CN105294771A - Anionic type iridium complex for oxygen sensing, and preparation method and application thereof - Google Patents
Anionic type iridium complex for oxygen sensing, and preparation method and application thereof Download PDFInfo
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- CN105294771A CN105294771A CN201510591038.5A CN201510591038A CN105294771A CN 105294771 A CN105294771 A CN 105294771A CN 201510591038 A CN201510591038 A CN 201510591038A CN 105294771 A CN105294771 A CN 105294771A
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Abstract
The invention discloses an anionic type iridium complex for oxygen sensing, and a preparation method and the application of the anionic type iridium complex. The anionic type iridium complex can be expressed by a general formula: [Ir(C-N)2(CN)2]-nBuN+, wherein a counter ion is a tetrabutyl ammonium ion nBuN+; a C-N ligand is selected from 2-phenylpyridine (ppy), 2,4-difluoro phenylpyridine (dfppy), 2-thiophene-quinoline (thq), 2-phenyl-quinoline (bqu) and 1-phenylisoquinoline (piq), and a molecular structure formula of the C-N ligand is as shown in the description. A preparation process of the anionic type iridium complex is simple and is easy to operate. The anionic type iridium complex can be used in the field of the oxygen sensing and has higher response sensitivity on oxygen and better selectivity; the anionic type iridium complex can also be used in the field of bio-sensing, can be used for carrying out oxygen detection in a cell or a living body and has good biocompatibility; the anionic type iridium complex has the characteristics of long phosphorescence lifetime, large Stokes shift, high light stability and the like, has relatively-sensitive luminous intensity on the oxygen and is a good oxygen probe.
Description
Technical field
The invention belongs to transition metal complex and luminescent material technical field, be specifically related to a class and there is the preparation of the anionic complex of iridium of oxygen response and the application in cell marking, imaging and oxygen sensor field thereof.
Technical background
In recent years, because the heavy metal atom in transition metal complex (as iridium, platinum, osmium, ruthenium etc.) has d
6, d
8and d
10electronic structure, can spin-orbit cou-pling be increased, make original triplet state add the character of some singlet state, increase intersystem crossing ability, make the triplet excited state of spin forbidden to ground state transition T
1→ S
0become part to allow, phosphorescence can be launched smoothly, improve luminous efficiency, internal quantum efficiency can reach 100%, makes these title complexs be used to the fields such as OLED, electrochemiluminescence, photocell, chemical sensitisation and bioprobe more and more.In these heavy metal complexes, because the lifetime of excited state of complex of iridium is shorter, at room temperature there is very high luminous efficiency, and glow color easily regulates and controls, particularly long lifetime triplet excited state iridium complexes can effectively by energy trasfer to triplet oxygen, cause the generation of luminous cancellation and singlet oxygen, thus this characteristic of iridium complexes can be used to be made into the probe to oxygen sensitive, medical science can be used in, chemistry and environmental monitoring aspect.Therefore, iridium complexes receives more extensively more deep research.
Complex of iridium is mainly divided into small molecules complex of iridium, complex of iridium and polymer-doped, title complex to be connected on polymeric based sensor three class on polymer chain by covalent linkage as oxygen sensor.Wherein complex of iridium and polymer-doped, title complex are existed by the polymeric based sensor that covalent linkage is connected on polymer chain and synthesize difficulty, and stability is good not, easily produces and is separated, and assembles the problems such as quench luminescence and limits its application.Small molecules complex of iridium can be divided into again cationic, anionic and neutral complex of iridium, cationic and neutral complex of iridium reaction conditions in building-up process require harsh, productive rate is low but negatively charged ion complex of iridium synthesis condition gentle and productive rate is higher.
The invention provides a kind of anionic complex of iridium that can be used for oxygen sensor, and specifically illustrate preparation method and the application of this title complex.The synthesis of this anionic complex of iridium is simple, higher to oxygen remolding sensitivity, selectivity better and also its glow color can be regulated by the structure changing part, achieve excited by visible light and glow color from indigo plant to red transformation.
Summary of the invention
In view of there is above-mentioned technical problem in prior art, a class is the object of the present invention is to provide to have the anionic complex of iridium of highly sensitive, highly selective to oxygen, and the method for preparation, and this kind of title complex is proposed at oxygen sensor, the application in bio-imaging.The technical solution used in the present invention is as described below.
The invention provides a kind of anionic complex of iridium that can be used for oxygen sensor, the main part of described transition metal complex of iridium is (C^N) bidentate ligand, available general formula [Ir (C^N)
2(CN)
2]
-nBuN
+represent, its molecular structure is as shown in following molecular formula general formula, and wherein, counter ion are TBuA radical ion nBuN
+, C^N part is selected from 2-phenylpyridine (ppy), 2,4 difluorobenzene yl pyridines (dfppy), 2-thiophene-quinoline (thq), 2-phenyl-quinolin (bqu), 1-phenyl isoquinolin quinoline (piq).
General formula
In formula:
Thus, the concrete structure formula of described anionic complex of iridium is as shown in following molecular formula formula 1-5:
Present invention also offers the preparation method of above-mentioned anionic complex of iridium.The C^N part of described anionic complex of iridium can be selected from the one in 2-phenyl-pyridin (ppy), 2,4 difluorobenzene yl pyridines (dfppy), 2-thiophene-quinoline (thq), 2-phenyl-quinolin (bqu), 1-phenyl isoquinolin quinoline (piq).The concrete steps preparing described anionic complex of iridium are as follows:
(A) dimer complex of iridium (C^N)
2ir (μ-Cl)
2ir (C^N)
2synthesis: three hydrated iridium trichloride (IrCl
33H
2o) react with C^N part small molecules, reaction molar ratio is n (IrCl
33H
2o): n (ppy/dfppy/thq/bpu/piq)=1:2 ~ 1:3.Reaction solvent is the mixed solvent of ethylene glycol ethyl ether and water, and its volume ratio is V (cellosolvo): V (H
2o)=3:1 ~ 5:1.Temperature of reaction is 110 ~ 120 DEG C, and under nitrogen atmosphere, return stirring reaction 24 ~ 30 hours, generates to there being precipitation.Stopped reaction, at room temperature filtering-depositing, with water and alcohol flushing product.
(B) preparation of anionic complex of iridium: dimer complex of iridium obtained for step (A) and tetrabutyl ammonium cyanide (n-BuN (CN)) are reacted, reaction molar ratio is n (n-BuN (CN)): n ((C^N)
2ir (μ-Cl)
2ir (C^N)
2)=6:1 ~ 12:1, dissolves with methylene dichloride, temperature of reaction 30 ~ 50 DEG C, reaction times is 6-15h, use methylene dichloride and distilled water to extract, then carry out column chromatography, vacuum-drying, obtain complex of iridium, the structural formula of described complex of iridium is respectively as above-mentioned molecular formula formula 1,2,3,4, shown in 5.
The chemical equation of the preparation method of above-mentioned anionic complex of iridium is as follows:
In formula:
Above-mentioned anionic complex of iridium, when being applied to oxygen sensor field, is positioned in environment to be detected by described complex of iridium, and uses on fluorophotometer and measure its luminous intensity.
Described complex of iridium is when being applied in bio-sensing, and described complex of iridium can either carry out oxygen detection in cell, can also carry out oxygen detection in live body.And, described complex of iridium in cell can duration of service resolution techniques and imaging technique detect the luminous intensity of intracellular complex of iridium, serviceable time resolution techniques and background fluorescence signal distinguish the signal to noise ratio and sensitivity that improve and detect mutually, and being applied to bio-imaging can reduce background fluorescence.
Simultaneously, the structure of complex of iridium material and intermediate is characterized, by the photophysical property of ultra-violet absorption spectrum, this anionoid type complex of iridium of fluorescence emission spectrum testing research by nucleus magnetic resonance (NMR), chromaticness online (GCMS), Matrix Assisted Laser Desorption time-of-fight mass spectrometry (MALDI-TOF-MS) etc.
The technical solution used in the present invention has following beneficial effect: 1, the synthesis of described anionic complex of iridium is simple, higher to oxygen response remolding sensitivity, selectivity is better; 2, the glow color of described anionic complex of iridium can regulate by changing the structure of part, achieves excited by visible light and glow color from indigo plant to red transformation; 3, described anionic complex of iridium has abundant photophysical property, and serviceable time resolution techniques and background fluorescence signal distinguish the signal to noise ratio and sensitivity that improve and detect mutually, and being applied to bio-imaging can reduce background fluorescence.
Accompanying drawing explanation
The absorption spectrum of Fig. 1 anionoid type complex of iridium of the present invention in acetonitrile solution;
Fig. 2 anionoid type complex of iridium of the present invention emmission spectrum in acetonitrile solution;
Fig. 3 [Ir (ppy) of the present invention
2(CN)
2]
-nBuN
+oxygen spectra for titration in acetonitrile solution;
Fig. 4 [Ir (dfppy) of the present invention
2(CN)
2]
-nBuN
+oxygen spectra for titration in acetonitrile solution;
Fig. 5 [Ir (thq) of the present invention
2(CN)
2]
-nBuN
+oxygen spectra for titration in acetonitrile solution;
Fig. 6 [Ir (thq) of the present invention
2(CN)
2]
-nBuN
+imaging under air conditions in viable cell;
Fig. 7 [Ir (thq) of the present invention
2(CN)
2]
-nBuN
+imaging under 5% Oxygen Condition in viable cell.
Embodiment
Below by concrete enforcement, the present invention is further illustrated, but these specific embodiments do not limit the scope of the invention in any form.
The present embodiment raw material used is known compound, commercially can buy, or be synthesized by methods known in the art.
Embodiment 1, negatively charged ion complex of iridium [Ir (dfppy)
2(CN)
2]
-nBuN
+preparation.
(1) determine and prepare C^N part, determining that C^N part is 2,4 difluorobenzene yl pyridines (dfppy), can obtain according to preparation method existing in prior art.
The reaction formula preparing fluoro-2 phenylpyridines of monomer 2,4-bis-is as follows.
Detailed process is: take 2-bromopyridine (1.0g, 6.37mmol), 2,4-difluorobenzene boric acid (1.03g, 6.5mmol) He four (triphenyl phosphorus) palladium (0.370g, 0.32mmol) add in 50mL two-mouth bottle, vacuumize bulging nitrogen circulation three times, inject toluene (9mL), saturated K successively
2cO
3(aq) (3mL), ethanol (3mL), 80 DEG C are refluxed 15 hours.Be cooled to room temperature, use methylene dichloride and distilled water extraction, merge organic phase, decompression is spin-dried for, and obtains 1.12g product, productive rate 90%.
1HNMR(400MHz,DMSO)δ8.68(ddd,J＝4.8,1.7,0.9Hz,1H),7.96(td,J＝9.0,6.8Hz,1H),7.86(td,J＝7.8,1.8Hz,1H),7.75–7.70(m,1H),7.40–7.29(m,2H),7.22–7.14(m,1H)。
(2) negatively charged ion complex of iridium [Ir (dfppy)
2(CN)
2]
-nBuN
+preparation:
(A) dimer complex of iridium (C^N)
2ir (μ-Cl)
2ir (C^N)
2synthesis, i.e. the synthesis of the fluoro-2 phenylpyridine dichloro bridges of 2.4-bis-, its reaction formula is as follows:
Take IrCl
3 .3H
2fluoro-2 phenylpyridines (dfppy) (500mg, 2.62mmol) of O (419.0mg, 1.20mmol) and 2.4-bis-add in 50mL two-mouth bottle, vacuumize bulging nitrogen circulation three times.Inject ethylene glycol ethyl ether (9mL) and distilled water (3mL) with syringe, temperature of reaction is 110 DEG C, and under nitrogen atmosphere, return stirring reacts 24 hours, generates to there being precipitation.After stopped reaction, be cooled to room temperature, at room temperature filtering-depositing, suction filtration obtains greenish yellow solid, first uses 20mL distilled water flushing product, then uses 20mL alcohol flushing product, and carries out vacuum-drying.Obtain yellow-green colour product, productive rate 80%.
(B) preparation of anionic complex of iridium, i.e. [Ir (dfppy)
2(CN)
2]
-nBuN
+preparation, concrete chemical equation is as follows.
Take the fluoro-2 phenylpyridine dichloro bridge [Ir (dfppy) of 2.4-bis-
2(Cl)
2] (200mg, 0.16mmol) and tetrabutyl ammonium cyanide (515mg, 1.92mmol) add in 50mL two-mouth bottle, vacuumizes bulging nitrogen circulation three times.Inject 30mL methylene dichloride, temperature of reaction is 40 DEG C, and the return stirring reaction times is 15 hours.Be cooled to room temperature, use methylene dichloride and distilled water to extract, decompression is spin-dried for, and carries out column chromatography, and vacuum-drying, obtain greenish yellow solid 145mg, productive rate 51%.
1HNMR(400MHz,DMSO)δ9.53(dd,J＝5.8,1.0Hz,2H),8.20(t,J＝13.3Hz,2H),8.06–7.96(m,2H),7.43(ddd,J＝7.4,5.9,1.4Hz,2H),6.59(ddd,J＝12.8,9.4,2.4Hz,2H),5.52(dd,J＝8.2,2.4Hz,2H),3.11(dd,J＝21.5,13.0Hz,8H),1.53(dt,J＝15.7,8.0Hz,8H),1.34–1.22(m,8H),0.90(t,J＝7.3Hz,12H)。
Embodiment 2, negatively charged ion complex of iridium [Ir (ppy)
2(CN)
2]
-nBuN
+preparation:
(1) determine and prepare C^N part, determining that C^N part is 2-phenylpyridine (ppy), can obtain according to preparation method existing in prior art.
(2) negatively charged ion complex of iridium [Ir (ppy)
2(CN)
2] -nBuN
+preparation:
(A) dimer complex of iridium (C^N)
2ir (μ-Cl)
2ir (C^N)
2synthesis, i.e. the synthesis of 2-phenylpyridine dichloro bridge, concrete reaction is: take IrCl
3 .3H
2o (528mg, 1.50mmol) and 2-phenylpyridine (ppy) (864mg, 4.50mmol) add in 50mL two-mouth bottle, vacuumize bulging nitrogen circulation three times.Inject ethylene glycol ethyl ether (15mL) and distilled water (3mL) with syringe, temperature of reaction is 100 DEG C, and under nitrogen atmosphere, return stirring reacts 36 hours, generates to there being precipitation.After stopped reaction, be cooled to room temperature, at room temperature filtering-depositing, suction filtration obtains yellow solid, first uses 25mL distilled water flushing product, then uses 20mL alcohol flushing product, and carries out vacuum-drying.Obtain yellow product, productive rate 85%.
(B) preparation of anionic complex of iridium, i.e. [Ir (ppy)
2(CN)
2]
-nBuN
+preparation, concrete synthetic method is:.
Take 2-phenylpyridine dichloro bridge [Ir (ppy)
2(Cl)
2] (250mg, 0.23mmol) and tetrabutyl ammonium cyanide (376mg, 1.40mmol) add in 50mL two-mouth bottle, vacuumizes bulging nitrogen circulation three times.Inject 30mL methylene dichloride, temperature of reaction is 50 DEG C, and the return stirring reaction times is 15 hours.Be cooled to room temperature, use methylene dichloride and distilled water to extract, decompression is spin-dried for, and carries out column chromatography, and vacuum-drying, obtain yellow solid, productive rate 60%.
1HNMR(400MHz,DMSO-d
6)δ＝9.52(dd,J1＝0.8Hz,J2＝6.0Hz,2H)；8.07(d,J＝8.4Hz,2H)；7.89(dt,J1＝1.6Hz,J2＝7.6Hz,2H)；7.66(d,J＝7.6Hz,2H)；7.31(dt,J1＝5.6Hz,J2＝7.2Hz,2H)；6.73(dt,J1＝1.2Hz,J2＝6.8Hz,2H)；6.61(dt,J1＝1.2Hz,J2＝7.2Hz,2H)；6.08(dd,J1＝1.2Hz,J2＝7.6Hz,2H)；3.17-3.13(m,8H)；1.60-1.52(m,8H)；1.34-1.25(m,8H)；0.93(t,J＝7.6Hz,12H).
13CNMR(100MHz,DMSO-d
6)δ＝168.02；163.78；153.48；144.55；136.42；131.48；130.88；128.50；123.81；122.74；120.24；119.14；57.71；23.21；19.36；13.64.
Embodiment 3, negatively charged ion complex of iridium [Ir (thq)
2(CN)
2]
-nBuN
+preparation.
(1) determine and prepare C^N part, determining that C^N part is 2-thiophene quinoline (thq), can obtain according to preparation method existing in prior art.
(2) negatively charged ion complex of iridium [Ir (thq)
2(CN)
2]
-nBuN
+preparation:
(A) dimer complex of iridium (C^N)
2ir (μ-Cl)
2ir (C^N)
2synthesis, i.e. the synthesis of 2-thiophene-quinoline dichloro bridge, its concrete synthetic method is: take IrCl
3 .3H
2o (500mg, 1.42mmol) and 2-thiophene-quinoline (thq) (600.0mg, 2.84mmol) adds in 50mL two-mouth bottle, vacuumizes bulging nitrogen circulation three times.Inject ethylene glycol ethyl ether (12mL) and distilled water (4mL) with syringe, temperature of reaction is 120 DEG C, and under nitrogen atmosphere, return stirring reacts 36 hours, generates to there being precipitation.After stopped reaction, be cooled to room temperature, at room temperature filtering-depositing, suction filtration obtains red solid, first uses 20mL distilled water flushing product, then uses 20mL alcohol flushing product, and carries out vacuum-drying.Obtain red product, productive rate 75%.
(B) preparation of anionic complex of iridium, i.e. [Ir (thq)
2(CN)
2]
-nBuN
+preparation, concrete synthetic method is:
Take 2-thiophene-quinoline dichloro bridge [Ir (thq)
2(Cl)
2] (300mg, 0.23mmol) and tetrabutyl ammonium cyanide (978mg, 2.78mmol) add in 50mL two-mouth bottle, vacuumizes bulging nitrogen circulation three times.Inject 30mL methylene dichloride, temperature of reaction is 30 DEG C, and the return stirring reaction times is 6 hours.Be cooled to room temperature, use methylene dichloride and distilled water to extract, decompression is spin-dried for, and carries out column chromatography, and vacuum-drying, obtain red solid, productive rate 65%.
1HNMR(400MHz,CDCl
3)δ＝9.99(d,J＝9.2Hz,2H)；7.97(d,J＝8.4Hz,2H)；7.68-7.65(m,4H)；7.60(d,J＝8.4Hz,2H)；7.42(t,J＝7.2Hz,2H)；7.03(d,J＝4.4Hz,2H)；6.09(d,J＝4.4Hz,2H)；3.11-3.07(m,8H)；1.47-1.39(m,2H)；1.11-1.06(m,2H)；0.77(t,J＝7.6Hz,12H).
13CNMR(100MHz,DMSO)δ＝170.91；166.82；149.43；140.58；138.80；132.64；130.38；130.31；130.29；129.68；128.17；125.52；125.15；117.13；57.54；23.07；19.23；13.52。
The absorption spectrum of anionic complex of iridium obtained in embodiment 1-3 in acetonitrile solution and emmission spectrum are as depicted in figs. 1 and 2, visible, three kinds of anionic complex of iridium can excite in visible-range, and the radiative wave band inspired of three is different, and luminescence also color is different.
Embodiment 4, oxygen titration experiments:
Three kinds of anionic complex of iridium obtained in embodiment 1-3 are mixed with finite concentration, get 2.5ml solution and in cuvette, pass into oxygen and nitrogen respectively and volume fraction shared by oxygen is respectively: 2.5%, 5%, 10%, 21%, 100%, fluorophotometer is surveyed its luminous intensity, and its spectra for titration as in Figure 3-5.As seen from the figure, three kinds of anionic complex of iridium are in different oxygen content situation, all very sensitive to the response of oxygen, and when different oxygen contents, its luminous intensity is different, can judge the content of oxygen according to luminous intensity.
Embodiment 5, viable cell imaging experiment:
The complex of iridium of preparation in embodiment 3 is mixed with the solution of 5mmol/L, pipettes 2 μ L solution and make its concentration dilution to 10 μM to 2mLPBS buffered soln.Use PBS buffer solution for cleaning 3 times after getting 2mL solution incubated cell 45min, collect corresponding luminescence band with 405nm wavelength activated cell co-focusing imaging.Test data shows: ionic type iridium complex has good Cell permeable, is distributed in cytosolic domain.Then be placed in incubator and pass into a certain proportion of nitrogen and oxygen mixed gas cultivation 1h, then collect corresponding luminescence band with cell co-focusing imaging.Accompanying drawing 6 and 7 is the imaging results of this anionic complex of iridium in viable cell under different oxygen content condition respectively.
Claims (5)
1. can be used for an anionic complex of iridium for oxygen sensor, it is characterized in that, described complex of iridium has following structural formula:
Wherein, counter ion are tetrabutylam-monium salt radical ion nBuN
+, C^N part is selected from 2-phenylpyridine, 2,4 difluorobenzene yl pyridines, 2-thiophene-quinoline, 2-phenyl-quinolin, 1-phenyl isoquinolin quinoline.
2. the preparation method of a complex of iridium as claimed in claim 1, the C^N part of described complex of iridium can be selected from 2-phenylpyridine, 2,4-difluorophenyl pyridinato, 2-thiophene-quinoline, 2-phenyl-quinolin, 1-phenyl isoquinolin quinoline, it is characterized in that, the concrete steps preparing described complex of iridium are as follows:
(A) dimer complex of iridium (C^N)
2ir (μ-Cl)
2ir (C^N)
2synthesis: three hydrated iridium trichloride and C^N part small molecules react, and molar ratio is n (IrCl
33H
2o): n (ppy/dfppy/thq/bqu/piq)=1:2 ~ 1:3, reaction solvent is the mixed solvent of ethylene glycol ethyl ether and water, and its volume ratio is V (cellosolvo): V (H
2o)=3:1 ~ 5:1, temperature of reaction is 100 ~ 120 DEG C, and under nitrogen atmosphere, stirring reaction 24 ~ 36 hours, generates to there being precipitation; Stopped reaction, at room temperature filtering-depositing, with water and alcohol flushing product;
(B) preparation of described anionic complex of iridium: dimer complex of iridium obtained for step (A) and tetrabutyl ammonium cyanide are reacted, reaction molar ratio is n (n-BuN (CN)): n ((C^N) 2Ir (μ-Cl) 2Ir (C^N) 2)=6:1 ~ 12:1, dissolve with methylene dichloride, temperature of reaction 30 ~ 50 DEG C, reaction times is 6-15h, with water and dichloromethane extraction, through column chromatography, vacuum-drying, obtains anionic complex of iridium.
3. the application of anionic complex of iridium as claimed in claim 1 in oxygen sensor, is characterized in that, is positioned in environment to be detected by described anionic complex of iridium, and uses on fluorophotometer and measure its luminous intensity.
4. the application of class anionic complex of iridium as claimed in claim 1 in bio-sensing, it is characterized in that, described complex of iridium can either carry out oxygen detection in cell, also can carry out oxygen detection in live body.
5. an application for anionic complex of iridium as claimed in claim 1, is characterized in that, such complex of iridium in cell by oxygen in TIME RESOLVED TECHNIQUE and image checking cell.
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| CN110857311A (en) * | 2018-08-12 | 2020-03-03 | 南京大学 | Ring metal iridium complex with tumor hypoxia sensing and optical activity and application thereof |
| CN113912650A (en) * | 2021-10-19 | 2022-01-11 | 苏州科技大学 | Fluorescent probe, method, composition and detection product for carbendazim residue detection |
| CN113912650B (en) * | 2021-10-19 | 2023-08-25 | 苏州科技大学 | Fluorescent probe, method, composition and detection product for detecting carbendazim residues |
| CN116396337A (en) * | 2023-04-01 | 2023-07-07 | 大连理工大学 | Preparation method and application of cationic cyclometallated iridium complex with oxygen sensitivity |
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