CN113603725B - Bithiazole type metal iridium complex, preparation method and application thereof - Google Patents
Bithiazole type metal iridium complex, preparation method and application thereof Download PDFInfo
- Publication number
- CN113603725B CN113603725B CN202110738940.0A CN202110738940A CN113603725B CN 113603725 B CN113603725 B CN 113603725B CN 202110738940 A CN202110738940 A CN 202110738940A CN 113603725 B CN113603725 B CN 113603725B
- Authority
- CN
- China
- Prior art keywords
- bithiazole
- viscosity
- iii
- complex
- iridium
- 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.)
- Active
Links
- SMSLWFZHCONMGQ-UHFFFAOYSA-N 2-(1,3-thiazol-2-yl)-1,3-thiazole Chemical compound C1=CSC(C=2SC=CN=2)=N1 SMSLWFZHCONMGQ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 20
- 239000002184 metal Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910052741 iridium Inorganic materials 0.000 title abstract description 24
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title abstract description 24
- 238000001514 detection method Methods 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052794 bromium Inorganic materials 0.000 claims abstract description 6
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000000460 chlorine Substances 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical class OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 7
- 239000000539 dimer Substances 0.000 claims description 7
- 239000012065 filter cake Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000004440 column chromatography Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- MILUBEOXRNEUHS-UHFFFAOYSA-N iridium(3+) Chemical compound [Ir+3] MILUBEOXRNEUHS-UHFFFAOYSA-N 0.000 claims 8
- 238000001816 cooling Methods 0.000 claims 1
- 238000005259 measurement Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 11
- -1 hexafluorophosphate Chemical compound 0.000 abstract description 11
- 239000000523 sample Substances 0.000 abstract description 6
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 abstract description 4
- UNTNRNUQVKDIPV-UHFFFAOYSA-N 3h-dithiazole Chemical compound N1SSC=C1 UNTNRNUQVKDIPV-UHFFFAOYSA-N 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 125000001424 substituent group Chemical group 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 230000000007 visual effect Effects 0.000 abstract description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 18
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 8
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 150000002503 iridium Chemical class 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- 210000004027 cell Anatomy 0.000 description 3
- 230000003834 intracellular effect Effects 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000012452 mother liquor Substances 0.000 description 3
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical group C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- BDWFYHUDXIDTIU-UHFFFAOYSA-N ethanol;propane-1,2,3-triol Chemical compound CCO.OCC(O)CO BDWFYHUDXIDTIU-UHFFFAOYSA-N 0.000 description 2
- 238000001917 fluorescence detection Methods 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- JRJJUHQRZYVQEX-UHFFFAOYSA-N 5-bromo-2-(5-bromo-4-butyl-1,3-thiazol-2-yl)-4-butyl-1,3-thiazole Chemical compound S1C(Br)=C(CCCC)N=C1C1=NC(CCCC)=C(Br)S1 JRJJUHQRZYVQEX-UHFFFAOYSA-N 0.000 description 1
- 101100136092 Drosophila melanogaster peng gene Proteins 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 125000006615 aromatic heterocyclic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 125000001246 bromo group Chemical group Br* 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 210000000805 cytoplasm Anatomy 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000004064 dysfunction Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 210000003743 erythrocyte Anatomy 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 239000007850 fluorescent dye Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- SFTOAWQJLAEXND-UHFFFAOYSA-N iridium(3+);2-phenylpyridine Chemical compound [Ir+3].C1=CC=CC=C1C1=CC=CC=N1.C1=CC=CC=C1C1=CC=CC=N1 SFTOAWQJLAEXND-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000010297 mechanical methods and process Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011897 real-time detection Methods 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 230000019491 signal transduction Effects 0.000 description 1
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
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N11/00—Investigating flow properties of materials, e.g. viscosity, plasticity; Analysing materials by determining flow properties
-
- 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
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
-
- 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
- G01N21/6447—Fluorescence; Phosphorescence by visual observation
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
-
- 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
- C09K2211/10—Non-macromolecular compounds
- C09K2211/1018—Heterocyclic compounds
- C09K2211/1025—Heterocyclic compounds characterised by ligands
- C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
- C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
-
- 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)
- Health & Medical Sciences (AREA)
- Immunology (AREA)
- Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Pathology (AREA)
- Organic Chemistry (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Optics & Photonics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The invention provides a dithiazole type metal iridium complex and a preparation method thereof, and provides application of the iridium complex in detection of solution viscosity, wherein the main structure of the iridium complex is bis (2-phenylpyridine) (4, 4 '-dibutyl-2, 2' -dithiazole) hexafluorophosphate without substituent groups, and R is one of hydrogen and bromine. The preparation method of the bithiazole metal iridium complex is simple, the compound presents weak fluorescence in a low-viscosity solvent, and presents strong fluorescence in a system with larger viscosity, so that the quick visual detection of the viscosity in a solution system can be realized, the compound can identify the viscosity with high selectivity, and a new development direction is provided for the synthesis of a novel viscosity probe.
Description
Technical field:
the invention belongs to the technical field of metal iridium complexes, and particularly relates to a bithiazole type metal iridium complex, a preparation method and application thereof.
The background technology is as follows:
viscosity plays an important role in many diffusion-mediated biological processes, including interactions between biological macromolecules, pharmacokinetics, signal transduction, electron transport, and metabolite diffusion. Abnormal changes in intracellular viscosity are closely related to diseases and dysfunctions, such as higher viscosity of platelet membranes and erythrocytes in diabetics. The literature reports that the viscosity of normal cytoplasm is about 1-2cP, whereas the viscosity in diseased cells can be significantly increased, up to 140cP and even higher. Therefore, it is of great importance to perform qualitative and quantitative determination of intracellular viscosity.
The traditional methods for viscosity detection include a capillary viscometer, a falling ball viscometer and a rotary viscometer, and the mechanical methods are complex in operation, low in working efficiency and cannot be used for measuring the intracellular viscosity. In recent years, the fluorescent probe has been widely researched and applied because of the advantages of high sensitivity, good biocompatibility, capability of realizing real-time detection and the like, so that the development of a simple and sensitive fluorescent sensing material has great significance for qualitative and quantitative detection of the environment and even the viscosity in cells. Based on the above, the invention provides a bithiazole type iridium complex, a preparation method and application thereof to solve the problems.
The invention comprises the following steps:
the first object of the invention is to provide a metal iridium complex with a thiazole structure, which is specifically two structures, aiming at the defects of the prior art;
the second object of the invention is to provide a preparation method of a dithiazole type metal iridium complex;
the third object of the invention is to provide the application of the bithiazole metal iridium complex in viscosity detection.
The invention adopts the following technical scheme:
the bithiazole type metal iridium complex has a molecular structure shown as the following formula:
wherein the main structure is bis (2-phenylpyridine) (4, 4 '-dibutyl-2, 2' -bithiazole) iridium (III) hexafluorophosphate without substituent groups, and R is hydrogen or bromine.
Further, in the molecular structural formula of the bithiazole type metal iridium complex, R is hydrogen, and the iridium complex is bis (2-phenylpyridine) hexafluorophosphate (5, 5' -dihydro-4, 4' -dibutyl-2, 2' -bithiazole) iridium (III) and has a structure of a formula I-A.
Further, in the molecular structural formula of the bithiazole type metal iridium complex, R is bromine, and the iridium complex is bis (2-phenylpyridine) hexafluorophosphate (5, 5' -dibromo-4, 4' -dibutyl-2, 2' -bithiazole) iridium (III) and has a structure of a formula I-B.
The invention also provides a preparation method of the bithiazole metal iridium complex, which comprises the following steps:
s1, adding a chlorine bridge dimer [ Ir (ppy) into a reaction vessel under the protection of argon atmosphere 2 Cl] 2 5,5' -di R-4,4 '-dibutyl-2, 2' -dithiazole and dehydrated glycol react at a certain temperature, and after the reaction is finished, the mixture is cooled to room temperature;
wherein the chloro-bridged dimer [ Ir (ppy) 2 Cl] 2 Reference a;
reference B is made to the preparation of 5,5' -di-R-4, 4' -dibutyl-2, 2' -bithiazole.
Reference a: suin Jo, Y.S. chok. Yellow light-emitting electrochemical cells utilizing iridium (III) phenanthroimidazole complexes [ J ]. Molecular Crystals and Liquid Crystals,2017,654 (1): 221-233;
reference B: tao T, peng Y X, huang W, et al Coplanar Bithiazole-Centered Heterocyclic Aromatic Fluorescent Compounds Having Different Donor/Acceptor Terminal Groups [ J ]. Journal of Organic Chemistry,2013,78 (6): 2472-2481;
s2, dropwise adding NH into the S1 reaction system while stirring 4 PF 6 The water solution has yellow solid precipitated, is filtered after stirring, is washed by water, and takes out a filter cake;
s3, separating the filter cake obtained in the S2 by gel column chromatography to obtain pure solid, namely the bithiazole metal iridium complex
Further, in S1, a chlorine bridge dimer [ Ir (ppy) is added 2 Cl] 2 And 5,5' -di R-4,4' -dibutyl-2, 2' -bithiazole in an amount of 1 (2-4).
In S1, the reaction temperature is 140-190 ℃ and the reaction time is 16-24 hours.
Further, in S2, NH 4 PF 6 In aqueous solution, NH 4 PF 6 The concentration is 0.1mol/L, and the stirring time is 2-3 hours.
Further, in 5,5' -di R-4,4' -dibutyl-2, 2' -bithiazole, R is hydrogen or bromine.
The invention also provides application of the bithiazole type metal iridium complex in viscosity detection.
The invention has the beneficial effects that:
the invention provides two kinds of bithiazole type metal iridium complexes and a preparation method thereof, and provides application of the iridium complexes in the aspect of solution viscosity detection. The preparation method of the dithiazole type metal iridium complex is simple, the compound presents weak fluorescence in a low-viscosity solvent, and presents strong fluorescence in a system with larger viscosity, so that the quick visual detection of the viscosity in a solution system can be realized. In the ethanol-glycerol system, as the solution viscosity increases from 1.36cP to 669cP, the fluorescence probe intensity also gradually increases, and the fluorescence intensity has good linear relation with the environment viscosity, so that the fluorescence probe can be used for quantitatively detecting the environment viscosity. Moreover, the compound can identify the viscosity with high selectivity, and provides a new development direction for the synthesis of novel viscosity probes in the future.
Description of the drawings:
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of bis (2-phenylpyridine) (5, 5' -dihydro-4, 4' -dibutyl-2, 2' -bithiazole) iridium (III) hexafluorophosphate prepared in example 1 of the present invention;
FIG. 2 is a graph showing fluorescence emission spectra of bis (2-phenylpyridine) (5, 5' -dihydro-4, 4' -dibutyl-2, 2' -bithiazole) iridium (III) hexafluorophosphate prepared in example 1 of the present invention in ethanol-glycerol mixed solutions of different viscosities;
FIG. 3 shows the logarithmic value (Log I) of fluorescence intensity at a wavelength of 620nm of bis (2-phenylpyridine) (5, 5' -dihydro-4, 4' -dibutyl-2, 2' -bisthiazole) iridium (III) hexafluorophosphate produced in example 1 of the present invention 620 nm) and viscosity (Log eta);
FIG. 4 is a graph showing the selectivity of iridium (III) bis (2-phenylpyridine) (5, 5' -dihydro-4, 4' -dibutyl-2, 2' -bisthiazole) hexafluorophosphate produced in example 1 of the present invention.
The specific embodiment is as follows:
for the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
5,5' -dihydro-4, 4' -dibutyl-2, 2' -dithiazole (0.05 g,0.18 mmol) and chlorobridging dimer [ Ir (ppy) were weighed out 2 Cl] 2 (0.10 g,0.09 mmol) and ethylene glycol (8 mL) were added to a single neck round bottom flask, protected with an argon bulb, heated to 150℃and allowed to react for 16 hours, wherein the preparation of 5,5' -dihydro-4, 4' -dibutyl-2, 2' -dithiazole was described in reference B. After the completion of the reaction, the reaction mixture was cooled to room temperature, and NH was added dropwise to the reaction system at a concentration of 0.1mol/L while stirring 4 PF 6 The aqueous solution, which has yellow solid precipitated, is stirred for 2-3 hours, then is filtered, washed, the filter cake is taken out, gel column chromatography is used for purification, dichloromethane is used as a leaching agent, and the red solid is obtained with the yield of 94 percent. The nuclear magnetic spectrum is shown in figure 1, 1 H NMR(400MHz,CDCl 3 ):δ7.91(d,2H,pyridine),7.81(t,2H,pyridine),7.61(dd,4H,benzene),7.30(s,2H,thiazole),7.16(t,2H,pyridine),6.95(t,2H,benzene),6.79(t,2H,pyridine),6.08(d,2H,benzene)。
from the above data, it can be seen that bis (2-phenylpyridine) (5, 5' -dihydro-4, 4' -dibutyl-2, 2' -bithiazole) hexafluorophosphate iridium (III) has the structure of formula I-A:
example 2
5,5' -dibromo-4, 4' -dibutyl-2, 2' -bithiazole (0.05 g,0.10 mmol) was weighed out, and a chlorobridge dimer [ Ir (ppy) 2 Cl] 2 (0.05 g,0.05 mmol) ethylene glycol (10 mL) was added to a single neck round bottom flask, protected with an argon bulb, heated to 150℃and allowed to react for 16 hours, wherein the preparation of 5,5' -dibromo-4, 4' -dibutyl-2, 2' -bisthiazole was described in reference B. After the completion of the reaction, the reaction mixture was cooled to room temperature, and NH was added dropwise to the reaction system at a concentration of 0.1mol/L while stirring 4 PF 6 The water solution has yellow solid precipitated, and is stirred for 2-3 hours, filtered and waterWashing, taking a filter cake, purifying by using gel column chromatography, and taking dichloromethane as a leaching agent to obtain red solid with the yield of 77%. 1 H NMR(400MHz,CDCl 3 ):δ7.91(d,2H,pyridine),7.81(t,2H,pyridine),7.61(dd,4H,benzene),7.16(t,2H,pyridine),6.95(t,2H,benzene),6.79(t,2H,pyridine),6.08(d,2H,benzene)。
From the above data, bis (2-phenylpyridine) hexafluorophosphate (5, 5' -dibromo-4, 4' -dibutyl-2, 2' -bithiazole) iridium (III) has the structure of formula I-B:
test example 1
A solution of the compound obtained in example 1 in Dimethylformamide (DMF) was prepared at a concentration of 0.1mM and used as a mother liquor.
10 sample bottles containing 1.00mL of mother liquor were aligned, 9.00mL of solutions of different viscosities (volume ratios of absolute ethanol to glycerol 10:0, 9:1, 8:2, 7:3, 6:4, 5:5, 4:6, 3:7, 2:8, 1:9) were pipetted into 10 bottles, respectively, shaken well, sonicated for 1 minute, compound final concentration 10. Mu.M, and fluorescence detection (lambda.) ex =400 nm), the fluorescence intensity in each system was scanned, as shown in fig. 2; log eta (eta is the viscosity value) is taken as the abscissa, log I 620 A standard curve of fluorescence intensity versus viscosity at 620nm was established on the ordinate, as shown in FIG. 3.
As can be seen from FIG. 2, the fluorescence intensity at 620nm gradually increases with increasing viscosity (in FIG. 2, the fluorescence intensity curves of 0%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% of glycerol content are shown in order from bottom to top). As can be seen from fig. 3, there is a good linear relationship between fluorescence intensity and viscosity, and the linear equation is y=1.99+0.33 x; the compound is demonstrated to be capable of quantitative detection of viscosity changes for solutions having viscosity values in the range of 1.36-49.6 cP.
The iridium complex prepared in example 2 was subjected to a viscosity test in accordance with the method of example 1,
the results show that the iridium complex prepared in example 2 gradually increases in fluorescence intensity at 635nm with increasing viscosity, and the fluorescence intensity has a good linear relationship with viscosity, and the linear equation is y=2.13+0.31 x; the compound is demonstrated to be capable of quantitative detection of viscosity changes for solutions having viscosity values in the range of 1.36-49.6 cP.
Therefore, the two bithiazole metal iridium complexes provided by the invention can be used for quantitatively detecting the viscosity of the environment.
Test example 2
A DMF solution of the compound obtained in example 1 was prepared at a concentration of 0.1mM and used as a test mother liquor.
7 parts of 1mL of mother solution was prepared, and then 9mL of 1mM active molecule (Cu 2+ 、Na + 、HSO 3 - 、H 2 O 2 GSH, gly), and glycerol was added in another portion to give a final concentration of 10 μm, followed by fluorescence detection (λex=400 nm). The fluorescence intensity is plotted on the abscissa with wavelength and on the ordinate with the corresponding active molecule on the abscissa and on the ordinate with the fluorescence intensity at 620nm on the ordinate with 4b. As can be seen from FIG. 4, the probe acted on other active molecules, the fluorescence intensity was not substantially enhanced, but the fluorescence intensity was significantly enhanced in glycerol, indicating that the compound was able to specifically respond to viscosity.
According to the method of example 1, the iridium complex prepared in example 2 is tested for specific response viscosity, and the result shows that the iridium complex has no effect on other active molecules, but the fluorescence intensity in glycerol is obviously enhanced, so that the two dithiazole type metal iridium complexes provided by the invention can have specific response viscosity.
The foregoing is merely a preferred embodiment of the present invention, and the scope of the present invention is not limited to the above embodiments, but all technical solutions falling under the concept of the present invention fall within the scope of the present invention, and it should be noted that, for those skilled in the art, several modifications and adaptations without departing from the principles of the present invention should and are intended to be regarded as the scope of the present invention.
Claims (5)
1. The application of the bithiazole type iridium (III) complex in viscosity detection is characterized in that the bithiazole type iridium (III) complex has a molecular structure shown in the following formula:
;
wherein R is hydrogen or bromine.
2. The use of the bithiazole-type iridium (III) complex according to claim 1 in viscosity detection, wherein the preparation method of the bithiazole-type iridium (III) complex comprises the following steps:
s1, adding a chlorine bridge dimer [ Ir (ppy) into a reaction vessel under the protection of argon atmosphere 2 Cl] 2 Reacting 5,5' -di R-4,4' -dibutyl-2, 2' -dithiazole with dehydrated ethylene glycol at a certain temperature, and cooling to room temperature after the reaction is finished; in the 5,5' -di R-4,4' -dibutyl-2, 2' -bithiazole, R is hydrogen or bromine;
s2, dropwise adding NH into the S1 reaction system while stirring 4 PF 6 The water solution has yellow solid precipitated, is filtered after stirring, is washed by water, and takes out a filter cake;
s3, separating the filter cake obtained in the step S2 by gel column chromatography to obtain a pure solid, namely the bithiazole type metal iridium (III) complex.
3. Use of the bithiazole iridium (III) complex as claimed in claim 2 for viscosity measurement, wherein in S1, a chlorobridge dimer [ Ir (ppy) is added 2 Cl] 2 The mass ratio of the 5,5' -di R-4,4' -dibutyl-2, 2' -dithiazole is 1 (2-4).
4. The use of the bithiazole iridium (III) complex as claimed in claim 2 in viscosity detection, wherein in S1, the reaction temperature is 140-190 ℃ and the reaction time is 16-24 hours.
5. Use of the bithiazole iridium (III) complex as claimed in claim 2 for viscosity detection, wherein in S2, NH 4 PF 6 In aqueous solution, NH 4 PF 6 The concentration is 0.1mol/L, and the stirring time is 2-3 hours.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110738940.0A CN113603725B (en) | 2021-06-30 | 2021-06-30 | Bithiazole type metal iridium complex, preparation method and application thereof |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110738940.0A CN113603725B (en) | 2021-06-30 | 2021-06-30 | Bithiazole type metal iridium complex, preparation method and application thereof |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113603725A CN113603725A (en) | 2021-11-05 |
CN113603725B true CN113603725B (en) | 2023-07-21 |
Family
ID=78337055
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110738940.0A Active CN113603725B (en) | 2021-06-30 | 2021-06-30 | Bithiazole type metal iridium complex, preparation method and application thereof |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113603725B (en) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005042106A (en) * | 2003-07-08 | 2005-02-17 | Univ Nihon | Process for preparation of aromatic-iridium complex phospholuminescent material, aromatic-iridium complex photoluminescent material and aromatic-iridium complex luminescent element |
JP2007070290A (en) * | 2005-09-07 | 2007-03-22 | Tama Tlo Kk | Method for producing ortho-metalated iridium complex, iodine-crosslinked iridium dimer complex and method for producing the same |
JP2009108041A (en) * | 2007-10-10 | 2009-05-21 | National Institute Of Advanced Industrial & Technology | Iridium complex and method for producing the same |
CN101787054A (en) * | 2010-03-23 | 2010-07-28 | 上海师范大学 | Water-soluble cationic iridium complex phosphorescence probe and preparation method |
CN111205335A (en) * | 2020-03-04 | 2020-05-29 | 兰州大学 | Iridium complex and preparation method and application thereof |
-
2021
- 2021-06-30 CN CN202110738940.0A patent/CN113603725B/en active Active
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2005042106A (en) * | 2003-07-08 | 2005-02-17 | Univ Nihon | Process for preparation of aromatic-iridium complex phospholuminescent material, aromatic-iridium complex photoluminescent material and aromatic-iridium complex luminescent element |
JP2007070290A (en) * | 2005-09-07 | 2007-03-22 | Tama Tlo Kk | Method for producing ortho-metalated iridium complex, iodine-crosslinked iridium dimer complex and method for producing the same |
JP2009108041A (en) * | 2007-10-10 | 2009-05-21 | National Institute Of Advanced Industrial & Technology | Iridium complex and method for producing the same |
CN101787054A (en) * | 2010-03-23 | 2010-07-28 | 上海师范大学 | Water-soluble cationic iridium complex phosphorescence probe and preparation method |
CN111205335A (en) * | 2020-03-04 | 2020-05-29 | 兰州大学 | Iridium complex and preparation method and application thereof |
Non-Patent Citations (9)
Title |
---|
Cationic IrIII Emitters with Near-Infrared Emission Beyond 800 nm and Their Use in Light-Emitting Electrochemical Cells;Guan-Yu Chen等;《Chem. Eur. J.》;第5489-5497页 * |
Coplanar Bithiazole-Centered Heterocyclic Aromatic Fluorescent Compounds Having Different Donor/Acceptor Terminal Groups;Tao Tao等;《J. Org. Chem.》;第2472-2481页 * |
Cyclometalated iridium(III) complexes containing bithiazole ligands for preferable viscosity detection;Jianrong Yin等;《Dyes and Pigments》;第1-10页 * |
Highly Stable Red-Light-Emitting Electrochemical Cells;Cathrin D. Ertl等;《J. Am. Chem. Soc.》;第3237-3248页 * |
Simple design to achieve red-to-near-infrared emissive cationic Ir(III) emitters and their use in light emitting electrochemical cells;Amlan K. Pal等;《RSC Adv》;第31833-31837页 * |
Synthesis, Characterization, and Optoelectronic Properties of Iridium Complexes Bearing Nonconjugated Six-Membered Chelating Ligands;Claus Hierlinger等;《Inorg. Chem.》;第2023-2034页 * |
Tuning the Spectroscopic, Electrochemical, and Single-Crystal Conductance Properties of a Series of Rhenium-Containing Bithiazoles with Different Donor/Acceptor Hybrids;Tao Tao等;《Organometallics》;第5120-5128页 * |
Yellow light-emitting electrochemical cells utilizing iridium(III) phenanthroimidazole complexes;Suin Jo等;《Molecular Crystals and Liquid Crystals》;第221-233页 * |
基于粘度响应的线粒体靶向铱配合物用于肿瘤的光动力治疗;欧阳艾等;《无机化学学报》;第37卷(第3期);第401-411页 * |
Also Published As
Publication number | Publication date |
---|---|
CN113603725A (en) | 2021-11-05 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US8962339B2 (en) | Fluorescent probe compounds, preparation method and application thereof | |
CN107721922B (en) | Quinoline biological thiol fluorescent probe and preparation and application thereof | |
CN108383823B (en) | Naphthopyran carbazone derivatives, and preparation method and application thereof | |
CN111205220B (en) | Fluorescent probe and preparation method and application thereof | |
CN110172070B (en) | Fluorescent probe for detecting viscosity and hydrogen peroxide as well as synthesis method and application thereof | |
CN108088828A (en) | A kind of twin columns aromatic hydrocarbons mercury ion fluorescent sensor and its preparation and application | |
CN103242327A (en) | P-N-methyl cyclopentaldehyde rhodamine 6G pH fluorescence molecular probe as well as preparation method and use thereof | |
CN107382977B (en) | Pyrazinepyrazole acylhydrazone derivative-based fluorescent probe and preparation method and application thereof | |
CN113603725B (en) | Bithiazole type metal iridium complex, preparation method and application thereof | |
Peng et al. | Colorimetric and fluorescent dual-signals probes for naked-eye detection of hydrogen peroxide and applications in milk samples and in vivo | |
CN113979890B (en) | Schiff base ligand and preparation method and application of polynuclear rare earth complex thereof | |
CN113201132B (en) | Rhodamine B derivative fluorescent probe molecule based on monodisperse four-arm polyethylene glycol and preparation method thereof | |
CN113402470B (en) | Multichannel reversible colorimetric mercury ion fluorescent probe, preparation method and application | |
CN115181068A (en) | TPI derivative fluorescent probe and application thereof in preparation of copper ion detection reagent | |
CN111233885B (en) | Fluorescent probe for detecting methanol and application thereof | |
CN109400616B (en) | Sulfur dioxide derivative fluorescent probe and preparation method and application thereof | |
CN114957180A (en) | Fluorescent probe for identifying pH value based on dual-excitation-wavelength fluorescence analysis method and preparation method and application thereof | |
CN114853743B (en) | Cytosine-based cyanine probe and preparation method and application thereof | |
CN116656147B (en) | Dye capable of quenching blood background fluorescence, hydrogen sulfide probe, preparation method and application thereof | |
CN114874111B (en) | Near infrared fluorescent probe for detecting temperature and preparation method and application thereof | |
CN114163423B (en) | Glutathione ratio reversible fluorescent probe capable of realizing cancer cell screening, preparation method and application | |
CN110938051B (en) | Probe for efficiently detecting mercury ions, preparation method and application | |
CN113121566B (en) | Pyrene derivative fluorescent molecule and preparation method and application thereof | |
CN118406055A (en) | Compound DNNP, preparation method thereof and application thereof in detection of hydrogen sulfide | |
CN118084696A (en) | Fluorescent probe, synthesis method and application thereof in detection of hydroxyl-containing solvent |
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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant |