CN116396336A - Preparation method and application of difluorophenyl modified aggregation-induced emission iridium complex - Google Patents
Preparation method and application of difluorophenyl modified aggregation-induced emission iridium complex Download PDFInfo
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 22
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 238000004220 aggregation Methods 0.000 title claims abstract description 17
- 230000002776 aggregation Effects 0.000 title claims abstract description 17
- 125000004212 difluorophenyl group Chemical group 0.000 title claims abstract description 8
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000003446 ligand Substances 0.000 claims abstract description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 150000002503 iridium Chemical class 0.000 claims abstract description 13
- -1 2- (4- (2, 4-difluorophenyl) phenyl) -5-trifluoromethyl pyridine Chemical compound 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 8
- SZXUTTGMFUSMCE-UHFFFAOYSA-N 2-(1h-imidazol-2-yl)pyridine Chemical compound C1=CNC(C=2N=CC=CC=2)=N1 SZXUTTGMFUSMCE-UHFFFAOYSA-N 0.000 claims abstract description 7
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 32
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 31
- 230000015572 biosynthetic process Effects 0.000 claims description 18
- 238000003786 synthesis reaction Methods 0.000 claims description 18
- 239000000543 intermediate Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- 238000004440 column chromatography Methods 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- QBLFZIBJXUQVRF-UHFFFAOYSA-N (4-bromophenyl)boronic acid Chemical compound OB(O)C1=CC=C(Br)C=C1 QBLFZIBJXUQVRF-UHFFFAOYSA-N 0.000 claims description 7
- GSKMWMFOQQBVMI-UHFFFAOYSA-N 2-bromo-5-(trifluoromethyl)pyridine Chemical compound FC(F)(F)C1=CC=C(Br)N=C1 GSKMWMFOQQBVMI-UHFFFAOYSA-N 0.000 claims description 7
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 6
- 239000013067 intermediate product Substances 0.000 claims description 6
- 239000012074 organic phase Substances 0.000 claims description 6
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 239000000243 solution Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 claims description 5
- 239000000376 reactant Substances 0.000 claims description 5
- QQLRSCZSKQTFGY-UHFFFAOYSA-N (2,4-difluorophenyl)boronic acid Chemical compound OB(O)C1=CC=C(F)C=C1F QQLRSCZSKQTFGY-UHFFFAOYSA-N 0.000 claims description 4
- 150000005360 2-phenylpyridines Chemical class 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 239000012043 crude product Substances 0.000 claims description 4
- 239000003480 eluent Substances 0.000 claims description 4
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000003208 petroleum Substances 0.000 claims description 4
- 229920006395 saturated elastomer Polymers 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- 238000004809 thin layer chromatography Methods 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 abstract description 36
- 150000001875 compounds Chemical class 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 8
- 239000002904 solvent Substances 0.000 description 6
- 238000000295 emission spectrum Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000004020 luminiscence type Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000002194 synthesizing effect Effects 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BSCHIACBONPEOB-UHFFFAOYSA-N oxolane;hydrate Chemical compound O.C1CCOC1 BSCHIACBONPEOB-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- 238000010791 quenching Methods 0.000 description 2
- 230000002000 scavenging effect Effects 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000002428 photodynamic therapy Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- 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 Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
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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
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
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Abstract
A preparation method and application of difluorophenyl modified aggregation-induced emission iridium complex, which belong to the field of phosphorescent materials. According to the invention, 2- (4- (2, 4-difluorophenyl) phenyl) -5-trifluoromethyl pyridine serving as a cyclometalated ligand and 2,2' -bipyridine and 2- (2-imidazolyl) pyridine serving as auxiliary ligands are used for preparing two iridium complexes, and the study on photophysical properties of the iridium complexes shows that the ratio of the emission intensity of the iridium complexes in an acetonitrile/water system to the emission intensity of the iridium complexes in the repulped acetonitrile exceeds 10, so that the iridium complexes prepared by the invention have excellent aggregation-induced emission properties and have important application values in the field of phosphorescent materials.
Description
Technical Field
The invention relates to a preparation method and application of a difluorophenyl modified aggregation-induced emission iridium complex, and belongs to the field of phosphorescent materials.
Background
Conventional fluorescent molecules typically have intense fluorescence in dilute solutions, which at high concentrations can decrease or even quench. In 2001, tang Benzhong et al found that a class of small organic molecules were substantially non-fluorescent in dilute solutions and exhibited bright fluorescent Emission in the aggregated state (chem. Commun.,2001,18,1740-1741), and they called this new phenomenon as Aggregation-Induced Emission (AIE). The discovery of aggregation-induced emission provides an effective thought for solving the important scientific problem of luminescence quenching caused by aggregation, and greatly promotes the application and development of high-efficiency solid-state luminescent materials. To date, the AIE molecules of all documents are mostly pure small organic molecules, and relatively few novel Aggregation-induced phosphorescent emission (AIPE) materials based on transition metal complexes are known. The iridium complex is widely used as a phosphorescent material in the fields of OLED (Small, 2017,1603780; J.Mater.chem.C,2018,6, 3298-3309), photodynamic therapy (adv.Sci., 2019,1802050), cell imaging (J.Mater.chem.C, 2014,2,5615-5628), and sensor (Dalton Trans,2022,52,128-135).
Disclosure of Invention
The invention aims to provide a preparation method of iridium complexes Ir1 and Ir2 with aggregation-induced emission properties and the aggregation-induced emission properties thereof.
The technical scheme adopted by the invention is as follows: the difluorophenyl modified aggregation-induced emission iridium complex is formed by taking a 2-phenylpyridine derivative as a cyclometalated ligand and an N-N auxiliary ligand to coordinate with iridium metal ions, and has the following structure:
the 2-phenylpyridine derivative is selected from 2- (4- (4- (2, 4-difluorophenyl) phenyl) -5-trifluoromethylpyridine; the N-auxiliary ligand is selected from 2,2' -bipyridine or 2- (2-imidazolyl) pyridine.
The synthesis steps of the iridium complex are as follows:
(1) Synthesis of cyclometallated ligand intermediates: taking 2-bromo-5-trifluoromethylpyridine and 4-bromophenylboronic acid as reactants, taking potassium carbonate as alkali and palladium acetate as a catalyst, carrying out Suzuki cross-coupling reaction in air at 80 ℃, tracking the reaction progress by thin layer chromatography, and separating by column chromatography after the reaction is complete to obtain a cyclometalated ligand intermediate 2- (4- (4-bromophenyl) phenyl) -5-trifluoromethylpyridine;
the 2-bromo-5-trifluoromethylpyridine: 4-bromophenylboronic acid: potassium carbonate: the molar ratio of palladium acetate is 1:2.5:2:0.015;
(2) Synthesis of cyclometallated ligand: takes a cyclometallation ligand intermediate and 2, 4-difluorophenylboronic acid as reactants, sodium carbonate as alkali and tetra (triphenylphosphine) palladium as a catalyst, N 2 Under the protection, carrying out Suzuki cross-coupling reaction at 70 ℃, and separating by column chromatography after 24 hours of reaction to obtain a cyclometalated ligand;
(3) Synthesis of iridium complexes: irCl was added to a round bottom flask 3 ·3H 2 O and 2.5 equivalents of cyclometallated ligand in a 3:1 volume ratio ethylene glycol monoethyl ether/water mixture, N 2 Magnetically stirring at 120 ℃ under protection, reacting for 24 hours, and concentrating the reaction solution under reduced pressure after the reaction is finished to obtain a dichloro bridge intermediate product; adding dichloro bridge intermediate product, 3.0 equivalent of N≡N auxiliary ligand 2,2' -bipyridine or 2- (2-imidazolyl) pyridine into a round bottom flask, and heating and refluxing for 24 hours at 120 ℃ under the protection of nitrogen; after the reaction was completed, the mixture was cooled to room temperature, and 20mL of KPF was further added 6 Saturated aqueous solution, stirring at room temperature for 12h; the reaction liquid is extracted by methylene dichloride, the collected organic phase is decompressed and concentrated to obtain a crude product, and the iridium complex is obtained by column chromatography separation and purification by taking methylene dichloride/petroleum ether as an eluent.
The iridium complex is applied to the field of phosphorescent materials.
Further, the iridium complexes Ir1 and Ir2 are prepared by synthesizing an intermediate from 2-bromo-5-trifluoromethylpyridine and 4-bromophenylboronic acid as reactants, simultaneously coordinating a cyclometalated ligand and an N+—N auxiliary ligand synthesized from the intermediate and 2, 4-difluorophenylboronic acid with iridium metal ions, and finally synthesizing by replacing anions, wherein the structure is as follows:
the preparation method of the cyclometalated ligand and iridium complexes Ir1 and Ir2 comprises the following specific synthesis steps:
(1) Synthesis of cyclometallated ligand intermediates: under the air condition, 1.0mmol of 2-bromo-5-trifluoromethylpyridine, 4-bromophenylboronic acid (2.5 equiv.), potassium carbonate (2.0 equiv.), palladium acetate (1.5% equiv.) and 12mL of ethanol-water mixed solution with the volume ratio of 3:1 are sequentially added into a round bottom flask, the reaction progress is tracked by thin layer chromatography through stirring under the magnetic force of 80 ℃ to carry out Suzuki cross-coupling reaction, dichloromethane is used for extraction three times after the reaction is completed, the organic phases are combined, reduced pressure concentration and separation through column chromatography are carried out, and the cyclometalated ligand intermediate 2- (4- (4-bromophenyl) phenyl) -5-trifluoromethylpyridine is prepared.
(2) Synthesis of cyclometallated ligand: to a round bottom flask, 1.0mmol of the intermediate of the cyclometallated ligand, 1.5equiv. of 2, 4-difluorophenylboronic acid, 2.0equiv. of sodium carbonate and 3.0% of tetrakis (triphenylphosphine) palladium were added in sequence, 16mL of a tetrahydrofuran-water mixed solution with a volume ratio of 5:3 was then added, and the mixture was magnetically stirred at 70℃under nitrogen protection to carry out Suzuki cross-coupling reaction, and after 24 hours of reaction, the mixture was extracted three times with dichloromethane, the organic phases were combined, concentrated under reduced pressure, and separated by column chromatography to obtain the cyclometallated ligand.
(3) Synthesis of iridium complexes: irCl was added to a round bottom flask 3 ·3H 2 O and 2.5 equivalents of cyclometallated ligand in a 3:1 volume ratio of ethylene glycol monoethyl ether/water mixture of oxygen scavenging, N 2 And magnetically stirring and reacting for 24 hours at 120 ℃ under the protection, and concentrating the reaction liquid under reduced pressure after the reaction is finished to obtain the dichloro bridge intermediate product. The dichloro bridge intermediate and 3.0 equivalents of N-N auxiliary ligand are added into a round bottom flask, ethylene glycol monoethyl ether is used as a solvent, and the mixture is heated and refluxed for 24 hours at 120 ℃ under the protection of nitrogen. After the reaction was completed, the mixture was cooled to room temperature, and 20mL of KPF was further added 6 The aqueous solution was saturated and stirred at room temperature for 12h. Extracting the reaction liquid with dichloromethane, concentrating under reduced pressure to obtain crude product, separating and purifying with dichloromethane/petroleum ether as eluent to obtain target product, and purifying with column chromatography to obtain product with structure of 1 H NMR and high resolution mass spectrometry corroboration.
The iridium complex includes the following derivatives:
compound Ir1: the cyclometallated ligand is selected from 2- (4- (4- (2, 4-difluorophenyl) phenyl) -5-trifluoromethylpyridine; the N-auxiliary ligand is selected from 2,2' -bipyridine;
compound Ir2: the cyclometallated ligand is selected from 2- (4- (4- (2, 4-difluorophenyl) phenyl) -5-trifluoromethylpyridine; the N-auxiliary ligand is selected from 2- (2-imidazolyl) pyridine.
The invention has the beneficial effects that:
1. the method for synthesizing the cyclometalated ligand by using the Suzuki cross-coupling reaction is environment-friendly, simple, convenient and efficient.
2. The iridium complex with excellent aggregation-induced emission property can be obtained through the modularized design of the cyclometallated iridium complex modified by different auxiliary ligands.
Drawings
FIG. 1 is a graph showing the emission spectrum of Ir1 (solvent acetonitrile/water, 5X 10) -5 mol/L)。
FIG. 2 is a graph showing the emission spectrum of Ir2 at various water contents (solvent acetonitrile/water, 5X 10) -5 mol/L)。
Detailed Description
EXAMPLE 1 Synthesis of Compound Ir1
(1) Synthesis of cyclometallated ligand intermediates:
under air condition, adding 1.0mmol of 2-bromo-5-trifluoromethylpyridine, 4-bromophenylboronic acid (2.5 equiv.), potassium carbonate (2.0 equiv.), and palladium acetate (1.5% equiv.) into a round bottom flask in sequence, adding 12mL of ethanol-water mixed solution with the volume ratio of 3:1, magnetically stirring at 80 ℃ for Suzuki cross-coupling reaction, tracking the reaction progress by thin layer chromatography, adding 20mL of saturated saline solution after the reaction is complete, extracting three times by using dichloromethane, merging organic phases, concentrating under reduced pressure, and separating by column chromatography to obtain a cyclic metal ligand intermediate with the yield of 50%.
(2) Synthesis of cyclometallated ligand:
to a round bottom flask was added sequentially 1.0mmol of the cyclometallated ligand intermediate, 1.5equiv. phenylboronic acid, 2.0equiv. sodium carbonate, 3.0% equiv. palladium tetrakis (triphenylphosphine) and then 16ml of a tetrahydrofuran-water mixed solution in a volume ratio of 5:3, n 2 Under the protection of the reaction, the Suzuki cross-coupling reaction is carried out under the magnetic stirring at 70 ℃, after the reaction is carried out for 24 hours, 20mL of saturated saline solution is added, the extraction is carried out for three times by using methylene dichloride, the organic phases are combined, the concentration is carried out under reduced pressure, and the cyclic metal ligand is obtained through column chromatography separation, wherein the yield is 79%.
(3) Synthesis of iridium complexes:
IrCl was added to a round bottom flask 3 ·3H 2 O and 2.5 equivalents of cyclometallated ligand in a 3:1 volume ratio of ethylene glycol monoethyl ether/water mixture of oxygen scavenging, N 2 Magnetically stirring at 120 ℃ under protection, reacting for 24 hours, and concentrating the reaction liquid under reduced pressure after the reaction is finished to obtain the dichloro bridge intermediate product. The dichloro-bridged intermediate, 3.0 equivalents of 2,2' -bipyridine, was added to a round-bottomed flask and reacted at 120℃for 24h under nitrogen protection using ethylene glycol monoethyl ether as solvent. After the reaction was completed, the mixture was cooled to room temperature, and 20mL of KPF was further added 6 The aqueous solution was saturated and stirred at room temperature for 12h. Extracting the reaction liquid with dichloromethane, concentrating under reduced pressure to obtain a crude product, separating and purifying by column chromatography with dichloromethane/petroleum ether as eluent to obtain a target product with 54% yield, wherein the structural characterization data is as follows: 1 H NMR(400MHz,DMSO-d 6 ) Delta 8.94 (d, j=8.3 hz, 2H), 8.61 (d, j=8.8 hz, 2H), 8.46 (dd, j=8.8, 1.6hz, 2H), 8.36 (td, 2H), 7.20 (d, j=8.3 hz, 2H), 8.07 (d, j=4.7 hz, 2H), 7.84-7.74 (m, 4H), 7.60 (td, j=8.9, 6.7hz, 2H), 7.56-7.51 (m, 4H), 7.49 (td, j=4.5, 2.4hz, 6H), 7.40-7.31 (m, 2H), 7.20 (td, j=8.3, 1.9hz, 2H), 6.47 (d, j=1.6 hz, 2H)/(m/ms-z) values are calculated. C (C) 58 H 34 F 10 N 4 Ir[M-PF 6 ] + 1169.2248, found: 1169.2272.
EXAMPLE 2 Synthesis of Compound Ir2
Example 2 was prepared in the same manner as example 1, except that: the N++N ancillary ligand used in the synthesis of iridium complexes in example 2 is 2- (2-imidazolyl) pyridine.
Ir2 yield 68% and structure characterization data were as follows: 1 H NMR(400MHz,DMSO-d 6 ) Delta 14.55 (s, 1H), 8.63-8.52 (m, 2H), 8.43 (d, j=9.5 hz, 3H), 8.30 (td, j=7.9, 1.4hz, 1H), 8.17 (t, j=8.1 hz, 2H), 7.95 (d, j=5.2 hz, 1H), 7.88 (d, j=12.4 hz, 2H), 7.82 (d, j=1.3 hz, 1H), 7.67-7.58 (m, 3H), 7.57-7.41 (m, 10H), 7.40-7.31 (m, 2H), 7.20 (td, j=8.3, 1.9hz, 2H), 6.74 (d, j=1.3 hz, 1H), 6.56 (d, j=1.7 hz, 1H), 6.46 (d, j=1.7 hz, 1H): malz-hrdi (m, 1H): m.v/z: c (C) 56 H 33 F 10 N 5 Ir[M-PF 6 ] + 1158.2200, found: 1158.2208.
EXAMPLE 3 AIE Property test of Compound Ir1
Ir1 is dissolved in acetonitrile to prepare the mixture with the concentration of 5 multiplied by 10 -4 mixing the above solution, acetonitrile and water at different volume ratios to obtain mixed solution (concentration of 5×10) -5 mol/L), followed by testing its emission spectrum. The results of FIG. 1 show that the luminescence of the compound is essentially unchanged with increasing water content of the poor solvent in the acetonitrile/water mixed solution, the emission wavelength is blue shifted and the emission intensity is significantly increased when the water content is increased to 70%, and the emission intensity reaches the maximum when the water content is 75%, I/I 0 Reaching 7.18 (I represents the emission intensity of Ir1 in acetonitrile/water system, I 0 Representing the emission intensity of Ir1 in pure acetonitrile). The results indicate that the compound Ir1 has excellent aggregation-induced emission properties.
EXAMPLE 4 AIE Property test of Compound Ir2
Ir2 is dissolved in acetonitrile to prepare the mixture with the concentration of 5 multiplied by 10 -4 mixing the above solution, acetonitrile and water at different volume ratios to obtain mixed solution (concentration of 5×10) -5 mol/L), followed by testing its emission spectrum. The results of FIG. 2 show that the luminescence of the compound gradually increases with increasing water content of the poor solvent in the acetonitrile/water mixed solution, and the emission intensity reaches the maximum at 70% water content, I/I 0 Reaching 10.92. The results indicate that the compound Ir2 has excellent aggregation-induced emission properties.
Claims (3)
1. The difluorophenyl modified aggregation-induced emission iridium complex is characterized in that: the iridium complex is formed by coordination of a 2-phenylpyridine derivative serving as a cyclometalated ligand and an N-N auxiliary ligand with iridium metal ions, and has the following structure:
the 2-phenylpyridine derivative is selected from 2- (4- (4- (2, 4-difluorophenyl) phenyl) -5-trifluoromethylpyridine; the N-auxiliary ligand is selected from 2,2' -bipyridine or 2- (2-imidazolyl) pyridine.
2. The method for preparing the difluorophenyl modified aggregation-induced emission iridium complex according to claim 1, wherein the method comprises the following steps: the synthesis steps of the iridium complex are as follows:
(1) Synthesis of cyclometallated ligand intermediates: taking 2-bromo-5-trifluoromethylpyridine and 4-bromophenylboronic acid as reactants, taking potassium carbonate as alkali and palladium acetate as a catalyst, carrying out Suzuki cross-coupling reaction in air at 80 ℃, tracking the reaction progress by thin layer chromatography, and separating by column chromatography after the reaction is complete to obtain a cyclometalated ligand intermediate 2- (4- (4-bromophenyl) phenyl) -5-trifluoromethylpyridine;
the 2-bromo-5-trifluoromethylpyridine: 4-bromophenylboronic acid: potassium carbonate: the molar ratio of palladium acetate is 1:2.5:2:0.015;
(2) Synthesis of cyclometallated ligand: takes a cyclometallation ligand intermediate and 2, 4-difluorophenylboronic acid as reactants, sodium carbonate as alkali and tetra (triphenylphosphine) palladium as a catalyst, N 2 Under the protection, carrying out Suzuki cross-coupling reaction at 70 ℃, and separating by column chromatography after 24 hours of reaction to obtain a cyclometalated ligand;
(3) Synthesis of iridium complexes: irCl was added to a round bottom flask 3 ·3H 2 O and 2.5 equivalents of cyclometallated ligand in a 3:1 volume ratio ethylene glycol monoethyl ether/water mixture, N 2 Magnetically stirring at 120 ℃ under protection, reacting for 24 hours, and concentrating the reaction solution under reduced pressure after the reaction is finished to obtain a dichloro bridge intermediate product; adding dichloro bridge intermediate product, 3.0 equivalent of N≡N auxiliary ligand 2,2' -bipyridine or 2- (2-imidazolyl) pyridine into a round bottom flask, and heating and refluxing for 24 hours at 120 ℃ under the protection of nitrogen; after the reaction was completed, the mixture was cooled to room temperature, and 20mL of KPF was further added 6 Saturated aqueous solution, stirring at room temperature for 12h; the reaction liquid is extracted by methylene dichloride, the collected organic phase is decompressed and concentrated to obtain a crude product, and the iridium complex is obtained by column chromatography separation and purification by taking methylene dichloride/petroleum ether as an eluent.
3. The use of difluorophenyl modified aggregation-induced emission iridium complex according to claim 1, wherein: the iridium complex is applied to the field of phosphorescent materials.
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