CN107955041A - A kind of complex of iridium with double emission characteristics and its preparation method and application - Google Patents
A kind of complex of iridium with double emission characteristics and its preparation method and application Download PDFInfo
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- CN107955041A CN107955041A CN201710977794.0A CN201710977794A CN107955041A CN 107955041 A CN107955041 A CN 107955041A CN 201710977794 A CN201710977794 A CN 201710977794A CN 107955041 A CN107955041 A CN 107955041A
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- iridium
- emission characteristics
- double emission
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 47
- 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 claims abstract description 11
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003446 ligand Substances 0.000 claims abstract description 15
- 238000001514 detection method Methods 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 37
- 150000001875 compounds Chemical class 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000003384 imaging method Methods 0.000 claims description 9
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 5
- 239000007850 fluorescent dye Substances 0.000 claims description 3
- 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
- 230000000694 effects Effects 0.000 abstract description 2
- 239000011365 complex material Substances 0.000 abstract 1
- 230000005284 excitation Effects 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 230000015572 biosynthetic process Effects 0.000 description 13
- 238000003786 synthesis reaction Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 8
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 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
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 5
- 239000007788 liquid Substances 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
- 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
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000005708 Sodium hypochlorite Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- OKKJLVBELUTLKV-VMNATFBRSA-N methanol-d1 Chemical compound [2H]OC OKKJLVBELUTLKV-VMNATFBRSA-N 0.000 description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 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
- VRVRGVPWCUEOGV-UHFFFAOYSA-N 2-aminothiophenol Chemical compound NC1=CC=CC=C1S VRVRGVPWCUEOGV-UHFFFAOYSA-N 0.000 description 2
- 229910021638 Iridium(III) chloride Inorganic materials 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
- 239000012295 chemical reaction liquid Substances 0.000 description 2
- 238000004440 column chromatography Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- 230000003834 intracellular effect Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 210000003739 neck Anatomy 0.000 description 2
- UOKZUTXLHRTLFH-UHFFFAOYSA-N o-phenylhydroxylamine Chemical group NOC1=CC=CC=C1 UOKZUTXLHRTLFH-UHFFFAOYSA-N 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000000523 sample 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
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012472 biological sample Substances 0.000 description 1
- 238000010504 bond cleavage reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 239000000417 fungicide Substances 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
- 208000014674 injury Diseases 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 210000002540 macrophage Anatomy 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 210000001616 monocyte Anatomy 0.000 description 1
- 210000004493 neutrocyte Anatomy 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 108040007629 peroxidase activity proteins Proteins 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002123 temporal effect Effects 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012800 visualization Methods 0.000 description 1
Classifications
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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
-
- 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
-
- G—PHYSICS
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Biomedical Technology (AREA)
- Molecular Biology (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
Abstract
The present invention provides a kind of complex of iridium with double emission characteristics and its preparation method and application, the structural formula of the complex of iridium is shown below：The complex is made of a metal iridium center, a neutrality N^N assistant ligand and two ring metal C^N ligands, and contains 4 amino phenyl ether groups on its C^N ligand.The ionic type iridium complex has obvious double emission characteristics.In addition, after being had an effect using carbon-oxygen bond in ligand and hypochlorite ion, carbon-oxygen bond can be broken, so as to cause the change of complex of iridium excitation state and photophysical property so as to fulfill the detection to hypochlorite ion.Phosphorescent iridium complex material of the present invention has important application prospect in terms of biology.
Description
Technical field
The invention belongs to organic photoelectric functional material technical field, and in particular to a kind of iridium with double emission characteristics coordinates
Thing and preparation method thereof and its hypochlorite context of detection application.
Background technology
Hypochlorite ion (ClO-) it is a kind of important active oxygen, it is a kind of important in various biological life activities
Intermediate product.Endogenous hypochlorous acid is occurred mainly with granulocyte (macrophage, monocyte and neutrophil leucocyte etc.), in marrow
There are chlorion and hydroperoxidation generation under the catalysis of peroxidase.Hypochlorous acid has the function of fungicide in body,
Play an important role in immune system.But hypochlorous acid is insufficient or excessively has injury to human body.Therefore, it is possible to it is quick,
It is particularly important that sensitively and accurately detecting the hypochlorous acid in biological sample.
The method that the luminescence imaging technology sensed using fluorescence chemical provides system uniqueness between visualization HOCl.Fluorescence passes
Imaging technique is felt due to high sensitivity, selectivity is good, and data acquisition is simple, and spatial resolution and temporal resolution are high, so that by
It is considered a kind of hypochlorous method of unique detection.There are some hypochlorous acid fluorescence probes to be synthesized in recent years, used
In the monitoring for carrying out hypochlorous acid generation in living cells.Weiying Lin have synthesized a kind of detection ClO-Ratio fluorescent probe, when
When acting on analyte, fluorescent emission ratio (I509/I439) can increase to 2.74 from 0.28, and have higher selectivity
(Chem.Eur.J.,2009,15,2305–2309).This probe is the detection based on fluorescence signal.Compared to fluorescence signal, phosphorus
Optical signal detecting has the advantage that：Transmitting with big Stokes displacements, excited by visible light, good photostability, length
The easily adjusting etc. of service life, high quantum efficiency and launch wavelength.Therefore, phosphorescence Ir (III) complexs are in phosphorescent biological sensing and life
There is important application in terms of thing imaging.The complex with double emission characteristics is used for ion detection except having the above concurrently
Outside, ratio test can also be realized, so as to further improve the signal-to-noise ratio of detection；, can when being applied to cell imaging
To realize that the ratio to intracellular object is imaged and detects.
The present invention gives a kind of complex of iridium with double emission characteristics of offer and preparation method thereof, and propose this kind of match somebody with somebody
Compound is in detection hypochlorite ion and its application in cell imaging.
The present invention obtains project of national nature science fund project (No.21671109), Jiangsu Natural Science Fund In The Light general project
The support of (No. BK20141422).
The content of the invention
Technical problem：It is an object of the invention to provide a kind of complex of iridium with double emission characteristics and its preparation side
Method, and propose this kind of complex in detection hypochlorite ion and its application in cell imaging.
Technical solution：A kind of complex of iridium with double emission characteristics, its structural formula are shown below：
Wherein, N^N ligandsOne kind in following five kinds of heterocyclic compounds：
The preparation method of the above-mentioned complex of iridium with double emission characteristics, including：
Wherein, N^N ligandsOne kind in following five kinds of heterocyclic compounds：
Preferably, in the step of 5 prepare compound 6 of compound, reaction dissolvent is the mixed liquor of cellosolvo and water,
Reaction condition is 110 DEG C, 24h.
The above-mentioned application that there is the complex of iridium of double emission characteristics in hypochlorite detection.
The above-mentioned application that there is the complex of iridium of double emission characteristics in ratio fluorescent probe.
The above-mentioned application that there is the complex of iridium of double emission characteristics in ratio imaging.
Beneficial effect：
The complex of iridium of the present invention has obvious double emission phenomena.Carbon-oxygen bond and hypochlorite ion in the complex of iridium
React, make C―O bond cleavage, so as to cause the photophysical property of complex of iridium to change, it is possible to achieve to hypochlorite
The detection of ion, for the ratio test of intracellular hypochlorite ion.
Brief description of the drawings
Fig. 1 is the complex Ir2's of embodiment 11H NMR spectras；
Fig. 2 is the mass spectrogram of the complex Ir2 of embodiment 1.
Fig. 3 is that the complex Ir2 of embodiment 1 adds the mass spectrogram after excessive hypochlorite ion.
Fig. 4 is double emission phenomena of the complex Ir2 of embodiment 1 in different solvents.
Embodiment
Technical scheme is described further below in conjunction with the accompanying drawings.
The complex of iridium of the present invention has following general structure：
Wherein, N^N ligandsOne kind in following five kinds of heterocyclic compounds：
The complex of iridium of the present invention is matched somebody with somebody by a metal iridium center, a neutrality N^N assistant ligand and two ring metal C^N
Body forms, and contains 4- amino phenyl ether groups on its C^N ligand.
The content of patent for a better understanding of the present invention, further illustrates the present invention's below by specific example
Technical solution.Specifically include synthesis, property measure, titration experiments, cell imaging etc..But these embodiments are not intended to limit this hair
It is bright.
Example 1
When N^N ligands areWhen, the preparation of complex of iridium Ir2, comprises the following steps that：
The synthesis of compound a：First, by 2- amino benzenethiol (4g, 32mmol), parahydroxyben-zaldehyde (4.12mL), add
Enter into 250mL twoport flasks, vacuumize on biexhaust pipe-inflated with nitrogen-to vacuumize, circulation is three times.Secondly, the N that will be steamed again, N
Dimethylformamide (5mL) is expelled in reaction system, and reaction system is protected with nitrogen.Finally, being warming up to reaction system
110 DEG C, stirring reaction 72h.After the reaction was complete, solvent is removed under reduced pressure, gray solid, i.e. compound are obtained using ethyl alcohol recrystallization
a.Yield：41.8%.
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).
The synthesis of compound b：By compound a (1.358g, 5mmol), p-fluoronitrobenzene (846mg, 6mmol), potassium carbonate
(1.382g, 10mmol), is added in twoport flask, is vacuumized on biexhaust pipe, and-inflated with nitrogen-vacuumizes, and circulates three times, finally
Reaction system is protected with nitrogen.Then, the n,N-Dimethylformamide steamed again (5mL) is expelled in reaction system, and will be anti-
Answer the temperature of system to be raised to 70 DEG C, react 24h.After the reaction was complete, extracted with water and ethyl acetate, decompression rotation removes solvent, silica gel
Column purifies, and obtains compound b.Yield：52.7%.
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)
The synthesis of dichloro bridge c：Compound b (348mg, 1mmol), hydrated iridium trichloride (176mg, 0.5mmol) are added
Into twoport flask, magneton is added, encapsulates condenser pipe, vacuum nitrogen gas 3 times, injects solvent cellosolvo with syringe
(9mL) and water (3mL), when 110 DEG C of reactions 24 are small.After the reaction was complete, reaction system is cooled to room temperature, add suitable quantity of water with
Ethanol (2:1), question response liquid stands a moment, has a large amount of solids to separate out, and filters reaction solution, and solid is dichloro bridge c, and drying is standby
With.
The synthesis of complex of iridium Ir1：Take dichloro bridge c (184mg, 0.1mmol) and assistant ligand 2,2'- bipyridyls (31mg,
0.2mmol), twoport flask is put into, adds magneton, encapsulates condenser pipe, vacuum nitrogen gas 3 times, injects appropriate two with syringe
Chloromethanes and methanol (volume ratio 3:1) temperature of reaction system, is raised to 40 DEG C, reacts 10h.A small amount of reaction solution is taken with long syringe needle
Extent of reaction is monitored, treating raw material, almost the reaction was complete, and temperature is adjusted to 25 DEG C, adds excessive Potassium Hexafluorophosphate, it is anti-to continue stirring
Answer liquid 4h.Question response liquid cools down, and with a small amount of dichloromethane and a large amount of water extractive reaction liquid 3 times, dichloromethane layer is product layer, rotation
It is dry, column chromatography purification.Yellow solid product is obtained, is complex Ir1.
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=7.7
Hz, 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 values：1043.13, experiment measures MS (MALDI-TOF) [m/z]:1042.031.
The synthesis of complex of iridium Ir2：The palladium carbon of the complex of iridium Ir1 and 20mg of 104mg are put into bottle with two necks, vacuumized
2 times, ethanol is added, then vacuumize once.Hydrazine hydrate is added, reacts 15h under 80 °.Mass Spectrometer Method is reacted.N-hexane and dichloro
Methane settles 3 times, obtains faint yellow solid 40mg, is complex of iridium Ir2.
Fig. 1 is the hydrogen spectrogram of gained complex of iridium Ir2, and MeOD makees solvent.As shown in Figure 1, the complex of synthesis is exactly this
Designed by 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 values：983.18, experiment measures MS (MALDI-TOF) [m/z]:982.197.
The mass spectrometric measurement of complex of iridium Ir2：
Complex of iridium Ir2 is tested respectively and its adds the mass spectrogram of excessive sodium hypochlorite, as a result as shown in Figures 2 and 3.
The result shows that its mass spectrographic molecular ion peak 982.197 and 983.18 (Ir2-PF of theoretical value6) consistent；In Ir2 plus
It is 799.163 to enter the molecular ion peak after excessive sodium hypochlorite, this remove with complex Ir2 two amino phenyl ether groups from
Sub- molecular weight is consistent, it may be determined that the detection mechanism to hypochlorite ion is shown below：
Emission spectrum of the complex of iridium Ir2 in different solvents：
Complex of iridium Ir2 solids are separately added into the solvent of deoxygenation, test its emission spectrum respectively, as a result such as attached drawing
Shown in 4.The result shows that it has obvious double emission phenomena inside toluene, chloroform, water.
Example 2：When N^N ligands areWhen, the preparation of complex of iridium Ir4, synthesis step is as follows：
The synthesis of compound a：First, by 2- amino benzenethiol (4g, 32mmol), parahydroxyben-zaldehyde (4.12mL), adds
Enter into 250mL twoport flasks, vacuumize on biexhaust pipe-inflated with nitrogen-to vacuumize, circulation is three times.Secondly, the N that will be steamed again, N
Dimethylformamide (5mL) is expelled in reaction system, and reaction system is protected with nitrogen.Finally, being warming up to reaction system
110 DEG C, stirring reaction 72h.After the reaction was complete, solvent is removed under reduced pressure, gray solid, i.e. compound are obtained using ethyl alcohol recrystallization
a.Yield：41.8%.
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).
The synthesis of compound b：By compound a (1.358g, 5mmol), p-fluoronitrobenzene (846mg, 6mmol), potassium carbonate
(1.382g, 10mmol), is added in twoport flask, is vacuumized on biexhaust pipe, and-inflated with nitrogen-vacuumizes, and circulates three times, finally
Reaction system is protected with nitrogen.Then, the n,N-Dimethylformamide steamed again (5mL) is expelled in reaction system, and will be anti-
Answer the temperature of system to be raised to 70 DEG C, react 24h.After the reaction was complete, extracted with water and ethyl acetate, decompression rotation removes solvent, silica gel
Column purifies, and obtains compound b.Yield：52.7%.
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)
The synthesis of dichloro bridge c：Compound b (348mg, 1mmol), hydrated iridium trichloride (176mg, 0.5mmol) are added
Into twoport flask, magneton is added, encapsulates condenser pipe, vacuum nitrogen gas 3 times, injects solvent cellosolvo with syringe
(9mL) and water (3mL), when 110 DEG C of reactions 24 are small.After the reaction was complete, reaction system is cooled to room temperature, add suitable quantity of water with
Ethanol (2:1), question response liquid stands a moment, has a large amount of solids to separate out, and filters reaction solution, and solid is dichloro bridge c, and drying is standby
With.
The synthesis of complex of iridium Ir3：Dichloro bridge c (184mg, 0.1mmol) and assistant ligand Phen are taken, is put into twoport
Flask, adds magneton, encapsulates condenser pipe, vacuum nitrogen gas 3 times, injects q. s. methylene chloride and methanol (volume with syringe
Than 3:1) temperature of reaction system, is raised to 40 DEG C, reacts 10h.A small amount of reaction solution monitoring extent of reaction is taken with long syringe needle, treats original
Almost the reaction was complete for material, and temperature is adjusted to 25 DEG C, adds excessive Potassium Hexafluorophosphate, continues to stir reaction solution 4h.Question response liquid is cold
But, with a small amount of dichloromethane and a large amount of water extractive reaction liquid 3 times, dichloromethane layer is product layer, is spin-dried for, column chromatography purification.
It is complex of iridium Ir3 to yellow solid product.
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).
The synthesis of complex of iridium Ir4：By nitro complex 1 and palladium carbon be put into bottle with two necks, vacuumize 2 times, add second
Alcohol, then vacuumize once.Hydrazine hydrate is added, reacts 15h at 80 DEG C.Mass Spectrometer Method is reacted.N-hexane and dichloromethane sedimentation
3 times, faint yellow solid is obtained, is complex of iridium Ir4.
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).
Mass Spectrometer Method is carried out to complex of iridium Ir4 and its after adding excessive sodium hypochlorite, it is as a result consistent with embodiment 1.Iridium
The mass spectrographic molecular ion peaks 1006.97 of complex Ir4 and 1006.18 (Ir4-PF of theoretical value6) consistent；Added excessive time in Ir4
Molecular ion peak after sodium chlorate is 824.24, this removes the ionic molecule amount of two amino phenyl ether groups with complex Ir4
Unanimously.Complex of iridium Ir4 can also be used for the detection of hypochlorite.
Complex of iridium Ir4 also has obvious double emission phenomena inside toluene, chloroform, water.
Claims (6)
- A kind of 1. complex of iridium with double emission characteristics, it is characterised in that：Its structural formula is shown below：Wherein, N^N ligandsOne kind in following five kinds of heterocyclic compounds：
- 2. the preparation method of the complex of iridium with double emission characteristics described in claim 1, it is characterised in that：Including：Wherein, N^N ligandsOne kind in following five kinds of heterocyclic compounds：
- 3. the preparation method of the complex of iridium according to claim 2 with double emission characteristics, it is characterised in that：Compound In the step of 5 prepare compound 6, reaction dissolvent is cellosolvo and the mixed liquor of water, and reaction condition is 110 DEG C, 24h.
- 4. there is application of the complex of iridium of double emission characteristics in hypochlorite detection described in claim 1.
- 5. there is application of the complex of iridium of double emission characteristics in ratio fluorescent probe described in claim 1.
- 6. there is application of the complex of iridium of double emission characteristics in ratio imaging described in claim 1.
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| CN110437286A (en) * | 2019-07-18 | 2019-11-12 | 常州大学 | The synthesis and its application of the double emissive materials of novel Cyclometalated platinum complexes |
| KR20200111375A (en) * | 2019-03-19 | 2020-09-29 | 서울대학교산학협력단 | Electrochemiluminescent probe for detection of thiophenol |
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| CN103937487A (en) * | 2014-03-25 | 2014-07-23 | 南京邮电大学 | Phosphorescent fluorinion probe, preparation and applications thereof |
| 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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| CN103937487A (en) * | 2014-03-25 | 2014-07-23 | 南京邮电大学 | Phosphorescent fluorinion probe, preparation and applications thereof |
| 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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| XIAO-HONG ZHOU ET AL.: "A naphthalene-based two-photon fluorescent probe for selective and sensitive detection of endogenous hypochlorous acid", 《TALANTA》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200111375A (en) * | 2019-03-19 | 2020-09-29 | 서울대학교산학협력단 | Electrochemiluminescent probe for detection of thiophenol |
| KR102179944B1 (en) | 2019-03-19 | 2020-11-17 | 서울대학교 산학협력단 | Electrochemiluminescent probe for detection of thiophenol |
| CN110437286A (en) * | 2019-07-18 | 2019-11-12 | 常州大学 | The synthesis and its application of the double emissive materials of novel Cyclometalated platinum complexes |
| CN110437286B (en) * | 2019-07-18 | 2021-09-03 | 常州大学 | Synthesis and application of novel cyclometalated platinum complex dual-emission material |
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