CN105461755B - Platinum complex with aggregation-induced red light emission and preparation method and application thereof - Google Patents
Platinum complex with aggregation-induced red light emission and preparation method and application thereof Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 26
- 238000004220 aggregation Methods 0.000 title claims abstract description 22
- 230000002776 aggregation Effects 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title abstract description 11
- 239000003446 ligand Substances 0.000 claims abstract description 5
- 238000005401 electroluminescence Methods 0.000 claims abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- -1 arylamine compound Chemical class 0.000 claims description 6
- 238000003384 imaging method Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
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- 238000000034 method Methods 0.000 claims description 5
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- 239000002262 Schiff base Substances 0.000 claims description 4
- 238000004440 column chromatography Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 229910006400 μ-Cl Inorganic materials 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 239000000706 filtrate Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 238000000967 suction filtration Methods 0.000 claims description 2
- 150000003057 platinum Chemical class 0.000 claims 2
- HWLDNSXPUQTBOD-UHFFFAOYSA-N platinum-iridium alloy Chemical compound [Ir].[Pt] HWLDNSXPUQTBOD-UHFFFAOYSA-N 0.000 claims 2
- 239000010410 layer Substances 0.000 claims 1
- 239000002356 single layer Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
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- 238000012984 biological imaging Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000008204 material by function Substances 0.000 abstract description 2
- 239000011365 complex material Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 17
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 238000000295 emission spectrum Methods 0.000 description 5
- 229910052741 iridium Inorganic materials 0.000 description 5
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 5
- 238000004020 luminiscence type Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
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- 238000005303 weighing Methods 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- NOXLGCOSAFGMDV-UHFFFAOYSA-N 2,3,4,5,6-pentafluoroaniline Chemical compound NC1=C(F)C(F)=C(F)C(F)=C1F NOXLGCOSAFGMDV-UHFFFAOYSA-N 0.000 description 2
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
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- 229910001385 heavy metal Inorganic materials 0.000 description 2
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- 230000007246 mechanism Effects 0.000 description 2
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- 230000000171 quenching effect Effects 0.000 description 2
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- 229910019029 PtCl4 Inorganic materials 0.000 description 1
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- 238000006073 displacement reaction Methods 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 description 1
- DQYBDCGIPTYXML-UHFFFAOYSA-N ethoxyethane;hydrate Chemical compound O.CCOCC DQYBDCGIPTYXML-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
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- 238000010859 live-cell imaging Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- GVOISEJVFFIGQE-YCZSINBZSA-N n-[(1r,2s,5r)-5-[methyl(propan-2-yl)amino]-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](N(C)C(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 GVOISEJVFFIGQE-YCZSINBZSA-N 0.000 description 1
- 230000005693 optoelectronics Effects 0.000 description 1
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- 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
- C07F15/0086—Platinum compounds
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Abstract
The invention belongs to the field of organic photoelectric functional materials; in particular to a platinum complex with aggregation-induced red light emission, a preparation method thereof and application of the material in the fields of organic electroluminescence and biological imaging; the material consists of a ring metal ligand, a metal platinum center and an auxiliary ligand, and the structural general formula is as follows; the material has simple synthesis steps and mild conditions, basically does not emit light in a solution state, but has strong red light emission in a solid state; the platinum complex material with aggregation-induced red light emission can be applied to organic electroluminescent devices and biological imaging.
Description
Technical Field
The invention belongs to the field of organic photoelectric functional materials. In particular to a platinum complex with aggregation-induced red light emission and the application field thereof in the fields of organic photoelectric functional devices and biological imaging.
Background
Phosphorescent transition metal complexes have received much attention from researchers due to their excellent luminescent properties and potential application values in the fields of optoelectronic devices, chemical/biological sensors and bio-imaging. However, as with other organic light-emitting materials, the phosphorescent emission intensity of the transition metal complex also tends to gradually decrease with increasing solution concentration, becoming almost non-light-emitting even in the aggregated state. For example, the more well-known Ir (ppy)3The phosphorescence quantum yield can reach 0.97 under the dilute solution, but the phosphorescence quantum yield drops to 0.03 under the solid thin film state. This is due to aggregation-induced quenching (ACQ), which severely hampers the application of transition metal complexes in many fields, especially those requiring phosphorescent metal complexes to be able to emit light in the aggregated form.
In 2001, Tangbenloyl et al found that silacyclopentadiene derivatives did not substantially emit light in solution, but rather enhanced the emission as the degree of aggregation of the molecules increased, a so-called aggregation-induced emission (AIE) property. The main cause of the formation of such an interesting phenomenon can be expressed as a luminescence enhancement mechanism caused by the inhibition of the rotation within the molecule in an aggregated state, and many organic light emitting molecules having excellent AIE properties have been developed on the basis of such a mechanism and widely used in the fields of organic light emitting diodes, sensing, bio-imaging, and the like. The development of the aggregation-induced emission compound opens up a new way for the wide application of organic light-emitting materials in solid devices. By utilizing the aggregation state induced luminescence property, the problem of reduced luminescence efficiency caused by concentration quenching effect can be solved to a certain extent, and a luminescent material does not need to be doped into a main material when a luminescent device is prepared, so that the preparation process of the device is simplified, and the manufacturing cost of the device is reduced. The work on this aspect is also based on organic fluorescent materials, and in the field of biological imaging, fluorescence as an output signal is often interfered by biological background fluorescence and scattered light [19 ]. An effective solution to this problem is to construct materials with aggregation-induced phosphorescent emission properties (AIPE) to replace the conventional organic fluorescent materials.
Besides the spin-orbit coupling of the phosphorescent iridium complex can be used for improving the quantum efficiency of electroluminescence, the relatively long phosphorescence life of the phosphorescent iridium complex makes the phosphorescent iridium complex become an ideal biological fluorescence imaging labeling dye. Currently, most of the commercial fluorescent dyes used in the field of cell imaging are small organic molecules. However, the organic molecules have poor light stability, large interference of background fluorescence, large cytotoxicity and other defects, which limit the application of the organic molecules in the field of biological imaging. In recent years, the phosphorescent heavy metal iridium complex has attracted great interest as a dye molecule of a fluorescence imaging technology, because the phosphorescent heavy metal iridium complex has the following characteristics different from organic molecules: the fluorescent light has large Stokes displacement and long emission life, the long emission life is beneficial to distinguishing phosphorescent signals from background fluorescent signals by using a time resolution technology, and the fluorescent light has excellent light stability and is convenient for long-time observation.
Disclosure of Invention
The technical problem is as follows: the invention aims to provide a platinum complex with aggregation-induced red light emission, a preparation method thereof and application of the complex in the fields of organic photoelectric devices, biomarkers and cell imaging.
The technical scheme is as follows: the invention relates to a platinum complex with aggregation-induced red light emission, which is characterized by having the following structural formula:
wherein, R can be any one of the following groups:
the preparation method of the platinum complex with aggregation-induced red light emission comprises the following steps:
reacting a fluorine-containing aromatic amine compound with o-hydroxybenzaldehyde, adding a drop of acetic acid into ethanol serving as a solvent to initiate reaction, and stirring for reaction for 2 hours at room temperature to obtain a Schiff base compound; the coordination reaction being in particular N2Under protection, 1 equivalent of potassium chloroplatinite (K)2PtCl4) Dissolving the compound and 2.5 equivalent of cyclometalated ligand in the mixed solution of ethylene glycol ether and water, and carrying out reflux stirring reaction for 12 hours; cooling to room temperature, precipitating, filtering, and drying under infrared lamp to obtain (C ^ N) Pt (mu-Cl)2A Pt (C ^ N) intermediate; then (C ^ N) Pt (mu-Cl)2Pt (C ^ N), 3.0 equivalent of Schiff base compound and 10.0 equivalent of Na2CO3Dissolving in ethylene glycol ethyl ether, and reacting for 12 hours under reflux and stirring; cooling to room temperature after reaction, carrying out suction filtration, carrying out reduced pressure spin-drying on the filtrate, adding dichloromethane for dissolution, and purifying by using a column chromatography method to obtain the platinum complex with aggregation-induced red light emission.
The platinum complex with aggregation-induced red light emission can be applied to the fields of organic electroluminescence, biological imaging and the like.
Has the advantages that:
1. the platinum complex involved in the invention has simple synthesis steps and mild conditions;
2. the platinum complex has strong red light emission in a solid state, and the luminous quantum efficiency in the solid state is more than 5 percent;
3. the platinum complex has large Stokes shift, can easily distinguish excitation from emission, has long luminescence life, can be distinguished from background fluorescence signals by using a time resolution technology so as to improve the signal-to-noise ratio and sensitivity of detection, can be excited by using visible light, and the like.
Drawings
FIG. 1 nuclear magnetic resonance hydrogen spectrum of complex 1 synthesized in the invention
FIG. 2 is a diagram showing the UV-VIS absorption spectrum of the complex 1 synthesized in the present invention in a tetrahydrofuran solution.
FIG. 3 is a graph showing the emission spectra of complex 1 synthesized in the present invention in a tetrahydrofuran solution and in a solid state, respectively.
FIG. 4 is a diagram showing the image of the cell of the complex 1 synthesized in the present invention.
Detailed Description
The invention relates to a structural general formula of a compound as follows:
wherein R may be the following group:
is a heterocyclic compound having the structure:
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, device preparation experiment, cell imaging and the like. These examples do not limit the invention.
Example 1 preparation of a platinum Complex when R isThe ligand is
The method comprises the following steps:
preparation of compound 1 a:
dissolving o-hydroxybenzaldehyde (2.3mL,22mmol) in 20mL ethanol, then weighing pentafluoroaniline (4.0g,22mmol) to be dissolved in 20mL ethanol, dropwise adding the pentafluoroaniline to the ethanol solution of o-hydroxybenzaldehyde, adding 1 drop of acetic acid as a catalyst, stirring and reacting for 2 hours at room temperature, concentrating the mixed solution after the reaction is finished, and performing column chromatography separation by using petroleum ether/dichloromethane as an eluent to obtain 5.4g of yellow solid, wherein the yield is as follows: 85 percent.1H NMR(400MHz,CDCl3)δ8.83(s,1H),7.49-7.40(m,2H),7.07-6.97(m,2H).
Platinum dichloropyridine bridge ((ppy) Pt (. mu. -Cl)2Preparation of Pt (ppy)): weighing potassium platinochloride (1mmol) and 2-phenylpyridine (2.5mmol), adding into a three-neck flask, vacuumizing on a double-row pipe, filling nitrogen, vacuumizing for three times, and finally protecting the reaction system with nitrogen. Injecting a mixture (3:1v/v) of ethylene glycol ethyl ether and water into a reaction system by using an injector, stirring, heating the reaction system to 110 ℃, and reacting for about 12 hours, wherein a precipitate is generated in the reaction process. The reaction was cooled to room temperature, then the precipitate was filtered and washed with water, ethanol to give a yellow-green solid product, yield: 80 percent.
Preparation of platinum Complex 1:
weighing 1 equivalent of platinum dichloro-bridge compound ((ppy) Pt (. mu. -Cl)2Adding Pt (ppy), 3 times of equivalent compound 1a (64mg) and 10 times of equivalent sodium carbonate into a three-mouth bottle, vacuumizing on a double-row pipe, filling nitrogen, vacuumizing for three times, and finally protecting the reaction system by using nitrogen; injecting ethylene glycol ethyl ether by using an injector, heating to 110 ℃, and stirring to react for 12 hours; concentrating the mixture, adding a large amount of water, separating out a platinum complex crude product, filtering, washing with water and diethyl ether, separating the filtered precipitate by column chromatography, removing the solvent in vacuum, and drying to obtain an orange-red solid. Yield: 50 percent.1H NMR(400MHz,DMSO)δ9.38(d,J＝5.5Hz,1H),8.73(s,1H),8.15–7.92(m,2H),7.73–7.55(m,2H),7.56–7.39(m,2H),7.05(d,J＝8.6Hz,1H),6.94(t,J＝7.0Hz,1H),6.81(t,J＝6.9Hz,1H),6.63(t,J＝7.4Hz,1H),5.55(d,J＝7.7Hz,1H).
Example 2: compound characterization
The compound (5-10mg) is dissolved in 0.5ml of deuterated reagent, and the structures of partial compounds are respectively characterized by a 400Hz nuclear magnetic resonance instrument, wherein the nuclear magnetic resonance hydrogen spectrum of the complex 1 in the example 1 is shown in the attached figure 1.
Example 3: ultraviolet-visible absorption spectrum test of complex in tetrahydrofuran solution
A10 mu mol/L tetrahydrofuran solution of the complex is prepared, and an ultraviolet-visible absorption spectrum of the tetrahydrofuran solution is tested on an ultraviolet spectrophotometer, and the absorption spectrum result of the complex 1 is shown in figure 2.
Example 4: emission spectrum of complex in tetrahydrofuran solution and solid state
The emission spectrum of the tetrahydrofuran solution and the emission spectrum of the solid powder of the complex are respectively tested on a fluorescence spectrometer, and the emission spectrum of the complex 1 is shown in figure 3.
Example 6: live cell imaging experiments:
the platinum complex was prepared as a 10mmol/L DMSO solution, and 20. mu.L of the solution was transferred to 2000. mu.L of PBS buffer solution to dilute the solution to a concentration of 10. mu.M. After 2mL of solution is taken to incubate cells for 30 minutes, the cells are washed for 3-5 times by PBS buffer solution, the cells are excited by 405nm wavelength to carry out confocal imaging, and Z scanning and nuclear co-staining data show that the complex has better cell penetration and is distributed in a cytoplasmic region. The image of the living cell of the complex 1 is shown in FIG. 4.
Claims (5)
1. A platinum complex having aggregation-induced red emission, characterized in that the platinum complex has the following structural formula:
wherein,
a group of any one of the following structures:
2. the method for preparing platinum complex with aggregation-induced red light emission according to claim 1, wherein the synthetic route is as follows:
specifically, firstly, the fluorine-containing arylamine compound reacts with o-hydroxybenzaldehyde, ethanol is used as a solvent, and thenAdding a drop of acetic acid to initiate the reaction, and stirring the mixture for reaction for 2 hours at room temperature to obtain a Schiff base compound; the coordination reaction being in particular N2Under protection, 1 equivalent of potassium chloroplatinite and 2.5 equivalents of a ring metal ligand compound are dissolved in mixed solution of ethylene glycol ether and water, and reflux stirring reaction is carried out for 12 hours; cooling to room temperature, precipitating, filtering, and drying under infrared lamp to obtain (C ^ N) Pt (mu-Cl)2A Pt (C ^ N) intermediate; then (C ^ N) Pt (mu-Cl)2Pt (C ^ N), 3.0 equivalent of Schiff base compound and 5.0 equivalent of Na2CO3Dissolving in ethylene glycol ethyl ether, and reacting for 12 hours under reflux and stirring; cooling to room temperature after reaction, carrying out suction filtration, carrying out reduced pressure spin-drying on the filtrate, adding dichloromethane for dissolution, and purifying by using a column chromatography method to obtain the platinum complex with aggregation-induced red light emission.
3. The application of the platinum complex with aggregation-induced red light emission as claimed in claim 1, wherein the platinum iridium complex is applied to the field of organic electroluminescence, and a device of the platinum iridium complex is of a single-layer or multi-layer structure.
4. Use of a platinum complex with aggregation-induced red emission according to claim 1, characterized in that the platinum complex is applicable for bio-imaging.
5. Use of platinum complexes with aggregation-induced red emission according to claim 1, characterized in that the platinum complexes are used for time-resolved bioimaging.
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