CN113980058B - Phenanthroline derivative-based binuclear iridium complex and preparation method and application thereof - Google Patents
Phenanthroline derivative-based binuclear iridium complex and preparation method and application thereof Download PDFInfo
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- 229910052741 iridium Inorganic materials 0.000 title claims abstract description 59
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 title claims abstract description 59
- NSMJMUQZRGZMQC-UHFFFAOYSA-N 2-naphthalen-1-yl-1H-imidazo[4,5-f][1,10]phenanthroline Chemical compound C12=CC=CN=C2C2=NC=CC=C2C2=C1NC(C=1C3=CC=CC=C3C=CC=1)=N2 NSMJMUQZRGZMQC-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 238000010668 complexation reaction Methods 0.000 title abstract description 4
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- 239000010949 copper Substances 0.000 claims description 68
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
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- 239000012085 test solution Substances 0.000 claims description 19
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- 238000000034 method Methods 0.000 claims description 16
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
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- 125000002091 cationic group Chemical group 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- QTIRZJMYAMMABQ-UHFFFAOYSA-N 2-[5-(1H-imidazo[4,5-f][1,10]phenanthrolin-2-yl)furan-2-yl]-1H-imidazo[4,5-f][1,10]phenanthroline Chemical compound N1C(=NC2=C3C=CC=NC3=C3N=CC=CC3=C21)C=1OC(=CC=1)C=1NC=2C(=C3C=CC=NC3=C3N=CC=CC=23)N=1 QTIRZJMYAMMABQ-UHFFFAOYSA-N 0.000 claims description 3
- SAUBNVRLVSOBJJ-UHFFFAOYSA-N 2-[5-(1h-imidazo[4,5-f][1,10]phenanthrolin-2-yl)thiophen-2-yl]-1h-imidazo[4,5-f][1,10]phenanthroline Chemical compound C12=CC=CN=C2C2=NC=CC=C2C2=C1NC(C1=CC=C(S1)C=1NC3=C(C4=CC=CN=C4C4=NC=CC=C43)N=1)=N2 SAUBNVRLVSOBJJ-UHFFFAOYSA-N 0.000 claims description 3
- IZHCSFYIHXPFQQ-UHFFFAOYSA-N 2-(2,4-difluorophenyl)pyridine Chemical compound FC1=CC(F)=CC=C1C1=CC=C=C[N]1 IZHCSFYIHXPFQQ-UHFFFAOYSA-N 0.000 claims 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 18
- 238000000862 absorption spectrum Methods 0.000 abstract description 14
- SSABEFIRGJISFH-UHFFFAOYSA-N 2-(2,4-difluorophenyl)pyridine Chemical compound FC1=CC(F)=CC=C1C1=CC=CC=N1 SSABEFIRGJISFH-UHFFFAOYSA-N 0.000 abstract description 13
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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 System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System compounds of the platinum group
- C07F15/0033—Iridium compounds
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- 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
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
-
- 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"
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- 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
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- 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
- G01N21/75—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated
- G01N21/77—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator
- G01N21/78—Systems in which material is subjected to a chemical reaction, the progress or the result of the reaction being investigated by observing the effect on a chemical indicator producing a change of colour
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- 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
-
- 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"
- G01N2021/6432—Quenching
Abstract
The invention relates to a phenanthroline derivative-based binuclear iridium complex and a preparation method and application thereof. The binuclear iridium complex takes 2- (2, 4-difluorophenyl) pyridine as a main ligand and respectively takes 2, 5-bis (1H-imidazo [4, 5-f)][1,10]Phenanthroline-2-yl) furan or 2, 5-bis (1H-imidazo [4, 5-f)][1,10]Phenanthroline-2-yl) thiophene is used as a neutral ligand, and hexafluorophosphate is used as a counter ion. The neutral ligand in the binuclear iridium complex contains uncoordinated nitrogen, oxygen or sulfur atoms, and the neutral ligand is coordinated with Cu through the vacant coordination points 2+ To realize complexation to Cu 2+ The selective recognition of (2) has higher sensitivity. Mixing Cu 2+ When the binuclear iridium complex is added into an acetonitrile solution, the mixed solution is observed to turn from yellow to green by naked eyes, intensity quenching at an emission peak can be seen in an emission spectrum, and the absorbance at 294nm of an ultraviolet-visible absorption spectrum is increased.
Description
Technical Field
The invention relates to the field of stoichiometric agents, in particular to synthesis and application of a binuclear iridium complex of a phenanthroline derivative containing an empty coordination site.
Background
Copper is a metal element, the simple substance is purple red, and the +2 valence is the most common valence state, and can form a salt with most common anions. Cu 2+ Is an indispensable micronutrient for maintaining human health, has important influence on the development and normal functions of blood, central nervous and immune systems, hair, skin and skeletal tissues, brain, liver, heart and the like, and plays an important role in many biological processes. However, excessive copper concentration in the human body can cause certain diseases, such as Alzheimer disease, wilson disease and the like, and also can cause pathological changes, such as degeneration of nervous system, progressive degeneration of memory function and cognitive function, liver damage, damage of central nervous system and the like. Meanwhile, since copper has wide application in industrial and agricultural production, cu discharged to the environment 2+ Also increased year by year, cu 2+ The accumulation in soil and crops can cause poor growth of the crops, pollute grain seeds and finally cause Cu 2+ The excessive enrichment in human body poses threat to human health. Therefore, the effective detection of copper ions is of great significance to life science and environmental science.
Detecting Cu 2+ Such as inductively coupled plasma mass spectrometry, atomic emission spectrometry and atomic absorption spectrometry have been widely used. However, these methods all require complex and precise instruments and require cumbersome and time-consuming pre-processing operations to complete the analysis process, and are therefore not suitable for in-situ and rapid detection of Cu 2+ . Optical analysis methods are widely concerned by people because of their simple operation, rapid reaction, high sensitivity and selectivity. The current phosphorescence chemical sensor based on iridium complex has relatively long service life (capable of eliminating fluorescence background) and larger Stokes shift (convenient for separating excitation and emission) due to the excellent photophysical characteristics (such as sensitivity of emission characteristics to local environmental change), and is convenient for removing fluorescence background) The advantages are of great interest, and the used phosphorescence chemical sensing and ultraviolet-visible absorption sensing methods are considered as the most effective tools in sensing applications due to high sensitivity, easy visualization and short detection response time. Compared with the mononuclear iridium complex, the binuclear iridium complex has richer excited states, the luminous efficiency can be regulated and controlled through the design of a bridging ligand, and the binuclear iridium complex is less applied in the field of optical sensing at present and has larger development space.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a phenanthroline derivative-based binuclear iridium complex and a preparation method and application thereof. The binuclear iridium complex takes 2- (2, 4-difluorophenyl) pyridine as a main ligand and respectively takes 2, 5-bis (1H-imidazo [4, 5-f)][1,10]Phenanthroline-2-yl) furan and 2, 5-bis (1H-imidazo [4, 5-f)][1,10]Phenanthroline-2-yl) thiophene is used as a neutral ligand, and hexafluorophosphate is used as a counter ion. The phenanthroline derivative in the binuclear iridium complex contains uncoordinated nitrogen, oxygen or sulfur atoms, and the coordination sites of the phenanthroline derivative and the Cu atoms are vacant 2+ To realize the complexation of Cu 2+ Has high sensitivity. Will contain Cu 2+ The solution is added into an acetonitrile solution of the binuclear iridium complex, the mixed solution is observed to be changed from yellow to green by naked eyes, the intensity quenching at an emission peak can be seen in an emission spectrum, the absorbance at 294nm of an ultraviolet-visible absorption spectrum is increased, and other metal ions do not interfere the detection process.
The technical scheme of the invention is as follows:
a phenanthroline derivative-based binuclear iridium complex is composed of two substances with the following structural formula:
the preparation method of the binuclear iridium complex based on the phenanthroline derivative comprises the following steps:
bis { di [2- (2, 4-difluorophenyl) pyridine under anhydrous and oxygen-free operating conditions]Iridium dichloride } withRefluxing neutral ligand in mixed solvent at 45-80 deg.c for 6-12 hr, and adding KPF into the system 6 Then stirring for 1-2 h at room temperature to obtain the cationic type binuclear iridium complex;
wherein the molar ratio is bis { di [2- (2, 4-difluorophenyl) pyridine]Iridium dichloride } neutral ligand KPF 6 ＝1:1.1～1.5:2.5～10.0；
The neutral ligand is 2, 5-bis (1H-imidazo [4,5-f ] [1,10] phenanthroline-2-yl) furan or 2, 5-bis (1H-imidazo [4,5-f ] [1,10] phenanthroline-2-yl) thiophene;
the mixed solvent is dichloromethane and methanol, and the volume ratio of the dichloromethane to the methanol is 1; 30 to 100 ml of mixed solvent is added to every millimole of bis { di [2- (2, 4-difluorophenyl) pyridine ] iridium dichloride }.
The application of the binuclear iridium complex based on the phenanthroline derivative is used for identifying Cu in a solution 2+ 。
The method specifically comprises the following steps:
the first method comprises the following steps:
adding a to-be-detected water solution into an acetonitrile solution of the binuclear iridium complex to obtain a mixed test solution; when the binuclear iridium complex is observed to be changed from original yellow to green by naked eyes, the situation that the aqueous solution to be detected contains Cu is indicated 2+ ；
Wherein, the concentration of the binuclear iridium complex in the mixed test solution is 1.0 multiplied by 10 -6 mol/L～5.0×10 -2 mol/L, cu in the mixed test solution 2+ The content range of the ions was 1.0X 10 -7 mol/L～5.0mol/L；
When the binuclear iridium complex is observed to be changed from yellow to green by naked eyes, the preferred judgment molar ratio is that the binuclear iridium complex: cu 2+ Ion =0.1 to 10;
or the second method comprises the following steps:
adding a to-be-tested aqueous solution into an acetonitrile solution of the binuclear iridium complex to obtain a mixed test solution; measuring the change of emission intensity of the mixed solution at the maximum emission peak by using a fluorescence spectrometer, and when the quenching amount of the emission intensity exceeds 10 percent, indicating that the water solution to be measured is dissolved in waterThe liquid contains Cu 2+ ；
Wherein, the concentration of the binuclear iridium complex in the mixed test solution is 1.0 multiplied by 10 -6 mol/L～5.0×10 -2 mol/L, cu in the mixed test solution 2+ The content range of the ions was 1.0X 10 -7 mol/L～5.0mol/L；
When the quenching amount of the emission intensity at the maximum emission peak exceeds 10%, it is preferable to determine the molar ratio as, the binuclear iridium complex: cu (copper) 2+ Ion =0.1 to 10;
or a third method, comprising the steps of:
adding a to-be-detected water solution into an acetonitrile solution of the binuclear iridium complex to obtain a mixed test solution; measuring the change of the absorption intensity of the mixed solution at 294nm by using an ultraviolet-visible absorption spectrophotometer, and when the increase of the absorbance value exceeds 10 percent, indicating that the aqueous solution to be measured contains Cu 2+ 。
Wherein, the concentration of the binuclear iridium complex in the mixed test solution is 1.0 multiplied by 10 -6 mol/L～5.0×10 -2 mol/L, cu in the mixed test solution 2+ The content range of the ions was 1.0X 10 -7 mol/L～5.0mol/L；
When the increase in the absorption intensity value at 294nm exceeds 10%, it is preferable to judge the molar ratio as, the binuclear iridium complex: cu 2+ Ion =0.1 to 10;
the aqueous solution to be measured contains Ag + ,Ca 2+ ,Cd 2+ ,Co 2+ ,Cr 3+ ,Fe 2+ ,Fe 3+ ,Hg 2+ ,K + ,Mg 2+ ,Na + ,Ni 2+ ,Pb 2+ ,Zn 2+ ,Cu 2+ One or more ions of (a).
The invention has the substantive characteristics that:
different from a mononuclear iridium complex which is widely researched, the binuclear ionic iridium complex disclosed by the invention is a binuclear ionic iridium complex which structurally contains two metal centers, and a neutral ligand for forming the complex contains two phenanthroline structural units and simultaneously contains nitrogen, oxygen or sulfur atoms with vacant coordination sites. The coordination sites of the complexes can be empty to Cu 2+ Selection of (2)And (5) sex identification.
The feeding ratio of bis { di [2- (2, 4-difluorophenyl) pyridine ] iridium dichloride } and a neutral ligand 2, 5-bis (1H-imidazo [4,5-f ] [1,10] phenanthroline-2-yl) furan or 2, 5-bis (1H-imidazo [4,5-f ] [1,10] phenanthroline-2-yl) thiophene in the preparation method is the key for preparing the binuclear iridium complex.
The invention has the beneficial effects that:
(1) The neutral ligand in the invention is a phenanthroline derivative, is a polydentate ligand, can form a dinuclear complex with metal iridium, and simultaneously maintains uncoordinated nitrogen, oxygen and sulfur atoms. Binuclear iridium complex is coordinated with Cu through empty coordination point 2+ Interaction of, to Cu 2+ And selective identification with short response time, high sensitivity, low detection limit and good reversibility is realized. In addition, the synthesis steps of the two complexes are simple, the luminous efficiency is high, and the detection sensitivity is effectively improved.
(2) The two ionic binuclear iridium complexes can realize the detection of Cu by different detection means 2+ When Cu is added into the acetonitrile solution of the complex 2+ When the binuclear iridium complex is used in an aqueous solution, the reduction value of the emission intensity of the binuclear iridium complex at the maximum emission peak is 10 to 98 percent; the absorbance value of the complex at 294nm is increased by 1.1-3.0 times, and meanwhile, the color of the mixed solution is changed from yellow to green, so that the visual detection is realized. For Cu 2+ The high sensitivity and selectivity detection of the two ionic binuclear iridium complexes show that the two ionic binuclear iridium complexes have application values in the fields of phosphorescence chemical sensing and ultraviolet absorption sensing respectively.
Drawings
FIG. 1 shows the UV-visible absorption spectra of complexes Ir1 and Ir2 in acetonitrile solution;
FIG. 2 the emission spectra of complexes Ir1 and Ir2 in acetonitrile solution;
FIG. 3 Complex Ir1 vs. Cu 2+ A change in the phosphorescence spectrum of the response;
FIG. 4 is a graph of the selectivity test results of the response of the complex Ir1 to several common metal ions;
FIG. 5 Complex Ir1 vs. Cu 2+ Graph of results of competitive tests with common metal ions;
FIG. 6 Complex Ir2 vs. Cu 2+ A responsive uv-vis absorption spectral change;
FIG. 7 is a graph of the results of selectivity tests of the response of complex Ir2 to several common metal ions;
FIG. 8 Complex Ir2 vs. Cu 2+ Graph of results of competitive tests with common metal ions.
Detailed Description
The invention is further illustrated by the following specific embodiments, which are not intended to be limiting of the invention.
The complexes of the invention can be synthesized by the following route:
example 1:
preparation of main ligand 2- (2, 4-difluorophenyl) pyridine: under the protection of nitrogen, 15mmol 2, 4-difluorophenylboronic acid, 10mmol 2-bromopyridine and 40mmol anhydrous Na 2 CO 3 And 0.15mmol of tetrakis (triphenylphosphine) palladium were dissolved in a mixed solution of tetrahydrofuran and water, and reacted at 90 ℃ for 24 hours. Cooling to room temperature, desolventizing, extracting with dichloromethane/water, anhydrous Na 2 SO 4 Drying and column chromatography purification are carried out, and the eluent is petroleum ether, ethyl acetate =5 and the ratio of 2- (2, 4-difluorophenyl) pyridine to white solid is as follows.
Example 2:
bis { di [2- (2, 4-difluorophenyl) pyridine]Preparation of synthetic iridium dichloride }: under the protection of nitrogen, 4.4mmol 2- (2, 4-difluorophenyl) pyridine and 2mmol IrCl 3 ·nH 2 O was dissolved in a mixed solvent of 2-ethoxyethanol and water (V/V = 3), refluxed at 140 ℃ for 24 hours, filtered, the cake was washed with ethanol, and dried in vacuo to give bis { bis [2- (2, 4-difluorophenyl) pyridine as a solid]Iridium dichloride }.
Example 3:
Example 4:
Example 5:
preparation of the ionic binuclear iridium complex Ir1: under the protection of nitrogen, 0.5mmol of 2, 5-bis (1H-imidazo [4, 5-f)][1,10]Phenanthrolin-2-yl) furan, 0.36mmol of bis { bis [2- (2, 4-difluorophenyl) pyridine]Iridium dichloride } was reacted in 20mL of a mixed solvent of methanol/dichloromethane (volume ratio 1 6 Stirring at room temperature for 2h, desolventizing, siO 2 And (3) performing column chromatography purification, wherein an eluent is dichloromethane-methanol = 15.
The complex Ir1 is subjected to 1 H NMR and mass spectral characterization confirmed the correct structure, and the data are as follows:
1 H NMR(400MHz,DMSO-d 6 )δ15.09(s,2H),9.32(d,J＝78.2,3H),8.36(t,J＝9.9Hz,4H),8.16–8.02(m,10H),7.90(t,J＝7.6Hz,4H),7.83(t,J＝7.8Hz,4H),7.72(s,1H),7.62(d,J＝6.5Hz,3H),7.42(s,3H),7.08(td,J＝10.2,9.5,5.2Hz,3H),5.47(d,J＝8.1Hz,3H).
MS (ESI): experimental values: m/z 1649.2606[ m-2 (PF) 6 )] 2+ (ii) a Theoretical value: m/z 1939.5388.
The relative molecular mass theoretical value of the complex Ir1 is 1939.5388, the peak of the maximum mass-to-charge ratio obtained by electrospray mass spectrometry is 1649.2606, and two hexafluorophosphates are removed from the ionic binuclear complex Ir1The relative molecular mass of the cation structure of the acid radical is consistent, and the synthesized complex is proved to be a target binuclear iridium complex; in Ir1 1 In the H NMR data, a single peak with a chemical shift value at 15.09 is assigned to the hydrogen at the imidazole group N-H of the neutral ligand in complex Ir1, and a double peak with a chemical shift value at 7.62 indicates that the neutral ligand constituting complex Ir1 contains a furan group. The nuclear magnetic resonance hydrogen spectrum and mass spectrum data show that the complex Ir1 is a binuclear iridium complex and contains empty coordination sites N and O atoms.
Example 6:
preparation of cationic binuclear iridium complex Ir2: under the protection of nitrogen, 0.5mmol of 2, 5-bis (1H-imidazo [4, 5-f)][1,10]Phenanthroline-2-yl) thiophene, 0.36mmol of bis { bis [2- (2, 4-difluorophenyl) pyridine]Iridium dichloride } was reacted in 20mL of a methanol/dichloromethane mixed solvent (volume ratio 1) 6 Stirring at room temperature for 2h, desolventizing, siO 2 And (3) performing column chromatography purification, wherein an eluent is dichloromethane-methanol = 15.
The complex Ir2 is subjected to 1 H NMR and mass spectral characterization confirmed the correct structure, and the data are as follows:
1 H NMR(400MHz,DMSO-d 6 )δ15.29(s,2H),9.26(s,3H),8.31(d,J＝8.9Hz,6H),8.24(d,J＝5.0Hz,4H),8.09(t,J＝7.1Hz,4H),7.99(t,J＝8.0Hz,5H),7.61(d,J＝5.8Hz,4H),7.09(t,J＝6.8Hz,4H),7.01(ddd,J＝12.2,9.4,2.4Hz,5H),5.73(d,J＝2.4Hz,3H).
MS (ESI): experimental values: m/z 1665.2338[ m-2 (PF) 6 )] 2+ (ii) a Theoretical values are as follows: m/z 1955.6044.
The relative molecular mass theoretical value of the complex Ir2 is 1955.6044, the peak of the maximum mass-to-charge ratio obtained by electrospray mass spectrometry is 1665.2338, and the relative molecular mass is consistent with that of the ionic type binuclear complex Ir2 with the cationic structure of two hexafluorophosphoric acid radicals removed, so that the synthesized complex is proved to be a target binuclear iridium complex; in Ir2 1 In H NMR data, a single peak with a chemical shift value of 15.29 is attributed to hydrogen at the neutral ligand imidazole group N-H in the complex Ir2, and a double peak with a chemical shift value of 7.61 indicates that the complex is formedThe neutral ligand of Ir2 contains a thienyl group. The nuclear magnetic resonance hydrogen spectrum and mass spectrum data show that the complex Ir2 is a binuclear iridium complex and contains N and S atoms with empty coordination sites.
Example 7:
the ultraviolet visible absorption spectrum and the emission spectrum of the complex Ir1 and Ir2 of the invention are as follows:
acetonitrile solution of complexes Ir1 and Ir2 (2.0X 10) -5 mol/L) is shown in figure 1, and the absorption peak position of Ir1 is: ir1: lambda abs And nm:244nm,285nm and 362nm. The absorption peak position of Ir2 is: ir2: lambda abs ，nm：250nm,294nm,394nm。
Acetonitrile solution of complexes Ir1 and Ir2 (5.0X 10) -4 mol/L) is shown in the attached figure 2, the maximum emission peak position of Ir1 is Ir1: lambda [ alpha ] em，max And nm:520nm and Ir2 have the maximum emission peak position as follows: ir2: lambda [ alpha ] em，max ，nm：509nm。
Example 8:
complex Ir1 vs. Cu 2+ Phosphorescence spectrum test of response: 2.0mL of 5.0X 10 was taken -4 Putting mol/L acetonitrile solution of complex Ir1 into a quartz cuvette with an optical path of 1cm, and respectively taking 5.0 multiplied by 10 -2 mol/L Cu 2+ Aqueous solutions of 2. Mu.L, 4. Mu.L, 6. Mu.L, 8. Mu.L, 10. Mu.L, 12. Mu.L, 14. Mu.L, 16. Mu.L, 18. Mu.L, 20. Mu.L, 25. Mu.L, 30. Mu.L, 35. Mu.L and 40. Mu.L were added to the cuvette step by step, and the emission spectrum of the test solution was measured after leaving it for 1min, with the results of the measurement shown in FIG. 3. As can be seen from the figure, with Cu 2+ With the addition of (1), the emission intensity at the maximum emission wavelength of 520nm is gradually reduced, and the complex and Cu are mixed 2+ In the range of 0 to 1, the emission intensity decreases linearly when Cu is added 2+ When the amount concentration of the substance(s) is equal to or greater than 1 equivalent, the emission intensity is almost unchanged, and the emission luminance of the solution is reduced under the irradiation of an ultraviolet lamp of 365 nm. Experimental results show that the binuclear iridium complex Ir1 can realize the Cu-Cu interaction by utilizing the phosphorescence emission spectrum 2+ The detection is effective.
Example 9:
complex Ir1 vs. Cu 2+ Selective testing of response: taking 15 quartz cuvettes of 1cm,2.0mL of 5.0X 10 was added -4 mol/L of complex Ir1 in acetonitrile, and then 20. Mu.L of 5.0X 10 solutions of complex Ir1 are added to the cuvette respectively - 2 mol/LAg + ,Ca 2+ ,Cd 2+ ,Co 2+ ,Cr 3+ ,Cu 2+ ,Fe 2+ ,Fe 3+ ,Hg 2+ ,K + ,Mg 2+ ,Na + ,Ni 2+ ,Pb 2+ ,Zn 2+ Standing the aqueous solution for 1min, respectively testing the emission spectra of the solutions, and the test results are shown in figure 4, except for Cu 2+ Other ions, e.g. Ag + ,Ca 2+ ,Cd 2+ ,Co 2+ ,Cr 3+ ,Fe 2+ ,Fe 3+ ,Hg 2+ ,K + ,Mg 2+ ,Na + ,Ni 2+ ,Pb 2+ ,Zn 2+ The addition of (a) has little influence on the luminescence intensity of the complex Ir1 solution. When Cu is added 2+ Then, the luminescence intensity of the complex is obviously changed, and the luminescence intensity at 520nm is quenched by 98%. The color of the emitted light was changed from yellow to green by naked eyes, and the emission luminance was reduced under the irradiation of 365nm ultraviolet light, and almost no emission was observed. Experimental results show that the complex Ir1 can realize the effect on Cu through the change of phosphorescence spectrum 2+ Specific recognition of (1).
Example 10:
complex Ir1 vs. Cu 2+ Competitive testing of responses: 14 1cm quartz cuvettes were taken and 2.0mL of 5.0X 10 cuvettes were added -4 mol/L of complex Ir1 in acetonitrile, and then 20 mu L of 5.0X 10 solution are respectively added into the cuvette - 2 mol/L of Ag + ,Ca 2+ ,Cd 2+ ,Co 2+ ,Cr 3+ ,Fe 2+ ,Fe 3+ ,Hg 2+ ,K + ,Mg 2+ ,Na + ,Ni 2+ ,Pb 2+ ,Zn 2+ The aqueous solution was allowed to stand for 1min, and the emission spectrum of each solution was measured, and it was observed that the emission peak intensity hardly changed. Under 365nm illumination, the luminous color and brightness are equal to those of the product without Ag + ,Ca 2+ ,Cd 2+ ,Co 2+ ,Cr 3+ ,Fe 2+ ,Fe 3+ ,Hg 2+ ,K + ,Mg 2+ ,Na + ,Ni 2+ ,Pb 2+ ,Zn 2+ The luminescence phenomenon of the solution is consistent. Then, 20. Mu.L of 5.0X 10 cells were added to each of these cuvettes -2 mol/L Cu 2+ An aqueous solution. The test spectrum is shown in figure 5, and the punctate packed column is the emission peak intensity value of an Ir1 acetonitrile solution at 520 nm; the transverse line packed column is formed by adding Ag into the cuvette respectively + ,Ca 2+ ,Cd 2+ ,Co 2+ ,Cr 3+ ,Fe 2+ ,Fe 3+ ,Hg 2+ ,K + ,Mg 2+ ,Na + ,Ni 2+ ,Pb 2+ ,Zn 2+ Emission peak intensity value at 520 nm; the slant line packed column is prepared by adding Cu into the mixed solution 2+ Followed by an emission peak intensity value at 520 nm. The comparison shows that the addition of Ag + ,Ca 2+ ,Cd 2+ ,Co 2+ ,Cr 3+ ,Fe 2+ ,Fe 3+ ,Hg 2+ ,K + ,Mg 2+ ,Na + ,Ni 2+ ,Pb 2+ ,Zn 2+ When the method is used, the variation range of the emission peak intensity is very small compared with that of a blank, the luminous color and the brightness are almost unchanged under 365nm irradiation, and Cu is added 2+ After that, the maximum emission peak intensity is significantly reduced. The result shows that the complex Ir1 can still realize the effect of Cu under the interference of other ions 2+ Detection of (3).
Example 11:
complex Ir2 vs. Cu 2+ Uv-vis absorption spectroscopy test of response: 2.0mL of 2.0X 10 was taken -5 Putting mol/L acetonitrile solution of complex Ir2 in a quartz cuvette with an optical path of 1cm, and taking the solution at 1.0 multiplied by 10 -3 mol/L of Cu 2+ Aqueous solutions of 4. Mu.L, 8. Mu.L, 12. Mu.L, 16. Mu.L, 20. Mu.L, 24. Mu.L, 28. Mu.L, 32. Mu.L, 36. Mu.L, 40. Mu.L, 50. Mu.L, 60. Mu.L, 70. Mu.L and 80. Mu.L were gradually added to a quartz cuvette, and after addition, the cuvette was allowed to stand for 1min, and then the change in the absorption spectrum was measured. The total amount of metal ions added should not exceed 100. Mu.L to ensure that there is no significant change in the volume of the complex solution. The test results are shown in FIG. 6. As can be seen in the figure, when the complex Ir2 is reacted with Cu 2+ When the molar ratio of (1) to (2) is 0 to 1, the absorption spectrum of the solution changes, the absorbance value gradually increases, and when the molar ratio exceeds 1Almost no change occurred. Using the absorbance value at 294nm as reference, when adding Cu 2+ Within 0-1 equivalent, the absorbance value is equal to that of Cu 2+ The concentration values are linear when Cu is added 2+ When the concentration is more than 1 equivalent, the absorbance value of the solution does not change. Comparison of Ir2 in acetonitrile with 2 equivalents of Cu 2+ The color of the complex solution can be found, and the solution changes from yellow to green under visible light. Experimental results show that the binuclear iridium complex Ir2 can realize the Cu-Cu interaction by utilizing the ultraviolet-visible absorption spectrum 2+ The detection is effective.
Example 12:
complex Ir2 vs. Cu 2+ Selectivity test of response: 15 1cm quartz cuvettes were added to 2.0mL of 2.0X 10 cells -5 mol/L of complex Ir2 in acetonitrile, and then 40. Mu.L of 1.0X 10 solution are added to the cuvette respectively - 3 mol/L of Ag + ,Ca 2+ ,Cd 2+ ,Co 2+ ,Cr 3+ ,Fe 2+ ,Fe 3+ ,Hg 2+ ,K + ,Mg 2+ ,Na + ,Ni 2+ ,Pb 2+ ,Zn 2+ ,Cu 2+ And (3) standing the aqueous solution for 1min, and testing the ultraviolet-visible absorption spectrum of the solution, wherein the test result is shown in the attached figure 7. When adding Ag to an acetonitrile solution of Ir2 + ,Ca 2+ ,Cd 2+ ,Co 2+ ,Cr 3+ ,Fe 2+ ,Fe 3+ ,Hg 2+ ,K + ,Mg 2+ ,Na + ,Ni 2+ ,Pb 2+ ,Zn 2+ When the complex is used as the aqueous solution, the ultraviolet-visible absorption spectrum of the solution is consistent with that of the complex Ir2, and the intensity change of each absorption peak is small. While adding Cu 2+ Then, the absorption spectrum of the complex is obviously changed, the absorbance value is increased, and the absorbance value at 294nm is increased by 3 times. The experimental result shows that the complex Ir2 can realize the effect on Cu by using the change of an ultraviolet-visible absorption spectrum 2+ Specific recognition of (1).
Example 13:
complex Ir2 vs. Cu 2+ Competitive response test for response: taking 14 quartz cuvettes of 1cm,respectively adding 2.0 mL2.0X 10 -5 mol/L of complex Ir2 in acetonitrile, and then 40. Mu.L of 1.0X 10 solution are added to the cuvette respectively -3 mol/L of Ag + ,Ca 2+ ,Cd 2+ ,Co 2+ ,Cr 3+ ,Fe 2+ ,Fe 3+ ,Hg 2+ ,K + ,Mg 2+ ,Na + ,Ni 2+ ,Pb 2+ ,Zn 2+ Testing the UV-visible absorption spectrum of the aqueous solution, and adding 40 μ L of 1.0 × 10 -3 mol/L Cu 2+ After 2 minutes, the UV-Vis absorption spectrum was again tested, the results of which are shown in FIG. 8. As can be seen from the figure, in the complexes Ir2 and Ag + ,Ca 2+ ,Cd 2+ ,Co 2+ ,Cr 3+ ,Fe 2+ ,Fe 3+ ,Hg 2+ ,K + ,Mg 2+ ,Na + ,Ni 2+ ,Pb 2+ ,Zn 2+ Adding Cu into the mixed solution 2+ After that, the absorption intensity at 294nm is significantly enhanced. The dotted packed column is the absorbance value of the blank sample at 294 nm; the transverse line packed column is the absorbance value of a mixed solution at 294nm obtained by respectively adding different metal ions into a solution of the complex Ir 2; the oblique line packed column is formed by adding Cu into a solution added with different metal ions 2+ Followed by absorbance value at 294 nm. Experimental results show that the complex Ir2 can still realize the effect of Cu even under the interference of other metal ions 2+ Detection of (3).
Example 14:
complex Ir2 vs. Cu 2+ Competitive testing of responses: 14 1cm quartz cuvettes were taken and 2.0mL of 1.0X 10 cells were added -6 mol/L of complex Ir2 in acetonitrile, and then 20. Mu.L of 1.0X 10 solution are added to the cuvette respectively - 4 mol/L of Ag + ,Ca 2+ ,Cd 2+ ,Co 2+ ,Cr 3+ ,Fe 2+ ,Fe 3+ ,Hg 2+ ,K + ,Mg 2+ ,Na + ,Ni 2+ ,Pb 2+ ,Zn 2+ Aqueous solution, and tested for uv-vis absorption spectrum. Then, 20. Mu.L of 1.0X 10 was added to the above mixed solution -4 mol/L Cu 2+ 2 minutes later, again test UV-KeSee absorption spectrum. Experiments show that only Cu is added 2+ Only result in an enhancement of the UV-visible absorption spectrum, while adding other metal ions, such as Ag + ,Ca 2+ ,Cd 2+ ,Co 2+ ,Cr 3+ ,Fe 2+ ,Fe 3+ ,Hg 2+ ,K + ,Mg 2+ ,Na + ,Ni 2+ ,Pb 2+ ,Zn 2+ The uv-vis absorption spectrum remains almost unchanged. Experimental results show that the complex Ir2 can still realize the effect of Cu even under the interference of other metal ions 2+ The detection of (3).
The invention is not the best known technology.
Claims (6)
1. A phenanthroline derivative-based binuclear iridium complex is characterized in that the complex is two substances with the following structural formula:
2. The method for preparing a phenanthroline derivative-based dinuclear iridium complex according to claim 1, wherein the method comprises the following steps:
bis { di [2- (2, 4-difluorophenyl) pyridine under anhydrous and oxygen-free operating conditions]Iridium dichloride } and a neutral ligand are refluxed in a mixed solvent with the temperature of 45-80 ℃ for 6h to 12h, and KPF is added into the system 6 Then stirring at room temperature for 1h to 2h to obtain a cationic binuclear iridium complex;
wherein the molar ratio is bis { di [2- (2, 4-difluorophenyl) pyridine]Iridium dichloride } neutral ligand KPF 6 =1 : 1.1~1.5 : 2.5~10.0；
The neutral ligand is 2, 5-bis (1H-imidazo [4,5-f ] [1,10] phenanthroline-2-yl) furan or 2, 5-bis (1H-imidazo [4,5-f ] [1,10] phenanthroline-2-yl) thiophene;
the mixed solvent is dichloromethane and methanol, and the volume ratio of the dichloromethane to the methanol is 1; 30 to 100 ml of a mixed solvent is added to every millimole of bis { bis [2- (2, 4-difluorophenyl) pyridine ] iridium dichloride }.
3. Use of phenanthroline derivative based dinuclear iridium complexes according to claim 1 for non-diagnostic purposes, characterised by the fact that they are used for the identification of Cu in solution 2+ 。
4. The use of phenanthroline derivative-based dinuclear iridium complexes according to claim 3 for non-diagnostic purposes, characterized in that it comprises in particular the following methods:
the method I comprises the following steps:
adding a to-be-detected water solution into an acetonitrile solution of the binuclear iridium complex to obtain a mixed test solution; when the binuclear iridium complex is observed to be changed from original yellow to green by naked eyes, the situation shows that the aqueous solution to be detected contains Cu 2+ ；
Wherein, the concentration of the binuclear iridium complex in the mixed test solution is 1.0 multiplied by 10 -6 mol/L~5.0×10 -2 mol/L, cu in the mixed test solution 2+ The content range of the ions was 1.0X 10 -7 mol/L~5.0mol/L；
Or the second method comprises the following steps:
adding a to-be-tested aqueous solution into an acetonitrile solution of the binuclear iridium complex to obtain a mixed test solution; measuring the change of emission intensity of the mixed solution at the maximum emission peak by using a fluorescence spectrometer, and when the quenching amount of the emission intensity exceeds 10 percent, indicating that the aqueous solution to be measured contains Cu 2+ ；
Wherein, the concentration of the binuclear iridium complex in the mixed test solution is 1.0 multiplied by 10 -6 mol/L~5.0×10 -2 mol/L, cu in the mixed test solution 2+ The content range of the ions was 1.0X 10 -7 mol/L~5.0mol/L；
Or a third method, comprising the steps of:
adding a to-be-detected aqueous solution into an acetonitrile solution of the binuclear iridium complexObtaining a mixed test solution; measuring the change of absorption intensity at 294nm of the mixed solution by using an ultraviolet-visible absorption spectrophotometer, and when the increase of the absorbance value exceeds 10%, indicating that the aqueous solution to be measured contains Cu 2+ ；
Wherein, the concentration of the binuclear iridium complex in the mixed test solution is 1.0 multiplied by 10 -6 mol/L~5.0×10 -2 mol/L, cu in the mixed test solution 2+ The content range of the ions was 1.0X 10 -7 mol/L~5.0mol/L。
5. The non-diagnostic use of phenanthroline derivative based dinuclear iridium complexes as claimed in claim 4, wherein:
in the first method, when the binuclear iridium complex is observed to change from original yellow to green by naked eyes, the molar ratio is determined as follows: cu (copper) 2+ Ion =0.1 to 10;
in the second, when the quenching amount of emission intensity at the maximum emission peak exceeds 10%, it is judged that the molar ratio is, binuclear iridium complex: cu 2+ Ion =0.1 to 10;
in the third, when the absorption intensity value at 294nm increases by more than 10%, it is judged that the molar ratio is, the binuclear iridium complex: cu 2+ Ion =0.1 to 10.
6. The non-diagnostic use of phenanthroline derivative based dinuclear iridium complexes as claimed in claim 4, wherein: the aqueous solution to be measured contains Ag + , Ca 2+ , Cd 2+ , Co 2+ , Cr 3+ , Fe 2+ , Fe 3+ , Hg 2+ , K + , Mg 2+ , Na + , Ni 2+ , Pb 2+ , Zn 2+ , Cu 2+ Of the ion(s).
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