CN102321468A - Cationic iridium complex phosphorescene probe as well as preparation method and application thereof - Google Patents
Cationic iridium complex phosphorescene probe as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a cationic iridium complex phosphorescene probe. The cationic iridium complex phosphorescene probe as a novel compound is bright yellow solid powder which is easily dissolved in organic solvents such as ethanol, chloroform and the like, is relatively soluble in water, is yellow in water and has very good stability; and the structural formula of the novel compound is shown as the specification. Amide imide pyridine groups of the iridium complex in the invention are intensely coordinated with copper ions to influence the spectral property of the generated product, and the copper ions are detected by using the change of the spectral property. When being excited by ultraviolet light of 365 nm, the iridium complex solution in the invention emits orange-red phosphorescence; after the iridium complex solution is reacted with the copper ions, the phosphorescence is quenched and the other metal ions are not interfered.
Description
Technical field
The present invention relates to phosphorescence chemical dosage facility technical field, be specifically related to a kind of cationic iridium complex phosphorescence probe.
Background technology
Copper is a kind of important element, has caused people's attention in each side such as physiology, medical research, environment murders by poisoning.Copper is the intravital essential elements of many biologies, in some biological tissues, plays a part complicatedly and important, will cause disease, particularly cardiovascular and cerebrovascular diseases in case lack, but it accumulates in human body when too many, also can cause a lot of toxic actions.Copper has extraordinary medical usage.China medical science inventor discovers that copper has extremely strong anti-cancer function, and successfully develops corresponding cancer therapy drug " gram cancer 7851 ", succeeds clinically.Cupric ion has the effect of intensive sterilization in addition, and its mechanism of action is: Cu is having the Cu that generates under the condition of water
2+Permeate through cell membranes, the inside of arrival cell is because Cu
2+Be heavy metal ion, can make some enzyme denaturation, thereby destroy their metabolism, kill microorganisms.Copper is a kind of heavy metal of serious environment pollution, and its pollution that causes generally is difficult to eliminate, and has caused many serious problems for environment and HUMAN HEALTH, more and more causes people's attention.Therefore, how to detect cupric ion effectively and significant meaning is all arranged for biological chemistry, environmental science and medical science etc.Developed for the detection people of cupric ion so far and several different methods, like atomic absorption spectrum, atomic emission spectrum etc., yet these methods have a lot of shortcomings, need pre-treatment, detect inadequately fast, detect and cost an arm and a leg etc. like sample.Therefore, in a lot of important use occasions, people press for fast, accurately, the low-cost also method of analyzing and testing cupric ion optionally.
In recent years, the phosphorescence heavy metal complex that has superior photophysical property is in the increasing concern of receiving of photochemistry field.They have following several characteristics: emission wavelength receives environmental influence of living in bigger, modulates the distinct transmit wavelength easily; Compare organic phosphorescent material and have bigger (stokes) Stokes displacement and long emission lifetime; And long emission lifetime helps the duration of service resolution techniques phosphorescent signal is distinguished with the phosphorescent signal of background mutually, thereby avoids the interference of background fluorescence effectively.Reported some phosphorescence heavy metal complexes at present,, be used as the phosphorescence chemical sensor that detects amino acid, negatively charged ion, oxygen concn and metals ion like platinum, rhenium and ruthenium complexe.To the report of the complex of iridium that has high-performance equally seldom, its using value at Optochemical sensor is fully developed far away.The present invention has further expanded the application of complex of iridium in the Optochemical sensor field.
Summary of the invention
The object of the present invention is to provide a kind of cationic iridium complex phosphorescence probe and preparation method thereof, the technical problem of analyzing with the rapid detection that solves cupric ion.
The object of the invention can be realized through following technical scheme:
A kind of cationic iridium complex phosphorescence probe, this novel cpd is the glassy yellow pressed powder, is soluble in organic solvents such as ethanol, chloroform, in water, has certain dissolubility, is yellow solution, and stability is fine, and its structural formula is:
The preparation method of above-mentioned cationic iridium complex phosphorescence probe is following:
(1) the adjacent luxuriant and rich with fragrance sound of vomiting quinoline-5-ethanamide of preparation 2-chloro-:
A, under nitrogen protection, take by weighing the amino adjacent luxuriant and rich with fragrance sound of vomiting quinoline of one times of normal 5-and put into three-necked flask, placed ice-water bath 0～10 hour;
B, to add volume ratio be 30～1: 1 the anhydrous tetrahydro furan and the mixing solutions of triethylamine, stirred 0～10 hour;
C, dropwise drip 0.1～10 times of normal chloroacetyl chloride in flask, rise to normal temperature, continue to stir 0～40 hour;
D, add an amount of 1～40% sodium hydrogen carbonate solution and transfer to mixing solutions for neutral, standing demix, get organic layer revolve dried, respectively washing, ethanol wash, ether wash the yellow solid product: the adjacent luxuriant and rich with fragrance sound of vomiting quinoline-5-ethanamide of 2-chloro-.
(2) preparation 2-phenylpyridine iridium dichloro bridge title complex, (ppy)
2IrCl
2Ir (ppy)
2, wherein ppy is the 2-phenylpyridine;
A, to take by weighing mol ratio be 3～0.1: 1 IrCl
33H
2O and 2-phenylpyridine join in the three-necked bottle;
B, to add volume ratio be 1～20: 1 the 2-ethylene glycol ethyl ether and the mixing solutions of water;
C, above-mentioned mixing solutions is heated to 70 ℃～150 ℃, stirs after 1～50 hour, be chilled to room temperature, have yellow mercury oxide to generate;
D, with above-mentioned gained deposition water and washing with alcohol respectively, vacuum-drying then obtains yellow solid 2-phenylpyridine iridium dichloro bridge title complex: (ppy)
2IrCl
2Ir (ppy)
2
(3) the adjacent luxuriant and rich with fragrance sound of vomiting quinoline-5-ethanamide iridium 2-phenylpyridine title complex of preparation 2-chloro-:
A, to take by weighing mol ratio be that the adjacent luxuriant and rich with fragrance sound of vomiting quinoline-5-ethanamide of 2～0.1: 1 2-phenylpyridine iridium dichloro bridge title complex and 2-chloro-joins in the three-necked bottle;
B, to add volume ratio be 1～20: 1 the methylene dichloride and the mixing solutions of methyl alcohol;
C, be heated to 30 ℃～65 ℃, stirring reaction was cooled to room temperature with reaction solution after 1～40 hour;
D, 1～20 times of normal Potassium Hexafluorophosphate of adding continue to stir 1～30 hour;
E, screw out most of solvent, add an amount of methylene dichloride, washing, collected organic layer is dry, revolves to do layer
Analyse post and get the adjacent luxuriant and rich with fragrance sound of vomiting quinoline-complex red solid phase prod of 5-ethanamide iridium 2-phenylpyridine of 2-chloro-; (4) preparation target title complex:
A, take by weighing 2-chloro-adjacent luxuriant and rich with fragrance sound of vomiting quinoline-5-ethanamide iridium 2-phenylpyridine title complex and 2-aminomethyl-pyridine in three-necked flask, its mol ratio is 1: 0.1～30;
B, add 0.01～20 times of normal potassiumiodide and triethylamine respectively;
C, an amount of anhydrous tetrahydro furan to the solid of adding dissolve fully, and controlled temperature reacted 1～40 hour at 30～65 ℃;
After D, reaction finish, filter, revolve driedly, add an amount of methylene dichloride, washing, collected organic layer is dry, revolves dried chromatography column and gets the yellow solid product.
The preparation of the target title complex described in the step (4) is to be catalyzer with the potassiumiodide, carries out the heated and stirred reaction at the mixed solvent of THF and triethylamine.
The acid amides '-imine pyridinyl group of the complex of iridium among the present invention and cupric ion generation intensive coordination, thus the spectral quality of the influence product that generates utilizes the change of this spectral quality to detect cupric ion.Complex of iridium solution among the present invention sends reddish orange phosphorescence when the 365nm ultraviolet excitation, and with the cupric ion effect after phosphorescence quenching, other metals ion does not disturb it.
Title complex is tested the UV spectrum of cupric ion response: the mensuration of UV spectrum is in the mixing solutions of micro ethanol and water, to carry out; Complex of iridium is dissolved in the mixing solutions of micro ethanol and water; The copper nitrate solution with pure water preparation that adds different concns is again tested after reaching balance.
Complex of iridium is tested the phosphorescence spectrum of cupric ion response: the mensuration of phosphorescence spectrum is in the mixing solutions of micro ethanol and water, to carry out; Complex of iridium is dissolved in the mixing solutions of micro ethanol and water; The copper nitrate solution with pure water preparation that adds different concns is again tested after reaching balance.
Advantage of the present invention: because metal iridium complex has long luminescent lifetime, can eliminate the interference of background fluorescence effectively, obtain very high detection sensitivity through the time resolved fluorescence technology.Metal iridium complex can detect cupric ion among the present invention, and other common metal ion is not disturbed this process.
Description of drawings
Fig. 1 is the UV spectrum variation of complex of iridium to the cupric ion response;
Fig. 2 is the phosphorescence spectrum variation of complex of iridium to the cupric ion response;
Fig. 3 is a complex of iridium to the phosphorescence spectrum selectivity test of several frequently seen metals ion response figure as a result;
Fig. 4 is the phosphorescence spectrum competitive test result figure of complex of iridium to cupric ion and common metal ion response.
Embodiment
Through embodiment the present invention is further specified below, but be not used for limiting the present invention.
Embodiment 1
The adjacent luxuriant and rich with fragrance sound of vomiting quinoline-5-ethanamide of 2-chloro-: under nitrogen protection, the amino adjacent luxuriant and rich with fragrance sound of vomiting quinoline of the 5-that takes by weighing (1.5mmol) is put into three-necked flask, places ice-water bath 1 hour; Add the 40.0ml anhydrous tetrahydro furan then; 2.0ml triethylamine stirred 1 hour, dropwise dripped the 0.5ml chloroacetyl chloride in flask; Rise to normal temperature, continue to stir 15 hours.Add an amount of 10% sodium hydrogen carbonate solution and transfer to neutral back layering, get organic layer revolve dried, respectively washing, ethanol wash, ether wash the yellow solid product.
1H?NMR(400MHz，DMSO)δ(ppm)：4.61(d，2H，)，7.99(d，2H)，8.36(s，1H，NH)，8.81(s，1H)，8.95(d，1H)，9.11(d，1H)，9.21(dd，1H).
Embodiment 2
The adjacent luxuriant and rich with fragrance sound of vomiting quinoline-5-ethanamide of 2-chloro-: under nitrogen protection, the amino adjacent luxuriant and rich with fragrance sound of vomiting quinoline of the 5-that takes by weighing (1.0mmol) is put into three-necked flask, places ice-water bath 0.5 hour; Add the 30.0ml anhydrous tetrahydro furan then; 1.5ml triethylamine stirred 1.5 hours, dropwise dripped the 0.5ml chloroacetyl chloride in flask; Rise to normal temperature, continue to stir 12 hours.Add an amount of 15% sodium hydrogen carbonate solution and transfer to neutrality, standing demix, get organic layer revolve dried, respectively washing, ethanol wash, ether wash the yellow solid product.
1H?NMR(400MHz，DMSO)δ(ppm)：4.60(d，2H，)，7.98(d，2H)，8.34(s，1H，NH)，8.83(s，1H)，8.85(d，1H)，9.13(d，1H)，9.24(dd，1H).
Embodiment 3
The adjacent luxuriant and rich with fragrance sound of vomiting quinoline-5-ethanamide of 2-chloro-: under nitrogen protection, the amino adjacent luxuriant and rich with fragrance sound of vomiting quinoline of the 5-that takes by weighing (1.3mmol) is put into three-necked flask, places ice-water bath 2.0 hours; Add the 35.0ml anhydrous tetrahydro furan then; 2.3ml triethylamine stirred 0.5 hour, dropwise dripped the 1.0ml chloroacetyl chloride in flask; Rise to normal temperature, continue to stir 10 hours.Add an amount of 20% sodium hydrogen carbonate solution and transfer to neutrality, standing demix, get organic layer revolve dried, respectively washing, ethanol wash, ether wash the yellow solid product.
1H?NMR(400MHz，DMSO)δ(ppm)：4.63(d，2H，)，7.97(d，2H)，8.39(s，1H，NH)，8.80(s，1H)，8.93(d，1H)，9.15(d，1H)，9.24(dd，1H).
Embodiment 4
2-phenylpyridine iridium dichloro bridge title complex [(ppy)
2IrCl
2Ir (ppy)
2] preparation: take by weighing IrCl
33H
2O (5.52mmol) and 2-phenylpyridine (11.04mmol) join in the three-necked flask, add the mixing solutions of 2-ethylene glycol ethyl ether and water, and the two volume ratio is 5: 1; So reaction mixture is heated to 110 ℃, stirring reaction 25 hours, after question response finished, cool to room temperature had yellow mercury oxide to generate.Cross and filter deposition, distinguish water and washing with alcohol then, and use vacuum-drying, obtain glassy yellow solid 2-phenylpyridine iridium dichloro bridge title complex, [(ppy)
2IrCl
2Ir (ppy)
2].
Embodiment 5
2-phenylpyridine iridium dichloro bridge title complex [(ppy)
2IrCl
2Ir (ppy)
2] preparation: take by weighing IrCl
33H
2O (4.2mmol) and 2-phenylpyridine (11.2mmol) join in the three-necked flask, add the mixing solutions of 2-ethylene glycol ethyl ether and water, and the two volume ratio is 5: 1; So reaction mixture is heated to 130 ℃, stirring reaction 15 hours, after question response finished, cool to room temperature had yellow mercury oxide to generate.Cross and filter deposition, distinguish water and washing with alcohol then, and use vacuum-drying, obtain glassy yellow solid 2-phenylpyridine iridium dichloro bridge title complex, [(ppy)
2IrCl
2Ir (ppy)
2].
Embodiment 6
2-phenylpyridine iridium dichloro bridge title complex [(ppy)
2IrCl
2Ir (ppy)
2] preparation: take by weighing IrCl
33H
2O (6.5mmol) and 2-phenylpyridine (14.0mmol) join in the three-necked flask, add the mixing solutions of 2-ethylene glycol ethyl ether and water, and the two volume ratio is 8: 1; So reaction mixture is heated to 120 ℃, stirring reaction 16 hours, after question response finished, cool to room temperature had yellow mercury oxide to generate.Cross and filter deposition, distinguish water and washing with alcohol then, and use vacuum-drying, obtain glassy yellow solid 2-phenylpyridine iridium dichloro bridge title complex, [(ppy)
2IrCl
2Ir (ppy)
2].
Embodiment 7
The adjacent luxuriant and rich with fragrance sound of vomiting quinoline-5-ethanamide iridium 2-phenylpyridine title complex of 2-chloro-: take by weighing the adjacent luxuriant and rich with fragrance sound of vomiting quinoline-5-ethanamide (0.5mmol) of 2-phenylpyridine iridium dichloro bridge title complex (0.2mmol) and 2-chloro-and join in the three-necked bottle; Adding the 50ml volume ratio is 6: 1 the methylene dichloride and the mixing solutions of methyl alcohol; Be heated to 50 ℃, stirring reaction was cooled to room temperature with reaction solution after 20 hours; Add 7 times of normal Potassium Hexafluorophosphates, continue to stir 20 hours.Reaction screws out most of solvent after finishing, and adds an amount of methylene dichloride, washing, and collected organic layer is dry, revolves dried chromatography column and gets the adjacent luxuriant and rich with fragrance sound of vomiting quinoline-5-ethanamide iridium 2-phenylpyridine title complex of 2-chloro-.
1H?NMR(400MHz，DMSO)δ(ppm)：4.56(s，2H)，6.27(t，2H)，6.96(m，4H)，7.05(t，2H)，7.47(t，2H)，7.87(m，2H)，7.94(d，2H)，8.00(q，1H)，8.10(m，2H)，8.24(m，3H)，8.64(s，1H)，8.88(q，1H)，8.98(q，1H)，10.82(s，1H).；MS(ESI
+)m/z：772.2([M+Na]
+).
Embodiment 8
The adjacent luxuriant and rich with fragrance sound of vomiting quinoline-5-ethanamide iridium 2-phenylpyridine title complex of 2-chloro-: take by weighing the adjacent luxuriant and rich with fragrance sound of vomiting quinoline-5-ethanamide (1.2mmol) of 2-phenylpyridine iridium dichloro bridge title complex (0.5mmol) and 2-chloro-and join in the three-necked bottle; Adding the 40ml volume ratio is 3: 1 the methylene dichloride and the mixing solutions of methyl alcohol; Be heated to 45 ℃, stirring reaction was cooled to room temperature with reaction solution after 10 hours; Add 7 times of normal Potassium Hexafluorophosphates, continue to stir 12 hours.Reaction screws out most of solvent after finishing, and adds an amount of methylene dichloride, washing, and collected organic layer is dry, revolves dried chromatography column and gets the adjacent luxuriant and rich with fragrance sound of vomiting quinoline-5-ethanamide iridium 2-phenylpyridine title complex of 2-chloro-.
1H?NMR(400MHz，DMSO)δ(ppm)：4.55(s，2H)，6.26(t，2H)，6.96(m，4H)，7.05(t，2H)，7.47(t，2H)，7.88(m，2H)，7.94(d，2H)，8.00(q，1H)，8.11(m，2H)，8.24(m，3H)，8.64(s，1H)，8.88(q，1H)，8.98(q，1H)，10.83(s，1H).；MS(ESI
+)m/z：772.2([M+Na]
+).
Embodiment 9
The adjacent luxuriant and rich with fragrance sound of vomiting quinoline-5-ethanamide iridium 2-phenylpyridine title complex of 2-chloro-: take by weighing the adjacent luxuriant and rich with fragrance sound of vomiting quinoline-5-ethanamide (0.9mmol) of 2-phenylpyridine iridium dichloro bridge title complex (0.3mmol) and 2-chloro-and join in the three-necked bottle; Adding the 350ml volume ratio is 5: 1 the methylene dichloride and the mixing solutions of methyl alcohol; Be heated to 50 ℃, stirring reaction was cooled to room temperature with reaction solution after 14 hours; Add 9 times of normal Potassium Hexafluorophosphates, continue to stir 15 hours.Reaction screws out most of solvent after finishing, and adds an amount of methylene dichloride, washing, and collected organic layer is dry, revolves dried chromatography column and gets the adjacent luxuriant and rich with fragrance sound of vomiting quinoline-5-ethanamide iridium 2-phenylpyridine title complex of 2-chloro-.
1H?NMR(400MHz，DMSO)δ(ppm)：4.56(s，2H)，6.27(t，2H)，6.96(m，4H)，7.04(t，2H)，7.47(t，2H)，7.87(m，2H)，7.94(d，2H)，8.01(q，1H)，8.10(m，2H)，8.24(m，3H)，8.65(s，1H)，8.88(q，1H)，8.98(q，1H)，10.82(s，1H).；MS(ESI
+)m/z：772.2([M+Na]
+).
Embodiment 10
The preparation of target title complex: take by weighing adjacent luxuriant and rich with fragrance sound of vomiting quinoline-5-ethanamide iridium 2-phenylpyridine title complex (0.5mmol) of 2-chloro-and 2-aminomethyl-pyridine (0.4ml) in three-necked flask; Add potassiumiodide (10mg) and triethylamine (0.5ml); Add the 60ml THF again; Controlled temperature is at 45 ℃, stirring reaction 25 hours.After question response finishes, filter, revolve driedly, add an amount of methylene dichloride, washing, collected organic layer is dry, revolves dried chromatography column and gets the yellow solid product.Fusing point: 238-241 ℃.
1H?NMR(400MHz，CDCl
3)δ(ppm)：9.30(d，1H，J＝8.4Hz)，8.76(s，1H)，8.55(d，1H，J＝4.4Hz)，8.50(d，1H，J＝8.4Hz)，8.28(d，1H，J＝4.8Hz)，8.17(d，1H，J＝4.8Hz)，7.93(m，4H)，7.72(m，6H)，7.52(d，1H，J＝7.6Hz)，7.42(d，1H，J＝5.6Hz)，7.33(d，1H，J＝5.6Hz)，7.19(q，1H，J＝4.0Hz)，7.09(m，2H)，6.98(q，3H，J＝6.67)，6.89(t，1H，J＝6.2Hz)，6.40(q，2H，J＝3.34Hz)，4.16(s，2H)，3.88(s，2H)，1.19(s，1H).
Embodiment 11
The preparation of target title complex: take by weighing adjacent luxuriant and rich with fragrance sound of vomiting quinoline-5-ethanamide iridium 2-phenylpyridine title complex (0.8mmol) of 2-chloro-and 2-aminomethyl-pyridine (1.0ml) in three-necked flask; Add potassiumiodide (15mg) and triethylamine (1.2ml); Add the 40ml THF again; Controlled temperature is at 50 ℃, stirring reaction 12 hours.After question response finishes, filter, revolve driedly, add the 40ml methylene dichloride, washing, collected organic layer is dry, revolves dried chromatography column and gets the yellow solid product.Fusing point: 238-241 ℃.
1H?NMR(400MHz，CDCl
3)δ(ppm)：9.31(d，1H，J＝8.4Hz)，8.76(s，1H)，8.55(d，1H，J＝4.4Hz)，8.50(d，1H，J＝8.4Hz)，8.28(d，1H，J＝4.8Hz)，8.18(d，1H，J＝4.8Hz)，7.93(m，4H)，7.73(m，6H)，7.52(d，1H，J＝7.6Hz)，7.42(d，1H，J＝5.6Hz)，7.33(d，1H，J＝5.6Hz)，7.16(q，1H，J＝4.0Hz)，7.09(m，2H)，6.99(q，3H，J＝6.67)，6.89(t，1H，J＝6.2Hz)，6.40(q，2H，J＝3.34Hz)，4.16(s，2H)，3.88(s，2H)，1.19(s，1H).
Embodiment 12
The preparation of target title complex: take by weighing adjacent luxuriant and rich with fragrance sound of vomiting quinoline-5-ethanamide iridium 2-phenylpyridine title complex (1.1mmol) of 2-chloro-and 2-aminomethyl-pyridine (1.3ml) in three-necked flask; Add potassiumiodide (18mg) and triethylamine (2.2ml); Add the 70ml THF again; Controlled temperature is at 53 ℃, stirring reaction 16 hours.After question response finishes, filter, revolve driedly, add the 50ml methylene dichloride, washing, collected organic layer is dry, revolves dried chromatography column and gets the yellow solid product.Fusing point: 238-241 ℃.
1H?NMR(400MHz，CDCl
3)δ(ppm)：9.30(d，1H，J＝8.4Hz)，8.76(s，1H)，8.55(d，1H，J＝4.4Hz)，8.50(d，1H，J＝8.4Hz)，8.29(d，1H，J＝4.8Hz)，8.16(d，1H，J＝4.8Hz)，7.94(m，4H)，7.72(m，6H)，7.53(d，1H，J＝7.6Hz)，7.46(d，1H，J＝5.6Hz)，7.38(d，1H，J＝5.6Hz)，7.19(q，1H，J＝4.0Hz)，7.09(m，2H)，6.98(q，3H，J＝6.67)，6.89(t，1H，J＝6.2Hz)，6.43(q，2H，J＝3.34Hz)，4.16(s，2H)，3.88(s，2H)，1.19(s，1H).
Embodiment 13
Complex of iridium is tested the UV spectrum of cupric ion response: complex of iridium is dissolved in the mixed solvent of micro ethanol and water, the concentration of complex of iridium is 10 μ mol/L, then adds the copper nitrate solution of the pure water configuration of equal-volume 0-2eq.After the ready to balance, measure UV spectrum, test result is seen Fig. 1: along with the adding of cupric ion, and original 248nm that is in, three strong absorption peak strength at 268nm and 375nm place weaken gradually, and strengthen gradually in the absorption intensity at 200-230nm place.X-coordinate is represented absorbing wavelength, and ordinate zou is represented absorbancy.
Embodiment 14
Complex of iridium is tested the fluorescence spectrum of cupric ion response: complex of iridium is dissolved in the mixed solvent of micro ethanol and water, the concentration of complex of iridium is 10 μ mol/L, then adds the copper nitrate solution of the pure water configuration of equal-volume 0-2eq.After the ready to balance, measure the fluorescence UV spectrum, test result is seen Fig. 2: along with the adding of cupric ion, fluorescence intensity (600nm) descends until quencher gradually.X-coordinate is represented emission wavelength, and ordinate zou is represented emissive porwer.
Embodiment 15
Selectivity test: complex of iridium is dissolved in that concentration is 10 μ mol/L in the mixed solvent of micro ethanol and water, adds 1 times of normal different metal ion, is respectively Cu
2+, Mn
2+, Ca
2+, Cd
2+, Ag
+, Co
2+, Cr
3+, Hg
2+, Zn
2+, Pb
2+, Ni
2+, Fe
3+, Mg
2+, to test after waiting to reach balance, test result is seen Fig. 3: have figure visible, have only cupric ion to make the phosphorescence of complex of iridium that tangible quencher take place.The ordinate zou representative is at the ratio of wavelength 600nm emissive porwer, and X-coordinate is represented the different metal ion, is respectively Cu
2+, Mn
2+, Ca
2+, Cd
2+, Ag
+, Co
2+, Cr
3+, Hg
2+, Zn
2+, Pb
2+, Ni
2+, Fe
3+, Mg
2+The representative of figure bend packed column does not add the iridium complex phosphorescence spectrum of metals ion in system, the iridium complex phosphorescence spectrographic changes the representative of horizontal line packed column adds the different metallic ion in system after.
Embodiment 16
Competitive test: complex of iridium is dissolved in that concentration is 10 μ mol/L in the mixed solvent of micro ethanol and water, 1 times of normal different metal ion of adding earlier, test spectral behind the ready to balance; Add 1 times of normal cupric ion again, wait to reach test once more after the balance, test result is seen Fig. 4: visible by figure, common metal ion is not disturbed the process that complex of iridium detects cupric ion.The ordinate zou representative is at the ratio of wavelength 600nm emissive porwer; X-coordinate is represented the different metal ion; The representative of figure bend packed column adds the iridium complex phosphorescence spectrum of common metal ion earlier in system, the iridium complex phosphorescence spectrographic changes the representative of horizontal line packed column adds cupric ion again in system after.
Claims (4)
1. cationic iridium complex phosphorescence probe, it is characterized in that: this compound is the glassy yellow pressed powder, is soluble in ethanol and chloroform, and dissolving is yellow solution in water, and its structural formula is:
2. the preparation method of the said cationic iridium complex phosphorescence probe of claim 1, it is characterized in that: its concrete steps are:
(1) the adjacent luxuriant and rich with fragrance sound of vomiting quinoline-5-ethanamide of preparation 2-chloro-:
A, under nitrogen protection, take by weighing the amino adjacent luxuriant and rich with fragrance sound of vomiting quinoline of one times of normal 5-and put into three-necked flask, place
In the ice-water bath 0～10 hour;
B, to add volume ratio be 30～1: 1 the anhydrous tetrahydro furan and the mixing solutions of triethylamine, stirred 0～10 hour;
C, dropwise drip 0.1～10 times of normal chloroacetyl chloride in flask, rise to normal temperature, continue to stir 0～40 hour;
D, add an amount of 1～40% sodium hydrogen carbonate solution and transfer to mixing solutions for neutral, standing demix,
Get organic layer revolve dried, washing respectively, ethanol washes, ether wash the yellow solid product: the 2-chloro-is adjacent luxuriant and rich with fragrance
Sound of vomiting quinoline-5-ethanamide.
(2) preparation 2-phenylpyridine iridium dichloro bridge title complex, (ppy)
2IrCl
2Ir (ppy)
2, wherein ppy is the 2-phenylpyridine;
A, to take by weighing mol ratio be 3～0.1: 1 IrCl
33H
2O and 2-phenylpyridine join in the three-necked bottle;
B, to add volume ratio be 1～20: 1 the 2-ethylene glycol ethyl ether and the mixing solutions of water;
C, above-mentioned mixing solutions is heated to 70 ℃～150 ℃, stirs after 1～50 hour, be chilled to room temperature, have yellow mercury oxide to generate;
D, with above-mentioned gained deposition water and washing with alcohol respectively, vacuum-drying then obtains yellow solid 2-phenylpyridine iridium dichloro bridge title complex: (ppy)
2IrCl
2Ir (ppy)
2
(3) the adjacent luxuriant and rich with fragrance sound of vomiting quinoline-5-ethanamide iridium 2-phenylpyridine title complex of preparation 2-chloro-:
A, to take by weighing mol ratio be that the adjacent luxuriant and rich with fragrance sound of vomiting quinoline-5-ethanamide of 2～0.1: 1 2-phenylpyridine iridium dichloro bridge title complex and 2-chloro-joins in the three-necked bottle;
B, to add volume ratio be 1～20: 1 the methylene dichloride and the mixing solutions of methyl alcohol;
C, be heated to 30 ℃～65 ℃, stirring reaction was cooled to room temperature with reaction solution after 1～40 hour;
D, 1～20 times of normal Potassium Hexafluorophosphate of adding continue to stir 1～30 hour;
E, screw out most of solvent, add an amount of methylene dichloride, washing, collected organic layer is dry, revolves dried chromatography column and gets the adjacent luxuriant and rich with fragrance sound of vomiting quinoline-complex red solid phase prod of 5-ethanamide iridium 2-phenylpyridine of 2-chloro-;
(4) preparation target title complex:
A, take by weighing 2-chloro-adjacent luxuriant and rich with fragrance sound of vomiting quinoline-5-ethanamide iridium 2-phenylpyridine title complex and 2-aminomethyl-pyridine in three-necked flask, its mol ratio is 1: 0.1～30;
B, add 0.01～20 times of normal potassiumiodide and triethylamine respectively;
C, an amount of anhydrous tetrahydro furan to the solid of adding dissolve fully, and controlled temperature reacted 1～40 hour at 30～65 ℃;
After D, reaction finish, filter, revolve driedly, add an amount of methylene dichloride, washing, collected organic layer is dry, revolves dried chromatography column and gets the yellow solid product.
3. according to the preparation method of the said cationic iridium complex phosphorescence probe of claim 2; It is characterized in that: the preparation of the target title complex described in the step (4); Be to be catalyzer with the potassiumiodide, carry out the heated and stirred reaction at the mixed solvent of THF and triethylamine.
4. cationic iridium complex phosphorescence probe as claimed in claim 1 is characterized in that: complex of iridium solution sends reddish orange phosphorescence when the 365nm ultraviolet excitation, and with the cupric ion effect after phosphorescence quenching, be applied to detect cupric ion.
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Cited By (3)
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| CN104086596A (en) * | 2014-05-08 | 2014-10-08 | 南京邮电大学 | Phosphorescent iridium complex, and preparation method and application thereof |
| CN106188149A (en) * | 2016-07-05 | 2016-12-07 | 上海师范大学 | A kind of near-infrared metal iridium complex and its preparation method and application |
| CN114057931A (en) * | 2021-12-06 | 2022-02-18 | 南京工业职业技术大学 | Temperature response polymer material with iridium complex and europium chelate as monomers, and preparation method and application thereof |
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| US20020045268A1 (en) * | 1997-02-28 | 2002-04-18 | Joseph R. Lakowicz | Measuring analytes with metal-ligand complex probes |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104086596A (en) * | 2014-05-08 | 2014-10-08 | 南京邮电大学 | Phosphorescent iridium complex, and preparation method and application thereof |
| CN104086596B (en) * | 2014-05-08 | 2017-01-25 | 南京邮电大学 | Phosphorescent iridium complex, and preparation method and application thereof |
| CN106188149A (en) * | 2016-07-05 | 2016-12-07 | 上海师范大学 | A kind of near-infrared metal iridium complex and its preparation method and application |
| CN106188149B (en) * | 2016-07-05 | 2019-03-22 | 上海师范大学 | A kind of near-infrared metal iridium complex and its preparation method and application |
| CN114057931A (en) * | 2021-12-06 | 2022-02-18 | 南京工业职业技术大学 | Temperature response polymer material with iridium complex and europium chelate as monomers, and preparation method and application thereof |
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