CN116396337A - Preparation method and application of cationic cyclometallated iridium complex with oxygen sensitivity - Google Patents
Preparation method and application of cationic cyclometallated iridium complex with oxygen sensitivity Download PDFInfo
- Publication number
- CN116396337A CN116396337A CN202310338952.3A CN202310338952A CN116396337A CN 116396337 A CN116396337 A CN 116396337A CN 202310338952 A CN202310338952 A CN 202310338952A CN 116396337 A CN116396337 A CN 116396337A
- Authority
- CN
- China
- Prior art keywords
- iridium complex
- cyclometallated
- ligand
- cationic
- reaction
- 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.)
- Pending
Links
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 48
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000001301 oxygen Substances 0.000 title claims abstract description 46
- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 35
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 125000002091 cationic group Chemical group 0.000 title claims abstract description 17
- 230000035945 sensitivity Effects 0.000 title claims abstract description 9
- 238000002360 preparation method Methods 0.000 title abstract description 5
- 239000003446 ligand Substances 0.000 claims abstract description 25
- 150000001450 anions Chemical class 0.000 claims abstract description 12
- 150000002503 iridium Chemical class 0.000 claims abstract description 9
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims description 30
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 29
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 13
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 8
- 238000004440 column chromatography Methods 0.000 claims description 8
- 229920006395 saturated elastomer Polymers 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- IFGLECYAEGYLSJ-UHFFFAOYSA-N 2-bromo-3-fluoropyridine Chemical compound FC1=CC=CN=C1Br IFGLECYAEGYLSJ-UHFFFAOYSA-N 0.000 claims description 7
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 6
- VZZUYEUNFYZVPF-UHFFFAOYSA-N 3-fluoro-2-phenylpyridine Chemical compound FC1=CC=CN=C1C1=CC=CC=C1 VZZUYEUNFYZVPF-UHFFFAOYSA-N 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 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
- 239000011780 sodium chloride Substances 0.000 claims description 6
- 238000006069 Suzuki reaction reaction Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000012295 chemical reaction liquid Substances 0.000 claims description 4
- 238000001816 cooling Methods 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
- 238000004809 thin layer chromatography Methods 0.000 claims description 4
- ODHXBMXNKOYIBV-UHFFFAOYSA-N triphenylamine Chemical compound C1=CC=CC=C1N(C=1C=CC=CC=1)C1=CC=CC=C1 ODHXBMXNKOYIBV-UHFFFAOYSA-N 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000003208 petroleum Substances 0.000 claims description 3
- -1 tetrafluoroborate Chemical compound 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000004044 response Effects 0.000 abstract description 14
- 238000010791 quenching Methods 0.000 abstract description 8
- 230000000171 quenching effect Effects 0.000 abstract description 7
- 230000003287 optical effect Effects 0.000 abstract description 5
- 150000005360 2-phenylpyridines Chemical class 0.000 abstract 1
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 7
- 239000001856 Ethyl cellulose Substances 0.000 description 7
- 235000019325 ethyl cellulose Nutrition 0.000 description 7
- 229920001249 ethyl cellulose Polymers 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005516 engineering process Methods 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
- 239000007789 gas Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000000295 emission spectrum Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004896 high resolution mass spectrometry Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Images
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 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
-
- 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
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
Abstract
A preparation method and application of a cationic cyclometallated iridium complex with oxygen sensitivity property belong to the technical field of photoelectric materials. The invention synthesizes three iridium complexes containing different anions by taking the diphenylamino-modified 2-phenylpyridine derivative as a cyclometalated ligand and taking 1, 10-phenanthroline as an auxiliary ligand, and the quenching ratio of the oxygen-sensitive film prepared by the iridium complexesI 0 /I 100 All exceed 30, and has the advantages of good light stability, high quenching ratio, quick response and the like. The cationic cyclometallated iridium complex has wide application prospect in the field of optical oxygen sensitive materials.
Description
Technical Field
The invention relates to a preparation method and application of three cationic cyclometallated iridium complexes with oxygen sensitivity, and belongs to the technical field of photoelectric materials.
Background
Oxygen is an indispensable chemical substance for human survival, and oxygen detection has been widely used in the fields of medicine, agriculture, environmental protection, etc. (chem. Soc. Rev.,2013,42,8700-8732). Among the Oxygen detection technologies, the optical Oxygen sensing technology has the advantages of good reversibility, high precision, no Oxygen consumption and the like, and the principle is that Oxygen molecules are used as triplet quenchers to quench phosphorescence (or delayed fluorescence) of Oxygen Sensitive Probes (OSPs) so as to realize the detection of the Oxygen concentration. Most of the current optical oxygen sensitive probes used are transition metal complexes. The iridium complex can have longer phosphorescence lifetime and higher phosphorescence quantum yield through molecular design, and is a potential optical oxygen-sensitive probe. However, most of the iridium complex oxygen-sensitive probes reported at present are neutral iridium complexes (Angew Chem Int Ed Engl, 2022,61,5738-5752;Sensor Actuat B-chem, 2022,374,794-806), few reports about cationic iridium complexes are provided, and no research has been reported on the influence of different counter anions on the oxygen-sensitive properties of iridium complexes. The counter anion is taken as an important component of the cationic cyclometallated iridium complex, has a critical influence on the luminescent property of the iridium complex in an aggregation state, and can flexibly adjust the luminescent property of the iridium complex in the aggregation state (Cryst Growth Des,2016,16,5738-5752;J Mater Chem C,2016,4,5731-5738). Therefore, the research on the structure-effect relationship between the structure of the cationic cyclometallated iridium complex and the oxygen sensitivity of the cationic cyclometallated iridium complex is of great significance in creating novel OSPs for luminescent oxygen sensing.
The cationic cyclometallated iridium complex modified by different counter anions can be used as a phosphorescence material to be applied to an oxygen sensitive probe of an oxygen sensitive device, and an oxygen sensitive film prepared by the cationic cyclometallated iridium complex has the advantages of good light stability, high quenching ratio, quick response to oxygen and the like.
Disclosure of Invention
The invention aims to provide a preparation method of cationic cyclometallated iridium complexes Ir1-Ir3 with oxygen sensitivity and the oxygen sensitivity thereof.
The technical scheme adopted by the invention is as follows: the iridium complex Ir1-Ir3 is prepared by synthesizing a cyclometalated ligand from 2-bromo-3-fluoropyridine and 4-triphenylamine borate, then simultaneously coordinating with 1, 10-phenanthroline and iridium metal ions, and finally replacing anions, wherein the structure is as follows:
the cyclometallated ligand is 2- (4-N, N-diphenylamino) phenyl-3-fluoropyridine; the different anions are respectively selected from chloride Cl - Hexafluorophosphate ion PF 6 - And tetrafluoroborate ion BF 4 - 。
The synthesis steps of the iridium complex are as follows:
(1) Synthesis of cyclometallated ligand: taking 2-bromo-3-fluoropyridine and 4-triphenylamine borate as reactants, taking potassium carbonate as alkali and palladium acetate as a catalyst, carrying out Suzuki cross-coupling reaction in the air at 80 ℃ under the condition of no additional ligand, tracking the reaction progress by thin layer chromatography, and separating by column chromatography after the reaction is complete to obtain a ring metal ligand;
the 2-bromo-3-fluoropyridine: triphenylamine 4-borate: potassium carbonate: the molar ratio of palladium acetate is 1:1.5:2:0.015;
(2) 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 Under the protection condition, magnetically stirring and reacting for 24 hours at 120 ℃, and concentrating the reaction liquid under reduced pressure after the reaction is finished to obtain a dichloro bridge intermediate product; adding dichloro bridge intermediate product and 3.0 equivalent of 1, 10-phenanthroline into a round-bottom flask, and heating and refluxing for 24 hours at 120 ℃ under nitrogen atmosphere; after the reaction, cooling to room temperature, adding 20mL of NaCl or KPF 6 Or KBF 4 Saturated aqueous solution, stirring at room temperature for 12h; extracting the reaction liquid with dichloromethane, concentrating the collected organic phase under reduced pressure to obtain a crude product, separating by column chromatography with dichloromethane/petroleum ether as eluent, and purifying to obtain the cationic cyclometallated iridium complex.
The cationic cyclometallated iridium complex is applied to the technical field of photoelectric materials.
Further, the specific synthesis steps are as follows:
(1) Synthesis of cyclometallated ligand: in the air, 1.0mmol of 2-bromo-3-fluoropyridine, triphenylamine 4-borate (1.5 equiv.), potassium carbonate (2.0 equiv.), and palladium acetate (1.5% equiv.) are sequentially added into a round bottom flask, then 12mL of an ethanol-water mixed solution with a volume ratio of 3:1 is added, the mixture is magnetically stirred at 80 ℃ for carrying out Suzuki cross-coupling reaction, the reaction progress is tracked by thin layer chromatography, methylene chloride is used for three times after the reaction is completed, organic phases are combined, reduced pressure concentration is carried out, and the cyclic metal ligand is prepared through column chromatography separation.
(2) Synthesis of iridium complexes: irCl was added to a round bottom two-neck flask 3 ·3H 2 O and 2.5 equivalents of cyclometallated ligand, N 2 Replacing for 3 times, injecting 8mL of ethylene glycol monoethyl ether/water (3:1, v/v) mixed solution by using a syringe, magnetically stirring and reacting for 24 hours at 120 ℃ under the protection of nitrogen, transferring the reaction solution into a single-mouth round-bottom flask after the reaction is finished, and concentrating under reduced pressure to obtain a dichloro bridge intermediate product; 3.0 equivalents of 1, 10-phenanthroline and 8mL of ethylene glycol monoethyl ether are added into a round bottom flask, and the mixture is magnetically stirred for 24 hours at 120 ℃ under the nitrogen atmosphere. After the reaction, cooling to room temperature, adding 20mL of NaCl or KPF 6 Or KBF 4 The aqueous solution was saturated and stirred at room temperature for 12h. After the reaction is finished, dichloromethane is used for extraction, and the organic phases are combined and concentrated under reduced pressure to obtain a crude product; dichloromethane/methanol is used as eluent, the target product is obtained by column chromatography separation and purification, and the product structure is achieved by 1 H NMR and high resolution mass spectrometry identification.
The iridium complex includes the following derivatives:
complex Ir1: the cyclometallated ligand is selected from 2- (4-N, N-diphenylamino) phenyl-3-fluoropyridine; counter anions are selected from Cl - ；
Complex Ir2: the cyclometallated ligand is selected from 2- (4-N, N-diphenylamino) phenyl-3-fluoropyridine; counter anions selected from PF 6 - ；
Complex Ir3: the cyclometallated ligand is selected from 2- (4-N, N-diphenylamino) phenyl-3-fluoropyridine; the counter anion being selected from BF 4 - 。
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 modified by different counter anions can obtain the iridium complex with excellent oxygen sensitivity through a modularized design. Quenching ratio I of oxygen sensitive film prepared from Ir1-Ir3 0 /I 100 36.7, 32.5 and 33.1 respectively. The quenching constant reaches 0.05466Torr -1 、0.04684Torr -1 And 0.05071Torr -1 . Meanwhile, the oxygen sensitive film has the advantages of good light stability, quick response to oxygen and the like. The compound Ir1-Ir3 synthesized by the method has wide application prospect in the field of optical oxygen sensitive materials.
Drawings
FIG. 1 is a dynamic phosphorescence response test of the complex Ir1 supported on an EC film.
FIG. 2 is a dynamic phosphorescence response test of the complex Ir2 supported on an EC film.
FIG. 3 is a dynamic phosphorescence response test of the complex Ir3 supported on an EC film.
FIG. 4 is the reversibility and response time of the complex Ir1 oxygen sensitive film.
FIG. 5 is the reversibility and response time of the complex Ir2 oxygen sensitive film.
FIG. 6 is the reversibility and response time of the complex Ir3 oxygen sensitive film.
Detailed Description
EXAMPLE 1 Synthesis of Complex Ir1
(1) Synthesis of cyclometallated ligand:
in air, adding 1.0mmol of 2-bromo-3-fluoropyridine, triphenylamine 4-borate (1.5 equiv.), potassium carbonate (2.0 equiv.), and palladium acetate (1.5% equiv.) into a round bottom flask, adding 8mL of an ethanol-water mixed solution with a volume ratio of 3:1, magnetically stirring at 80 ℃ to perform Suzuki cross-coupling reaction, tracking the reaction progress by thin layer chromatography, adding 20mL of saturated saline after the reaction is completed, extracting with dichloromethane, merging organic phases, concentrating under reduced pressure, separating by column chromatography to obtain a cyclometal ligand intermediate with a yield of 55%.
(2) Synthesis of iridium complexes:
IrCl was added to a round bottom two-neck flask 3 ·3H 2 O and 2.5 equivalents of cyclometallated ligand, N 2 Replacing for 3 times, injecting 8mL of ethylene glycol monoethyl ether/water (3:1, v/v) mixed solution by a syringe, magnetically stirring at 105 ℃ for reaction for 24 hours under the protection of nitrogen, transferring the reaction solution into a single-mouth round-bottom flask after the reaction is finished, and distilling under reduced pressure to obtain a dichloro bridge intermediate product. 3.0 equivalents of 1, 10-phenanthroline and 8mL of ethylene glycol monoethyl ether are added under nitrogenThe reaction was carried out under magnetic stirring at 120℃for 24h. After the reaction, the mixture was cooled to room temperature, and then 20mL of a saturated aqueous solution of NaCl was added thereto, followed by stirring at room temperature for 12 hours. After the reaction is finished, dichloromethane is used for extraction, and the organic phases are combined and concentrated under reduced pressure to obtain a crude product; the target product is obtained by column chromatography separation and purification with methylene dichloride/petroleum ether as an eluent, and the yield is 41%. The structural characterization data are as follows: 1 H NMR(400MHz,DMSO-d 6 )δ8.91(d,J＝8.3Hz,2H),8.40(d,J＝4.6Hz,4H),8.13(dd,J＝8.3,5.1Hz,2H),7.87(d,J＝8.7Hz,2H),7.48(dd,J＝11.6,8.3Hz,2H),7.27(t,J＝7.9Hz,8H),7.09(t,J＝7.4Hz,4H),7.01(d,J＝8.0Hz,10H),6.65-6.51(m,4H),5.77(d,J＝2.4Hz,2H).HRMS(MALDI-TOF,m/z):calcd for C 58 H 40 N 6 F 2 Ir[M-Cl] + 1051.2906,found:1051.2900.
EXAMPLE 2 Synthesis of Complex Ir2
Example 2 was prepared in the same manner as example 1, except that: the iridium complex reaction in example 2 was completed, cooled to room temperature, and 20mL of KPF was added 6 The saturated aqueous solution replaces the saturated aqueous solution of NaCl.
Ir2 yield 37%, structural characterization data were as follows: 1 H NMR(400MHz,DMSO-d 6 )δ8.91(d,J＝8.1Hz,2H),8.39(d,J＝4.6Hz,4H),8.13(dd,J＝8.2,5.1Hz,2H),7.88(d,J＝8.7Hz,2H),7.48(dd,J＝11.6,8.6Hz,2H),7.28(t,J＝7.7Hz,8H),7.10(t,J＝7.4Hz,4H),7.02(d,J＝8.0Hz,10H),6.70-6.48(m,4H),5.77(d,J＝2.3Hz,2H).HRMS(MALDI-TOF,m/z):calcd for C 58 H 40 N 6 F 2 Ir[M-PF 6 ] + 1051.2906,found:1051.2909.
EXAMPLE 3 Synthesis of Complex Ir3
Example 3 was prepared in the same manner as in example 1, except that: the iridium complex reaction in example 3 was completed, and 20mL KBF was added after cooling to room temperature 4 The saturated aqueous solution replaces the saturated aqueous solution of NaCl.
Ir3 yield 31%, structural characterization data were as follows: 1 H NMR(400MHz,DMSO-d 6 )δ8.91(d,J＝8.2Hz,2H),8.38(d,J＝4.6Hz,4H),8.13(dd,J＝8.2,5.0Hz,2H),7.87(d,J＝8.7Hz,2H),7.48(dd,J＝11.8,8.3Hz,2H),7.28(t,J＝7.7Hz,8H),7.09(t,J＝7.4Hz,4H),7.01(d,J＝7.6Hz,10H),6.64-6.52(m,4H),5.77(d,J＝2.7Hz,2H).HRMS(MALDI-TOF,m/z):calcd for C 58 H 40 N 6 F 2 Ir[M-BF 4 ] + 1051.2906,found:1051.2933.
example 4 test of the Complex Ir1-Ir3 oxygen sensitive film dynamic phosphorescent response Curve
Ir1-Ir3 complexes were supported on Ethylcellulose (EC) to produce EC films with a thickness of about 5.8 μm and a loading of 0.5%. Placing the prepared EC film in a flow cell, and introducing O with different volume ratios by controlling a gas flowmeter 2 /N 2 Testing the iridium complex oxygen sensing film on different O by mixed gas 2 Emission spectrum at volume fraction, obtain p O 2 Is a sensitive data of (a). The results of FIGS. 1-3 show that when the Ir1-Ir3 oxygen sensitive film is at 100% N 2 In the atmosphere, the Ir1-Ir3 oxygen sensitive film has stable luminous intensity. As the oxygen concentration increases, the luminescence intensity of the oxygen sensitive film decreases, and corresponding phosphorescence quenching dynamic responses are presented for different oxygen concentrations.
Example 5 test of the oxygen sensitive film reversibility and response time of the Complex Ir1-Ir3
Alternately switching pure N within a time range of 2000s 2 And pure O 2 The reversibility and response time are tested through the change of the luminous intensity of the iridium complex Ir1-Ir3 oxygen sensitive film, and the reusability of the iridium complex after being prepared into OSPs is examined. As can be seen from FIGS. 4-6, when N is greater than 100% 2 Atmosphere switch to 100% O 2 In the atmosphere, the luminous intensity of the Ir1-Ir3 oxygen sensitive film is rapidly reduced; while when from 100% O 2 Atmosphere conversion to 100% N 2 In the atmosphere, the luminous intensity rapidly increases and returns to the initial value. The phosphorescence quenching process and the phosphorescence recovery process are reversible and repeated a plurality of times N 2 /O 2 The luminous intensity can be recovered rapidly after circulation, which shows that the Ir1-Ir3 oxygen sensitive film has good stability, excellent reversibility and rapid response to oxygen concentration change.
Claims (3)
1. A cationic cyclometallated iridium complex with oxygen sensitivity is characterized in that: the iridium complex is formed by coordination of 2- (4-N, N-diphenylamino) phenyl-3-fluoropyridine serving as a cyclometalated ligand and 1, 10-phenanthroline serving as an auxiliary ligand and iridium metal ions and matching with different anions, and has the following structure:
the cyclometallated ligand is 2- (4-N, N-diphenylamino) phenyl-3-fluoropyridine; the different anions are respectively selected from chloride Cl - Hexafluorophosphate ion PF 6 - And tetrafluoroborate ion BF 4 - 。
2. The method for producing a cationic cyclometallated iridium complex according to claim 1, wherein: the synthesis steps of the iridium complex are as follows:
(1) Synthesis of cyclometallated ligand: taking 2-bromo-3-fluoropyridine and 4-triphenylamine borate as reactants, taking potassium carbonate as alkali and palladium acetate as a catalyst, carrying out Suzuki cross-coupling reaction in the air at 80 ℃ under the condition of no additional ligand, tracking the reaction progress by thin layer chromatography, and separating by column chromatography after the reaction is complete to obtain a ring metal ligand;
the 2-bromo-3-fluoropyridine: triphenylamine 4-borate: potassium carbonate: the molar ratio of palladium acetate is 1:1.5:2:0.015;
(2) 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 Under the protection condition, magnetically stirring and reacting for 24 hours at 120 ℃, and concentrating the reaction liquid under reduced pressure after the reaction is finished to obtain a dichloro bridge intermediate product; adding dichloro bridge intermediate product and 3.0 equivalent of 1, 10-phenanthroline into a round-bottom flask, and heating and refluxing for 24 hours at 120 ℃ under nitrogen atmosphere; after the reaction, cooling to room temperature, adding 20mL of NaCl or KPF 6 Or KBF 4 Saturated aqueous solution, stirring at room temperature12h; extracting the reaction liquid with dichloromethane, concentrating the collected organic phase under reduced pressure to obtain a crude product, separating by column chromatography with dichloromethane/petroleum ether as eluent, and purifying to obtain the cationic cyclometallated iridium complex.
3. Use of an ionic cyclometallated iridium complex according to claim 1, characterized in that: the cationic cyclometallated iridium complex is applied to the technical field of photoelectric materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310338952.3A CN116396337A (en) | 2023-04-01 | 2023-04-01 | Preparation method and application of cationic cyclometallated iridium complex with oxygen sensitivity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310338952.3A CN116396337A (en) | 2023-04-01 | 2023-04-01 | Preparation method and application of cationic cyclometallated iridium complex with oxygen sensitivity |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116396337A true CN116396337A (en) | 2023-07-07 |
Family
ID=87011753
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310338952.3A Pending CN116396337A (en) | 2023-04-01 | 2023-04-01 | Preparation method and application of cationic cyclometallated iridium complex with oxygen sensitivity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116396337A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951707A (en) * | 2014-05-13 | 2014-07-30 | 深圳市华星光电技术有限公司 | Green ray iridium (III) complex as well as preparation method and application thereof |
| CN105294771A (en) * | 2015-09-16 | 2016-02-03 | 南京邮电大学 | Anionic type iridium complex for oxygen sensing, and preparation method and application thereof |
| CN106188151A (en) * | 2016-07-06 | 2016-12-07 | 南京邮电大学 | A kind of ion-type phosphorescent iridium complex probe based on pyridiniujm and preparation method thereof and biologic applications |
| CN111253443A (en) * | 2020-03-25 | 2020-06-09 | 大连理工大学 | Preparation method and application of electroblotting group modified cyclometalated iridium complex |
| WO2022262300A1 (en) * | 2021-06-15 | 2022-12-22 | 江苏科技大学 | Neutral iridium complex containing biphenyl derivative ligand, preparation method therefor, and application thereof |
-
2023
- 2023-04-01 CN CN202310338952.3A patent/CN116396337A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103951707A (en) * | 2014-05-13 | 2014-07-30 | 深圳市华星光电技术有限公司 | Green ray iridium (III) complex as well as preparation method and application thereof |
| CN105294771A (en) * | 2015-09-16 | 2016-02-03 | 南京邮电大学 | Anionic type iridium complex for oxygen sensing, and preparation method and application thereof |
| CN106188151A (en) * | 2016-07-06 | 2016-12-07 | 南京邮电大学 | A kind of ion-type phosphorescent iridium complex probe based on pyridiniujm and preparation method thereof and biologic applications |
| CN111253443A (en) * | 2020-03-25 | 2020-06-09 | 大连理工大学 | Preparation method and application of electroblotting group modified cyclometalated iridium complex |
| WO2022262300A1 (en) * | 2021-06-15 | 2022-12-22 | 江苏科技大学 | Neutral iridium complex containing biphenyl derivative ligand, preparation method therefor, and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| LEI WANG: "Synthesis and properties of fluorinated cyclometalated Ir(III) complexes", TETRAHEDRON, vol. 76, 10 July 2020 (2020-07-10), pages 131390, XP086229326, DOI: 10.1016/j.tet.2020.131390 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110818743B (en) | Preparation method and application of cyclometalated platinum complex with aggregation-induced emission property | |
| Yang et al. | Postclustering dynamic covalent modification for chirality control and chiral sensing | |
| CN111187301B (en) | Preparation method and application of aggregation-induced emission iridium complex | |
| Li et al. | Multistimuli-responsive fluorescent organometallic assemblies based on mesoionic carbene-decorated tetraphenylethene ligands and their applications in cell imaging | |
| Chen et al. | Multifunctional behavior of a novel tetraphenylethylene derivative: Mechanochromic luminescence, detection of fluoride ions and trace water in aprotic solvents | |
| He et al. | AIPE-active cationic Ir (III) complexes for efficient detection of 2, 4, 6-trinitrophenol and oxygen | |
| CN111253443B (en) | Preparation method and application of electroblotting group modified cyclometalated iridium complex | |
| CN111875641B (en) | Preparation method and application of trifluoromethyl modified platinum complex | |
| CN111961085B (en) | Preparation method and application of aggregation-induced emission halogen-modified platinum complex | |
| CN111875634A (en) | Benzimidazole bidentate ligand-based luminescent copper compound and preparation method thereof | |
| CN111793095A (en) | Preparation method and application of cyclometalated platinum complex | |
| CN111039970A (en) | Pyridyl boron dipyrromethene derivative dye ligand and preparation method thereof | |
| CN109776614B (en) | Cuprous complex fluorescent sensing material selectively responding to 4-methylpyridine steam | |
| CN116396337A (en) | Preparation method and application of cationic cyclometallated iridium complex with oxygen sensitivity | |
| Field et al. | Non-covalent interactions between cations in the crystal structure of [Pt {4′-(p-tolyl) trpy} Cl] SbF6, where trpy is 2, 2′: 6′, 2 ″-terpyridine, underpin the salt’s complex solid-state luminescence spectrum | |
| Shen et al. | New 2-phenyl-5-nitropyridyl containing iridium (III) cyclometalated complexes: syntheses, structures, electrochemistry and photophysical properties | |
| CN102503993B (en) | Water-soluble cyclized metal iridium complex with sugary ligand and application of complex | |
| CN110117283B (en) | N heterocyclic benzophenone derivative containing hydrogenated phenothiazine group and preparation method thereof | |
| CN115093572B (en) | Polypyridine ring metal iridium supermolecular material, preparation method and application | |
| CN113773328B (en) | Fluorenyl carbazole macrocyclic compound and preparation method and application thereof | |
| CN104447874B (en) | The preparation of metal complex and its application process | |
| CN1651444A (en) | Ruthenium (II) compounding material used for pH sensing and its preparation method | |
| Son et al. | Electrochemical and fluorescent properties of ferrocenyl-chalcone with N-ethyl carbazole group | |
| CN114106058B (en) | Preparation method and application of aggregation-induced emission platinum complex | |
| CN111196776B (en) | Cyanoimine substituted pyrene derivative and synthetic method thereof |
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 |