermolecule compound and a preparation method thereof, in particular to an aromatic heterocyclic s-triazine organic metal complex and a preparation method thereof, and specifically relates to a layered structure s-triazine imine zinc complex and a synthesis method thereof.
Background
In recent ten years, coordinated supramolecular chemistry has been rapidly developed, and coordinated supramolecular chemistry can be regarded as the combination of multiple branch subjects such as inorganic chemistry, supramolecular chemistry, organic chemistry and the like, and a nitrogen-containing supramolecular complex is mainly formed by taking an upper metal ion and a lower metal ion as nodes through an N → M coordinate bond and a dynamic C ═ N covalent bond in a ligand molecule. The supermolecule complex has the common characteristics of a complex and supermolecules, absorbs various physical and chemical properties of metal ions and metal clusters, changes the cutting, modification and design means of the detection, and provides a wide platform for the rapid development of the supermolecule synthesis technology.
The design and construction of supramolecular complexes are hot spots in current research. Different amines and aldehydes are selected as secondary components, so that a preset highly symmetrical ligand can be obtained, and then the ligand is coordinated with metal ions and can be arranged and combined to form different geometric structures, and the supermolecule complex has obvious internal cavities which can contain some object molecules and special host-guest chemical properties, so that the supermolecule complex has potential application values in the fields of molecular recognition and exchange, selective catalysis, drug delivery and the like.
In addition, the supermolecule complex has good fluorescence effect, and provides a good foundation for the subsequent creation research of luminescent materials.
Disclosure of Invention
The invention aims to provide an s-triazine imine zinc complex with a layered structure.
Another object of the present invention is to provide a process for the preparation of the above complexes.
The technical scheme of the invention comprises the following steps:
a layered structure s-triazine imine zinc complex is shown as a general formula (I):
a process for the synthesis of the complex (I) according to claim 1. M-nitrophenol and cyanuric chloride are used as raw materials to prepare tri-m-nitrophenoxy s-triazine, and the tri-m-aminophenoxy s-triazine is obtained by iron powder reduction; the complex is synthesized by the self-assembly of tri-m-aminophenoxy s-triazine, zinc perchlorate hexahydrate and pyridine-2-formaldehyde. The reaction process is as follows:
the conditions in reaction (2) were: the reaction solvent can be acetonitrile, methanol and pyridine, and acetonitrile is preferred; the reaction temperature can be selected from 30-70 ℃, and preferably 30 ℃. The invention adopts a self-assembly synthesis method, and directly obtains the target complex through simple post-treatment and one-step reaction.
The complex (I) emits stronger fluorescence under the excitation of ultraviolet light, so that the complex becomes a potential high-quality luminescent material.
Drawings
FIG. 1 shows the fluorescence spectrum of complex (I)
Detailed Description
Example 1
This example illustrates the preparation of tri-m-aminophenoxy s-triazine
3.00g (25.2mmol) of m-nitrophenol, 1g (25.2mmol) of sodium hydroxide, 100mL of water and 20mL of acetone were sequentially charged into a 500mL four-necked flask. After stirring for 30min, slowly dropwise adding 100mL acetone solution dissolved with 1.5g (8.2mmol) of cyanuric chloride at room temperature, reacting for 2h at 60 ℃, and obtaining 2.76g of white tri-m-nitrophenoxy s-triazine after suction filtration, washing and drying, wherein the yield is as follows: 68%, melting point: is > 300 ℃.1H NMR(400MHz，CD3CN)：7.75(s，1H，ben zene-H)，7.72(d，J＝8.2Hz，1H，benzene-H)，7.61(t，J＝2.3Hz，1H，benzene-H)，7.21(d， J＝8.2Hz，1H，benzene-H)。
Three portions were added to a 250mL flask in sequence1.78g (3.7mmol) of nitrophenoxy-s-triazine, 3g (55mmol) of ammonium chloride, 60mL of ethanol and 20mL of water are stirred and heated to 80 ℃. Adding 3g (55mmol) of high-activity reduced iron powder into the mixture for three times, refluxing for 3 hours, filtering while the mixture is hot, washing a filter cake for multiple times by using hot ethanol, adjusting the pH of the obtained filtrate to about 9 by using sodium bicarbonate, filtering, desolventizing, drying the obtained crude product, dissolving the dried crude product by using 0.5mol/L hydrochloric acid, filtering, adding 5% of sodium hydroxide solution into the filtrate to adjust the pH to about 7, filtering, washing by using clear water to obtain 0.75g of white m-aminophenoxy s-triazine, wherein the yield is 45%, and the melting point is as follows: 243 ℃ and 245 ℃.1H NMR(400MHz，CD3CN)：7.10(t，J＝8.0Hz，1H，benzene-H)，6.53(d，J＝8.5Hz，1H，benzene-H)，6.43(s，1H，benzene-H)，6.41(d，J＝8.5Hz，1H，benzene-H)，4. 32(s，2H，imine-H)。
Example 2
This example illustrates the preparation of layered sym-triazine imine zinc complexes and the determination of the fluorescence properties
(1) Preparation of the Complex
In a 25mL flask were charged 25mg (0.062mmol) of tris-m-aminophenoxy-s-triazine, 35mg (0.093mmol) of zinc perchlorate hexahydrate, 20mg (0.186mmol) of pyridine-2-carbaldehyde and 5mL of acetonitrile in this order, and reacted at 30 ℃ for 36 hours. After the reaction, 10mL of isopropyl ether is added to separate out a solid, a yellow solid is obtained after centrifugal separation, and the isopropyl ether is washed and dried to obtain a product of 31 mg. The yield was 44.7%, the melting point > 300 ℃.1H NMR(400MHz，CD3CN)：9.18(d，J＝4.2Hz，1H，pyridine-H)，8.48 (s，1H，imine-H)，8.29(s，1H，pyridine-H)，8.07(d，J＝5.4Hz，1H，pyridine-H)，7.88(d，J＝7.6Hz， 1H，pyridine-H)，7.21(s，1H，benzene-H)，7.15(d，J＝8.2Hz，1H，benzene-H)，7.07(t，J＝8.1Hz， 1H，benzene-H)，6.74(d，J＝7.7Hz，1H，benzene-H)。
(2) Measurement of fluorescent Properties of Complex
The fluorescence spectrum data of the complex (I) is shown in figure 1. As can be seen from the attached figure 1, the complex (I) emits stronger fluorescence at the wavelength of 484nm under the excitation of ultraviolet light, which shows that the complex (I) has good fluorescence characteristics.
Claims (3)
1. A layered structure s-triazine imine zinc complex is shown as a general formula (I):
2. a process for the preparation of a compound of formula (I) as claimed in claim 1. The complex is synthesized by the self-assembly of tri-m-aminophenoxy s-triazine, zinc perchlorate hexahydrate and pyridine-2-formaldehyde. The reaction process is as follows:
3. the production method according to claim 2, wherein: the reaction solvent in the reaction (1) is selected from acetonitrile, methanol and pyridine, and is preferably acetonitrile; the reaction temperature is 30-70 ℃, and preferably 30 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202010379583.9A CN111592523A (en) | 2020-05-07 | 2020-05-07 | Layered structure sym-triazine imine zinc complex |
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| CN202010379583.9A CN111592523A (en) | 2020-05-07 | 2020-05-07 | Layered structure sym-triazine imine zinc complex |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109438420A (en) * | 2018-11-08 | 2019-03-08 | 南京工业大学 | A kind of imines zinc s-triazine complex |
| CN110041308A (en) * | 2018-01-16 | 2019-07-23 | 南京工业大学 | A kind of high symmetry sandwich structure imines Zn complex |
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2020
- 2020-05-07 CN CN202010379583.9A patent/CN111592523A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110041308A (en) * | 2018-01-16 | 2019-07-23 | 南京工业大学 | A kind of high symmetry sandwich structure imines Zn complex |
| CN109438420A (en) * | 2018-11-08 | 2019-03-08 | 南京工业大学 | A kind of imines zinc s-triazine complex |
Non-Patent Citations (2)
| Title |
|---|
| LIQIAN XU等: "Highly crystalline covalent organic frameworks from flexible building blocks", 《CHEM. COMMUN.》 * |
| WEN-YUAN WU等: "Self-assembly and peripheral guest-binding of [Zn3L2(H2O)6]6+ triangular double helicate", 《INORGANIC CHEMISTRY COMMUNICATIONS》 * |
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