CN107955041B - Iridium complex with dual-emission property and preparation method and application thereof - Google Patents
Iridium complex with dual-emission property and preparation method and application thereof Download PDFInfo
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 46
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title abstract description 9
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Inorganic materials Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003446 ligand Substances 0.000 claims abstract description 17
- 238000001514 detection method Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 150000001875 compounds Chemical class 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000003384 imaging method Methods 0.000 claims description 9
- 230000009977 dual effect Effects 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 5
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 4
- 229940093475 2-ethoxyethanol Drugs 0.000 claims description 4
- 239000007850 fluorescent dye Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 229940125898 compound 5 Drugs 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- -1 hypochlorite ions Chemical class 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- HLBLWEWZXPIGSM-UHFFFAOYSA-N 4-Aminophenyl ether Chemical group C1=CC(N)=CC=C1OC1=CC=C(N)C=C1 HLBLWEWZXPIGSM-UHFFFAOYSA-N 0.000 abstract description 2
- 230000007935 neutral effect Effects 0.000 abstract description 2
- 239000011365 complex material Substances 0.000 abstract 1
- 230000005281 excited state Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 238000003786 synthesis reaction Methods 0.000 description 11
- 229910052757 nitrogen Inorganic materials 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 5
- RGHHSNMVTDWUBI-UHFFFAOYSA-N 4-hydroxybenzaldehyde Chemical compound OC1=CC=C(C=O)C=C1 RGHHSNMVTDWUBI-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- 239000005708 Sodium hypochlorite Substances 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 150000001793 charged compounds Chemical class 0.000 description 4
- 239000012295 chemical reaction liquid Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
- 238000004949 mass spectrometry Methods 0.000 description 3
- OKKJLVBELUTLKV-VMNATFBRSA-N methanol-d1 Chemical compound [2H]OC OKKJLVBELUTLKV-VMNATFBRSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- WFQDTOYDVUWQMS-UHFFFAOYSA-N 1-fluoro-4-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=C(F)C=C1 WFQDTOYDVUWQMS-UHFFFAOYSA-N 0.000 description 2
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 description 2
- GOJFAKBEASOYNM-UHFFFAOYSA-N 2-(2-aminophenoxy)aniline Chemical group NC1=CC=CC=C1OC1=CC=CC=C1N GOJFAKBEASOYNM-UHFFFAOYSA-N 0.000 description 2
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical compound NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 150000002503 iridium Chemical class 0.000 description 2
- YOLNUNVVUJULQZ-UHFFFAOYSA-J iridium;tetrachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Ir] YOLNUNVVUJULQZ-UHFFFAOYSA-J 0.000 description 2
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 102000003896 Myeloperoxidases Human genes 0.000 description 1
- 108090000235 Myeloperoxidases Proteins 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 210000003714 granulocyte Anatomy 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 210000000987 immune system Anatomy 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 210000002540 macrophage Anatomy 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 210000001616 monocyte Anatomy 0.000 description 1
- 210000000440 neutrophil Anatomy 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
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- 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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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6486—Measuring fluorescence of biological material, e.g. DNA, RNA, cells
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- 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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Abstract
The invention provides an iridium complex with dual-emission property, a preparation method and application thereof, wherein the iridium complex has a structural formula shown as the following formula:
the complex consists of a metal iridium center, a neutral N ^ N auxiliary ligand and two ring metal C ^ N ligands, and the C ^ N ligands contain 4-aminophenyl ether groups. The ionic iridium complex has obvious dual-emission property. In addition, after the carbon-oxygen bond in the ligand is reacted with hypochlorite ions, the carbon-oxygen bond is broken, so that the excited state and the photophysical properties of the iridium complex are changed, and the detection of the hypochlorite ions is realized. The phosphorescent iridium complex material has important application prospect in the biological aspect.
Description
Technical Field
The invention belongs to the technical field of organic photoelectric functional materials, and particularly relates to an iridium complex with dual-emission property, a preparation method thereof and application thereof in hypochlorite detection.
Background
Hypochlorite ion (ClO)-) Is an important active oxygen and an important intermediate product in various biological life activities. Endogenous hypochlorous acid is mainly produced in granulocytes (macrophages, monocytes, neutrophils, etc.) and is generated by the reaction of chloride ions and hydrogen peroxide catalyzed by myeloperoxidase. Hypochlorous acid has the function of a bactericide in the body and plays an important role in the immune system. However, hypochlorous acid is harmful to the human body when insufficient or excessive. Therefore, it is important to be able to detect hypochlorous acid in a biological sample quickly, sensitively and accurately.
Luminescence imaging technology using fluorescence chemosensing provides a unique method of visualizing inter-HOCl systems. The fluorescence sensing imaging technology is considered as a unique method for detecting hypochlorous acid due to high sensitivity, good selectivity, simple data acquisition and high spatial resolution and time resolution. In recent years, some hypochlorous acid fluorescent probes have been synthesized for monitoring hypochlorous acid production in living cells. Weiying Lin synthesizes a method for detecting ClO-When used for an analyte, the fluorescence emission ratio (I509/I439) can be increased from 0.28 to 2.74 with higher selectivity (chem. Eur. J.,2009,15, 2305-2309). The probe is based on the detection of a fluorescent signal. Phosphorescent signal detection has the following advantages compared to fluorescent signals: the quantum well quantum. Therefore, the phosphorescent Ir (III) complex has important application in phosphorescent biosensing and bioimaging. The complex with dual-emission property used for ion detection has the advantages, and can realize ratio detection, so that the signal-to-noise ratio of detection can be further improved; when the method is applied to cell imaging, ratio imaging and detection of target objects in cells can be realized.
The invention provides an iridium complex with dual-emission property and a preparation method thereof, and provides application of the complex in detecting hypochlorite ions and in cell imaging.
The invention is supported by the national science fund project (No.21671109) and the Jiangsu science fund surface project (No. BK 20141422).
Disclosure of Invention
The technical problem is as follows: the invention aims to provide an iridium complex with dual-emission property and a preparation method thereof, and provides application of the complex in detecting hypochlorite ions and in cell imaging.
The technical scheme is as follows: an iridium complex with dual-emission property has a structural formula shown as the following formula:
wherein, N ^ N ligand
One of the following five heterocyclic compounds:
the preparation method of the iridium complex with dual-emission property comprises the following steps:
wherein, N ^ N ligand
One of the following five heterocyclic compounds:
preferably, in the step of preparing the compound 6 from the compound 5, the reaction solvent is a mixed solution of 2-ethoxyethanol and water, and the reaction conditions are 110 ℃ and 24 hours.
The iridium complex with dual-emission property is applied to hypochlorite detection.
The iridium complex with dual-emission property is applied to ratiometric fluorescent probes.
The use of the above iridium complexes with dual emission properties in ratio imaging.
Has the advantages that:
the iridium complex has an obvious dual-emission phenomenon. The carbon-oxygen bond in the iridium complex reacts with hypochlorite ions to break the carbon-oxygen bond, so that photophysical properties of the iridium complex are changed, the hypochlorite ions can be detected, and the method is used for detecting the ratio of the intracellular hypochlorite ions.
Drawings
FIG. 1 shows preparation of the complex Ir2 from example 11H NMR spectrum;
FIG. 2 is a mass spectrum of complex Ir2 of example 1.
FIG. 3 is a mass spectrum of complex Ir2 of example 1 after addition of excess hypochlorite ion.
FIG. 4 shows the double emission of the complex Ir2 from example 1 in different solvents.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
The iridium complex has the following structural general formula:
wherein, N ^ N ligand
One of the following five heterocyclic compounds:
the iridium complex consists of a metal iridium center, a neutral N ^ N auxiliary ligand and two ring metal C ^ N ligands, and the C ^ N ligands contain 4-aminophenyl ether groups.
In order to better understand the contents of the present patent, the following further illustrates the technical solution of the present invention by specific examples. The method specifically comprises synthesis, property determination, titration experiment, cell imaging and the like. These examples do not limit the invention.
Example 1
When the N ^ N ligand is
The specific steps of preparing the iridium complex Ir2The following were used:
synthesis of Compound a: first, 2-aminobenzenethiol (4g, 32mmol), p-hydroxybenzaldehyde (4.12mL) were added to a 250mL two-necked flask, and vacuum-charged with nitrogen-evacuated on the double drain, and the cycle was repeated three times. Next, redistilled N, N-dimethylformamide (5mL) was injected into the reaction system, and the reaction system was protected with nitrogen. Finally, the temperature of the reaction system is raised to 110 ℃, and the reaction is stirred for 72 hours. After the reaction was complete, the solvent was removed under reduced pressure and recrystallized from ethanol to give a grey solid, compound a. Yield: 41.8 percent.
1H NMR(400MHz,d6-DMSO):δ＝10.21(s,1H),8.07(d,J＝7.9Hz,1H),8.00–7.87(m,3H),7.53–7.45(m,1H),7.43–7.33(m,1H),6.97–6.88(m,2H).
Synthesis of Compound b: adding the compound a (1.358g, 5mmol), p-fluoronitrobenzene (846mg, 6mmol) and potassium carbonate (1.382g, 10mmol) into a double-neck flask, vacuumizing on a double-row pipe, filling nitrogen and vacuumizing for three times, and finally protecting the reaction system by using nitrogen. Then, redistilled N, N-dimethylformamide (5mL) was injected into the reaction system, and the temperature of the reaction system was raised to 70 ℃ to react for 24 hours. After the reaction is completed, extracting with water and ethyl acetate, removing the solvent by rotary removal under reduced pressure, and purifying with a silica gel column to obtain a compound b. Yield: 52.7 percent.
1H NMR(400MHz,CDCl3):δ＝8.28–8.23(m,2H),8.16(d,J＝8.8Hz,2H),8.08(d,J＝8.2Hz,1H),7.93(d,J＝8.0Hz,1H),7.52(t,J＝7.6Hz,1H),7.42(t,J＝8.0Hz,1H),7.21(d,J ＝8.8Hz,2H),7.12(d,J＝9.3Hz,2H).
Synthesis of dichloro bridge c: compound b (348mg, 1mmol), iridium trichloride hydrate (176mg, 0.5mmol) were charged into a two-necked flask, magnetons were added, a condenser tube was sealed, vacuum was applied 3 times with nitrogen, and the solvents 2-ethoxyethanol (9mL) and water (3mL) were injected by syringe and reacted at 110 ℃ for 24 hours. After the reaction is completed, cooling the reaction system to room temperature, adding a proper amount of water and ethanol (2:1), standing the reaction solution for a moment, separating out a large amount of solids, filtering the reaction solution in a suction manner, and drying the reaction solution for later use, wherein the solids are the dichloro-bridge c.
Synthesis of iridium complex Ir 1: taking dichloro-bridge c (184mg, 0.1mmol) and auxiliary ligand 2,2' -bipyridine (31mg, 0.2mmol), putting into a double-neck flask, adding magnetons, packaging a condenser tube, vacuumizing and filling nitrogen for 3 times, injecting a proper amount of dichloromethane and methanol (volume ratio of 3:1) by using an injector, raising the temperature of a reaction system to 40 ℃, and reacting for 10 hours. And (3) taking a small amount of reaction liquid by using a long needle to monitor the reaction progress, adjusting the temperature to 25 ℃ when the raw materials almost completely react, adding excessive potassium hexafluorophosphate, and continuously stirring the reaction liquid for 4 hours. And (3) cooling the reaction solution, extracting the reaction solution for 3 times by using a small amount of dichloromethane and a large amount of water, taking a dichloromethane layer as a product layer, spin-drying, and purifying by column chromatography. The yellow solid product is the complex Ir 1.
1H NMR(400MHz,d6-DMSO):δ＝8.82(d,J＝8.3Hz,2H),8.31(t,J＝7.8Hz,2H),8.10(d,J＝4.8,2H),8.07(d,J＝8.4,2H),8.03–7.93(m,6H),7.84–7.78(m,2H),7.24(t,J＝7.7Hz,2H),7.10(t,J＝7.0Hz,2H),7.08–7.03(m,4H),6.94(dd,J＝8.5,2.4Hz,2H),5.94(d,J＝ 8.4Hz,2H),5.59(d,J＝2.4Hz,2H)。
Theoretical MS value: 1043.13, MS (MALDI-TOF) [ m/z ] 1042.031.
Synthesis of iridium complex Ir 2: 104mg of iridium complex Ir1 and 20mg of palladium on carbon are placed in a two-necked flask, evacuated 2 times, added with ethanol and evacuated once more. Hydrazine hydrate was added and the reaction was carried out at 80 ℃ for 15 h. And (4) detecting the reaction by mass spectrometry. And settling the n-hexane and the dichloromethane for 3 times to obtain a light yellow solid of 40mg, namely the iridium complex Ir 2.
FIG. 1 shows a hydrogen spectrum of the iridium complex Ir2 obtained with MeOD as solvent. As can be seen from FIG. 1, the synthesized complex is designed by the present invention.
1H NMR(400MHz,MeOD):δ＝8.60(d,J＝8.0Hz,2H),8.17-8.11(m,4H),7.88(d,J＝8.1 Hz,2H),7.73(d,J＝8.5Hz,2H),7.65–7.59(m,2H),7.27(t,J＝7.5Hz,2H),6.96(t,J＝7.8Hz, 2H),6.67(dd,J＝8.5,2.3Hz,2H),6.46-6.22(m,8H),5.98(d,J＝8.5Hz,2H),5.47(d,J＝2.3 Hz,2H)。
Theoretical MS value: 983.18, MS (MALDI-TOF) [ m/z ] 982.197.
Mass spectrometric testing of iridium complexes Ir 2:
the mass spectra of the iridium complex Ir2 and its added excess sodium hypochlorite were tested separately and the results are shown in FIGS. 2 and 3.
The results show that the molecular ion peak 982.197 of the mass spectrum is equal to the theoretical value 983.18(Ir 2-PF)6) The consistency is achieved; the molecular ion peak after adding excessive sodium hypochlorite into Ir2 is 799.163, which is consistent with the molecular weight of the complex Ir2 for removing two aminophenyl ether groups, and the detection mechanism of hypochlorite ions can be determined as shown in the following formula:
emission spectra of iridium complex Ir2 in different solvents:
the iridium complex Ir2 solid is respectively added into the deoxygenated solvent, and the emission spectrum is respectively tested, and the result is shown in the attached figure 4. The results show that the double-emission phenomenon is obvious in toluene, chloroform and water.
Example 2: when the N ^ N ligand is
The preparation method of the iridium complex Ir4 comprises the following synthetic steps:
synthesis of Compound a: first, 2-aminobenzenethiol (4g, 32mmol), p-hydroxybenzaldehyde (4.12mL) was added to a 250mL two-necked flask, and vacuum-charged with nitrogen-evacuated on the double drain, and the cycle was repeated three times. Next, redistilled N, N-dimethylformamide (5mL) was injected into the reaction system, and the reaction system was protected with nitrogen. Finally, the temperature of the reaction system is raised to 110 ℃, and the reaction is stirred for 72 hours. After the reaction was complete, the solvent was removed under reduced pressure and recrystallized from ethanol to give a grey solid, compound a. Yield: 41.8 percent.
1H NMR(400MHz,d6-DMSO):δ＝10.21(s,1H),8.07(d,J＝7.9Hz,1H),8.00–7.87(m,3H),7.53–7.45(m,1H),7.43–7.33(m,1H),6.97–6.88(m,2H).
Synthesis of Compound b: adding the compound a (1.358g, 5mmol), p-fluoronitrobenzene (846mg, 6mmol) and potassium carbonate (1.382g, 10mmol) into a double-neck flask, vacuumizing on a double-row pipe, filling nitrogen and vacuumizing for three times, and finally protecting the reaction system by using nitrogen. Then, redistilled N, N-dimethylformamide (5mL) was injected into the reaction system, and the temperature of the reaction system was raised to 70 ℃ to react for 24 hours. After the reaction is completed, extracting with water and ethyl acetate, removing the solvent by rotary removal under reduced pressure, and purifying with a silica gel column to obtain a compound b. Yield: 52.7 percent.
1H NMR(400MHz,CDCl3):δ＝8.28–8.23(m,2H),8.16(d,J＝8.8Hz,2H),8.08(d,J＝8.2Hz,1H),7.93(d,J＝8.0Hz,1H),7.52(t,J＝7.6Hz,1H),7.42(t,J＝8.0Hz,1H),7.21(d,J ＝8.8Hz,2H),7.12(d,J＝9.3Hz,2H).
Synthesis of dichloro bridge c: compound b (348mg, 1mmol), iridium trichloride hydrate (176mg, 0.5mmol) were charged into a two-necked flask, magnetons were added, a condenser tube was sealed, vacuum was applied 3 times with nitrogen, and the solvents 2-ethoxyethanol (9mL) and water (3mL) were injected by syringe and reacted at 110 ℃ for 24 hours. After the reaction is completed, cooling the reaction system to room temperature, adding a proper amount of water and ethanol (2:1), standing the reaction solution for a moment, separating out a large amount of solids, filtering the reaction solution in a suction manner, and drying the reaction solution for later use, wherein the solids are the dichloro-bridge c.
Synthesis of iridium complex Ir 3: taking dichloro-bridge c (184mg, 0.1mmol) and auxiliary ligand phenanthroline, putting the dichloro-bridge c and the auxiliary ligand phenanthroline into a double-neck flask, adding magnetons, packaging a condenser tube, vacuumizing and filling nitrogen for 3 times, injecting a proper amount of dichloromethane and methanol (volume ratio is 3:1) by using an injector, raising the temperature of a reaction system to 40 ℃, and reacting for 10 hours. And (3) taking a small amount of reaction liquid by using a long needle to monitor the reaction progress, adjusting the temperature to 25 ℃ when the raw materials almost completely react, adding excessive potassium hexafluorophosphate, and continuously stirring the reaction liquid for 4 hours. And (3) cooling the reaction solution, extracting the reaction solution for 3 times by using a small amount of dichloromethane and a large amount of water, taking a dichloromethane layer as a product layer, spin-drying, and purifying by column chromatography. Obtaining a yellow solid product, namely the iridium complex Ir 3.
1H NMR(400MHz,d6-DMSO):δ＝8.62(d,J＝8.3Hz,2H),8.01(t,J＝7.8Hz,2H),8.07(d,J＝8.4,2H),8.23–7.63(m,6H),7.82–7.58(m,2H),7.59(dd,J＝6.0,0.7Hz,2H),7.22(t,J ＝7.7Hz,2H),7.20(t,J＝7.0Hz,2H),7.08–7.03(m,4H),6.84(dd,J＝8.5,2.4Hz,2H),5.84 (d,J＝8.4Hz,2H),5.62(d,J＝2.4Hz,2H)。
Synthesis of iridium complex Ir 4: putting the nitro complex 1 and palladium-carbon into a double-mouth bottle, vacuumizing for 2 times, adding ethanol, and vacuumizing once again. Hydrazine hydrate is added and the reaction is carried out for 15h at 80 ℃. And (4) detecting the reaction by mass spectrometry. And settling the normal hexane and the dichloromethane for 3 times to obtain a light yellow solid, namely the iridium complex Ir 4.
1H NMR(400MHz,MeOD):δ＝8.62(d,J＝8.0Hz,2H),8.27-8.31(m,4H),7.63(d,J＝8.5 Hz,2H),7.34(dd,J＝6.0,0.7Hz,2H),7.44–7.33(m,2H),7.27(t,J＝7.5Hz,2H),7.01(t,J＝ 7.8Hz,2H),6.69(dd,J＝8.5,2.3Hz,2H),6.36-6.22(m,8H),6.00(d,J＝8.5Hz,2H),5.57(d, J＝2.3Hz,2H)。
The iridium complex Ir4 and the mass spectrometry detection result of the iridium complex Ir4 added with excessive sodium hypochlorite are consistent with the result of example 1. Molecular ion peak 1006.97 and theoretical value 1006.18(Ir 4-PF) of iridium complex Ir4 mass spectrum6) The consistency is achieved; the molecular ion peak after the addition of excess sodium hypochlorite to Ir4 was 824.24, which is consistent with the ionic molecular weight of complex Ir4 for the removal of two aminophenyl ether groups. The iridium complex Ir4 may also be used for the detection of hypochlorite.
The iridium complex Ir4 has obvious dual-emission phenomenon in toluene, chloroform and water.
Claims (6)
1. An iridium complex having dual emission properties, characterized in that: the structural formula is shown as the following formula:
wherein, N ^ N ligand
One of the following five heterocyclic compounds:
2. the method for producing an iridium complex having a dual emission property as claimed in claim 1, wherein: the method comprises the following steps:
wherein, N ^ N ligand
One of the following five heterocyclic compounds:
3. the method for producing an iridium complex having a dual emission property as claimed in claim 2, wherein: in the step of preparing the compound 6 from the compound 5, the reaction solvent is a mixed solution of 2-ethoxyethanol and water, and the reaction conditions are 110 ℃ and 24 hours.
4. Use of the iridium complex with dual emission property according to claim 1 in hypochlorite detection.
5. Use of an iridium complex with dual emission properties according to claim 1 in ratiometric fluorescent probes.
6. Use of an iridium complex with dual emission properties according to claim 1 in ratio imaging.
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| CN106892947A (en) * | 2017-02-28 | 2017-06-27 | 陕西师范大学 | One kind contains（Hydrazinocarbonyl）Complex of iridium of ferrocene ligands and its preparation method and application |
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