CN109020828B - Schiff base copper complex and preparation method and application thereof - Google Patents
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- -1 Schiff base copper complex Chemical class 0.000 title claims abstract description 44
- 239000002262 Schiff base Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000000243 solution Substances 0.000 claims abstract description 46
- 239000003446 ligand Substances 0.000 claims abstract description 42
- UFFBMTHBGFGIHF-UHFFFAOYSA-N 2,6-dimethylaniline Chemical compound CC1=CC=CC(C)=C1N UFFBMTHBGFGIHF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000007787 solid Substances 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 13
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- FUGKCSRLAQKUHG-UHFFFAOYSA-N 5-chloro-2-hydroxybenzaldehyde Chemical compound OC1=CC=C(Cl)C=C1C=O FUGKCSRLAQKUHG-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- 238000010992 reflux Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 239000000706 filtrate Substances 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 229960000583 acetic acid Drugs 0.000 claims description 6
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012362 glacial acetic acid Substances 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims 3
- DZCLVBQEPZQZNN-UHFFFAOYSA-N copper;phenol Chemical compound [Cu].OC1=CC=CC=C1 DZCLVBQEPZQZNN-UHFFFAOYSA-N 0.000 claims 1
- 150000004753 Schiff bases Chemical class 0.000 abstract description 13
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 abstract description 3
- 150000004699 copper complex Chemical class 0.000 description 14
- 238000010521 absorption reaction Methods 0.000 description 9
- 239000010949 copper Substances 0.000 description 6
- 238000004770 highest occupied molecular orbital Methods 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 5
- 239000013522 chelant Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 238000005401 electroluminescence Methods 0.000 description 4
- 238000005424 photoluminescence Methods 0.000 description 4
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- 150000001879 copper Chemical class 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910002480 Cu-O Inorganic materials 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005274 electronic transitions Effects 0.000 description 2
- 125000000879 imine group Chemical group 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- QNZWAJZEJAOVPN-UHFFFAOYSA-N 4-chloro-2-hydroxybenzaldehyde Chemical compound OC1=CC(Cl)=CC=C1C=O QNZWAJZEJAOVPN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910001410 inorganic ion Inorganic materials 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000003115 supporting electrolyte Substances 0.000 description 1
- KBLZDCFTQSIIOH-UHFFFAOYSA-M tetrabutylazanium;perchlorate Chemical compound [O-]Cl(=O)(=O)=O.CCCC[N+](CCCC)(CCCC)CCCC KBLZDCFTQSIIOH-UHFFFAOYSA-M 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/02—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of compounds containing imino groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C251/00—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C251/02—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups
- C07C251/24—Compounds containing nitrogen atoms doubly-bound to a carbon skeleton containing imino groups having carbon atoms of imino groups bound to carbon atoms of six-membered aromatic rings
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- 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
- C09K2211/18—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)
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Abstract
The invention discloses a Schiff base copper complex and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) dissolving 5-chlorosalicylaldehyde in ethanol to obtain a solution I; dissolving 2, 6-dimethylaniline in ethanol to obtain a solution II; adding the solution II into the solution I to obtain a solution III; adding acetic acid into the solution III to obtain a reaction solution; heating and refluxing the reaction solution for 1h, cooling to room temperature, standing to precipitate a solid, filtering, and washing the solid with cold ethanol to obtain a ligand finally; (2) dissolving the ligand synthesized in the step (1) in ethanol to obtain a solution IV; dissolving copper nitrate in ethanol to obtain a solution V; adding the solution V into the solution IV to obtain a mixed solution; carrying out reflux reaction on the mixed solution for 1.5h, carrying out hot filtration, cooling the filtrate, and standing to separate out black blocky crystals, namely the complex; the invention explores the potential application value of the Schiff base complex in the field of luminescent materials.
Description
Technical Field
The invention belongs to the technical field of organic electroluminescent materials and preparation methods thereof, and particularly relates to a Schiff base copper complex and a preparation method and application thereof.
Background
The continuous and rapid development of information technology puts higher demands on brightness, color, resolution, energy consumption and the like of an information display system. Light emitting diodes, thin film electroluminescence and thick dielectric electroluminescence are already mature to be used in display technology, and among them, Organic Light Emitting Diodes (OLEDs) are the main market participants. In recent years, with the increasing market demand for high-quality, high-reliability and large-information-volume display devices, the OLED technology has been developed greatly, and various OLED products are put into the market.
The organic electroluminescent material is a high-molecular or small-molecular organic material capable of emitting light under the action of an electric field, and usually has strong photoluminescence in a solid state, the electroluminescent efficiency of the material is determined by the photoluminescence efficiency, and only the material with high photoluminescence efficiency can be a good organic electroluminescent material. The small molecule organic luminescent material has higher electroluminescent efficiency and better carrier transmission performance, wherein the unique photophysical property of the metal organic complex is more and more concerned in the field of luminescent materials, and the luminescent capability of the complex formed by metal ions and organic ligands has a great relationship with the organic ligands and the structural characteristics of the metal ions. Schiff bases are taken as a representative organic ligand, imine groups can be introduced into a system through design, and the Schiff bases have the capability of chelating metals and can be self-assembled with various metal cations to form metal complexes.
Schiff bases and their metal complexes have attracted considerable scientific attention in many fields due to their specific structures and unique electrochemical and optical properties. The Schiff base metal complex has quite considerable application prospect in the field of organic electroluminescence, in particular to salicylaldehyde. After different substituents such as halogen and the like are introduced to the benzene ring of the salicylaldehyde, the application performance of the Schiff base and the metal complex synthesized after the Schiff base is greatly influenced due to the influence of an electronic effect and a space effect. At present, synthesis and crystal structures of 5-chlorosalicylaldehyde, 2, 6-dimethylaniline Schiff base and copper complexes thereof are not reported, and the Schiff base copper complex is synthesized, the photoluminescence performance of the Schiff base copper complex is researched, and the potential application value of the Schiff base complex in the field of luminescent materials is explored.
Disclosure of Invention
The invention provides a Schiff base copper complex and a preparation method and application thereof, wherein a Schiff base ligand is obtained by condensing 5-chlorosalicylaldehyde and 2, 6-dimethylaniline, then the Schiff base ligand reacts with copper nitrate to enable copper ions to enter a cavity formed by the Schiff base ligand N, N, O, O to form the Schiff base copper complex, and the performance of the Schiff base copper complex as a luminescent material is detected.
The invention is realized by the following technical scheme.
The invention aims to provide a Schiff base copper complex, and the preparation method of the Schiff base copper complex comprises the following steps:
(1) synthesis of 4-chloro-2- (2, 6-dimethylanilinomethyl) phenol ligand: dissolving 5-chlorosalicylaldehyde in ethanol to obtain a solution I; dissolving 2, 6-dimethylaniline in ethanol to obtain a solution II; adding the solution II into the solution I to obtain a solution III; adding glacial acetic acid into the solution III to obtain a reaction solution; heating the reaction solution to 76-78 ℃ for reflux reaction for 1h, cooling to room temperature, standing to separate out a solid, filtering, and washing the solid with cold ethanol to obtain an orange-red solid, namely the 4-chloro-2- (2, 6-dimethylanilinomethyl) phenol ligand;
the 5-chloro salicylaldehyde: the molar ratio of the 2, 6-dimethylaniline is 1:1, the total mass concentration of the solute III in the solution is 0.05 g/mL-0.09 g/mL, and the adding volume of the glacial acetic acid is 0.1% -0.2% of the volume of the solution III;
(2) synthesis of 4-chloro-2- (2, 6-dimethylanilinomethyl) phenol copper complex: dissolving the 4-chloro-2- (2, 6-dimethylanilinomethyl) phenol ligand synthesized in the step (1) in ethanol to obtain a solution IV; dissolving copper nitrate trihydrate in ethanol to obtain a solution V; adding the solution V into the solution IV to obtain a mixed solution; heating the mixed solution to 76-78 ℃ for reflux reaction for 1.5h, carrying out hot filtration, cooling the filtrate, and standing to separate out black blocky crystals, namely the 4-chloro-2- (2, 6-dimethylanilinomethyl) phenol copper complex;
the 4-chlorosalicylaldehyde condensed 2, 6-dimethylaniline ligand: the molar ratio of the copper nitrate trihydrate is 2:1, and the total mass concentration of the solute of the mixed solution is 0.01 g/mL-0.02 g/mL.
Compared with the prior art, the invention has the following beneficial effects: the preparation method disclosed by the invention is simple in principle, mild in condition and easy to operate, the 5-chlorosalicylaldehyde and the 2, 6-dimethylaniline are condensed to obtain the Schiff base ligand, and the Schiff base ligand is reacted with the copper nitrate to form the Schiff base copper complex, so that the coordination of inorganic ions and organic matters containing photosensitive groups is realized, a novel luminescent material is developed, the potential application value of the Schiff base in the field of organic electroluminescence is explored, and a foundation is laid for the subsequent research.
Drawings
FIG. 1 is a flow chart showing the preparation of a 4-chloro-2- (2, 6-dimethylanilinomethyl) phenol copper complex in accordance with the present invention;
FIG. 2 is a crystal structure diagram of a 4-chloro-2- (2, 6-dimethylanilinomethyl) phenol copper complex prepared in the present invention;
FIG. 3 is a chart of the IR spectrum of 4-chloro-2- (2, 6-dimethylanilinomethyl) phenol ligand and its copper complex;
FIG. 4 is a graph of the UV absorption of 4-chloro-2- (2, 6-dimethylanilinomethyl) phenol ligand and its copper complex;
FIG. 5 is a fluorescent spectrum of 4-chloro-2- (2, 6-dimethylanilinomethyl) phenol copper complex;
FIG. 6 is a calculated HOMO, LUMO and energy bands for 4-chloro-2- (2, 6-dimethylanilinomethyl) phenol ligands and their complexes;
FIG. 7 is an electrochemical diagram of cyclic voltammetry measurements of 4-chloro-2- (2, 6-dimethylanilinomethyl) phenol ligands and their copper complexes.
Detailed Description
In order to make the technical solutions of the present invention better understood and enable those skilled in the art to practice the present invention, the following examples and data are provided for further illustration, but the examples are not intended to limit the present invention.
The experimental methods and the detection methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
Example 1
The preparation process shown in figure 1 is used for preparing the 4-chloro-2- (2, 6-dimethylanilinomethyl) phenol copper complex, and comprises the following specific steps:
(1) synthesis of 4-chloro-2- (2, 6-dimethylanilinomethyl) phenol ligand: weighing 1.56g of 5-chlorosalicylaldehyde into a 100mL round-bottom flask, adding 30mL of ethanol, stirring for dissolving, then adding 20mL of ethanol solution of 1.21g of 2, 6-dimethylaniline, and adding 0.05mL of glacial acetic acid to obtain reaction liquid; heating the reaction solution to 76 ℃, carrying out reflux reaction for 1h, cooling to room temperature, standing to separate out a solid, filtering, and washing the solid with cold ethanol to obtain an orange-red solid, namely the 4-chloro-2- (2, 6-dimethylanilinomethyl) phenol ligand;
(2) synthesis of 4-chloro-2- (2, 6-dimethylanilinomethyl) phenol copper complex: weighing 0.52g to 100mL of round-bottom flask of the 4-chloro-2- (2, 6-dimethylanilinomethyl) phenol ligand synthesized in the step (1), adding 30mL of ethanol, stirring for dissolving, and then adding 20mL of 0.24g of ethanol solution of copper nitrate trihydrate to obtain mixed solution; heating the mixed solution to 76 ℃, carrying out reflux reaction for 1.5h, carrying out heat filtration, cooling the filtrate, and standing to separate out black blocky crystals, namely the 4-chloro-2- (2, 6-dimethylanilinomethyl) phenol copper complex.
Example 2
The preparation process shown in figure 1 is used for preparing the 4-chloro-2- (2, 6-dimethylanilinomethyl) phenol copper complex, and comprises the following specific steps:
(1) synthesis of 4-chloro-2- (2, 6-dimethylanilinomethyl) phenol ligand: weighing 1.56g of 5-chlorosalicylaldehyde into a 100mL round-bottom flask, adding 30mL of ethanol, stirring for dissolving, then adding 20mL of ethanol solution of 1.21g of 2, 6-dimethylaniline, and adding 0.1mL of glacial acetic acid to obtain reaction liquid; heating the reaction solution to 78 ℃, carrying out reflux reaction for 1h, cooling to room temperature, standing to separate out a solid, filtering, and washing the solid with cold ethanol to obtain an orange-red solid, namely the 4-chloro-2- (2, 6-dimethylanilinomethyl) phenol ligand;
(2) synthesis of 4-chloro-2- (2, 6-dimethylanilinomethyl) phenol copper complex: weighing 0.52g to 100mL of round-bottom flask of the 4-chloro-2- (2, 6-dimethylanilinomethyl) phenol ligand synthesized in the step (1), adding 30mL of ethanol, stirring for dissolving, and then adding 20mL of 0.24g of ethanol solution of copper nitrate trihydrate to obtain mixed solution; heating the mixed solution to 78 ℃, carrying out reflux reaction for 1.5h, carrying out heat filtration, cooling the filtrate, and standing to separate out black blocky crystals, namely the 4-chloro-2- (2, 6-dimethylanilinomethyl) phenol copper complex.
Taking example 1 as an example, the structures and luminescence properties of the synthesized 4-chloro-2- (2, 6-dimethylanilinomethyl) phenol ligand and its copper complex were examined, and the results were as follows:
as can be seen from FIG. 2, the crystal structure of the copper complex is composed of two ligands and a Cu (II), the central Cu (II) ion has a four-coordination geometry, and coordinates with two N atoms and two O atoms in the two bidentate ligands respectively to form a planar tetragonal configuration; the Cu-N bond length value formed by Cu (II) and ligand is 0.19772(16) nm-0.20004 (15) nm, the bond angle with Cu (II) as center is 87.72(16) DEG-180.0 DEG, and the Cu-O bond length value is 0.18788(15) nm-0.1884 (14) nm. In order to reduce steric hindrance, the dihedral angle between two benzene rings in the ligand in the copper complex is 89.3 degrees; two five-membered chelate rings formed by coordination of a Cu (II) ion and a ligand (chelate ring A and chelate ring B are C1, C6, C7, N1, O1, Cu1, Cu1, O1A, C1A, C6A, C7A and N1A, and the dihedral angle between the two chelate rings is 0 ℃). As can be seen from FIG. 3, 1620cm are present in the ligand-1The C-N stretching vibration absorption peak of imine group appears at 1608cm-1In contrast, a red shift occurs; stretching vibration of Ar-O occurred at 1281cm in the ligand-1Wave number, and appears at 1322cm in the copper complex-1At least one of (1) and (b); at 753-770cm-1The new peak appeared can be assigned as the absorption peak of Cu-N, indicating that imine (C ═ N) participates in coordination; at the same time, at 605--1The new peak appeared and can be assigned as the absorption peak of Cu-O, which indicates that the oxygen of phenolic hydroxyl participates in the coordination.
As can be seen from the UV absorption diagrams of the ligand and the copper complex in FIG. 4, the ligand has two strong absorption peaks at 262nm and 337nm, while the copper complex has three absorption peaks at 260nm, 300nm and 381nm, which are caused by charge transfer between the metal and the ligand and charge transfer in the ligand; the ultraviolet absorption sideband of the ligand is 3.22eV and the ultraviolet absorption sideband of the copper complex is 2.85eV according to the map, which indicates that the latter is easier to perform electron transition than the former. As can be seen from the fluorescence spectrum of FIG. 5, the optimum excitation wavelength of the copper complex was 450nm, the maximum emission wavelength was 508nm, and it was found to emit bluish-green light in the DMSO solvent. FIG. 6 shows that the band of the ligand is 4.07eV, while that of the copper complex is 3.29eV, the latter being larger than the former, indicating that the copper complex is more susceptible to electronic transition than the ligand, which is consistent with the result of the trend of electronic transition by optical calculation.
And measuring the electrochemical diagrams of the ligand and the copper complex by cyclic voltammetry by using ferrocene as an internal standard and tetra-n-butyl ammonium perchlorate as a supporting electrolyte, wherein the initial oxidation potential of the ligand is 1.06eV and the initial oxidation potential of the copper complex is 1.15eV according to the graph shown in FIG. 7, and the measured results are obtained according to HOMO ═ - [ (E)onset-Eferrocene)+4.80](eV) and LUMO ═ Egopt+ HOMO calculation the HOMO and LUMO energy levels of the ligands and copper complexes, respectively: a ligand, HOMO ═ 5.33eV and LUMO ═ 2.62eV, and an energy band of 3.40V; the copper complex had a HOMO value of-5.42 eV and a LUMO value of-2.57 eV, and an energy band of 2.85.
The map is shown in the attached drawing in detail.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, it is intended that such changes and modifications be included within the scope of the appended claims and their equivalents.
Claims (3)
1. A preparation method of a Schiff base copper complex is characterized by comprising the following steps:
(1) synthesis of 4-chloro-2- (2, 6-dimethylanilino methine) phenol ligand: dissolving 5-chlorosalicylaldehyde in ethanol to obtain a solution I; dissolving 2, 6-dimethylaniline in ethanol to obtain a solution II; adding the solution II into the solution I to obtain a solution III; adding glacial acetic acid into the solution III to obtain a reaction solution; heating the reaction liquid to 76-78 ℃, carrying out reflux reaction for 1h, cooling to room temperature, standing to separate out a solid, filtering, and washing the solid with cold ethanol to obtain an orange-red solid, namely the 4-chloro-2- (2, 6-dimethylanilino-methine) phenol ligand;
the 5-chloro salicylaldehyde: the molar ratio of the 2, 6-dimethylaniline is 1:1, the total mass concentration of the solute III in the solution is 0.05-0.09 g/mL, and the adding volume of the glacial acetic acid is 0.1-0.2% of the volume of the solution III;
(2) 4-chloro-2- (2, 6-dimethylanilino methyl) phenol copper complex synthesis: dissolving the 4-chloro-2- (2, 6-dimethylanilinomethine) phenol ligand synthesized in the step (1) in ethanol to obtain a solution IV; dissolving copper nitrate trihydrate in ethanol to obtain a solution V; adding the solution V into the solution IV to obtain a mixed solution; heating the mixed solution to 76-78 ℃, carrying out reflux reaction for 1.5h, carrying out heat filtration, cooling the filtrate, and standing to separate out black blocky crystals, namely the 4-chloro-2- (2, 6-dimethylanilino-methine) phenol copper complex;
the 4-chloro-2- (2, 6-dimethylanilino methyl) phenol ligand: the molar ratio of the copper nitrate trihydrate is 2:1, and the total mass concentration of the solute of the mixed solution is 0.01 g/mL-0.02 g/mL.
2. The schiff base copper complex prepared by the preparation method according to claim 1.
3. Use of the schiff base copper complex according to claim 2 in the field of luminescent materials.
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| CN110229176A (en) * | 2019-07-17 | 2019-09-13 | 山西农业大学 | A kind of fragrance plane schiff bases copper complex and its preparation method and application |
| CN111018893B (en) * | 2019-11-25 | 2020-09-25 | 桂林医学院 | Sulfur-containing amino alcohol Schiff base copper complex and preparation and application thereof |
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| CN103896800A (en) * | 2014-04-23 | 2014-07-02 | 桂林理工大学 | Iodine-containing sandwich copper compound and application thereof |
| CN107840807A (en) * | 2017-10-01 | 2018-03-27 | 桂林理工大学 | A kind of schiff bases copper complex and preparation method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103896800A (en) * | 2014-04-23 | 2014-07-02 | 桂林理工大学 | Iodine-containing sandwich copper compound and application thereof |
| CN107840807A (en) * | 2017-10-01 | 2018-03-27 | 桂林理工大学 | A kind of schiff bases copper complex and preparation method thereof |
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| Schiff碱金属配合物的研究进展;于静，等;《化学研究》;20161130;第779-785页 * |
| Synthesis, mesomorphic and photo-physical properties of few d- and f- block metals coordinated to polar Schiff"s bases;Lopamudra Chakraborty，等;《Liquid Crystals》;20120321;第39卷(第5期);第657页scheme1、第666页左栏第7.2小节、第666页右栏第7.3小节 * |
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