CN1087745C - Composite photosensing agnet of eosin-dipyridine ruthonium and its synthesis process and application - Google Patents
Composite photosensing agnet of eosin-dipyridine ruthonium and its synthesis process and application Download PDFInfo
- Publication number
- CN1087745C CN1087745C CN99119650A CN99119650A CN1087745C CN 1087745 C CN1087745 C CN 1087745C CN 99119650 A CN99119650 A CN 99119650A CN 99119650 A CN99119650 A CN 99119650A CN 1087745 C CN1087745 C CN 1087745C
- Authority
- CN
- China
- Prior art keywords
- eosin
- ruthonium
- agnet
- dipyridine
- photosensing
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Pyridine Compounds (AREA)
Abstract
The present invention belongs to the field of photosensitizer of chemical reaction. The general formula of a structure of a target compound is disclosed in the specification, wherein R is substituent radicals, such as methyl, ethyl, propyl, or butyl, etc., of low grade fat alkane. The target compound is synthesized by two steps: step one: preparing eosin-alkyl radical bipyridine compounds (EO-I) of which the yield is from 0.30 to 0.20 with I from I1 to I4 (the substitute radicals are from methyl to butyl); step two: preparing the target compound of which the yield is from 0.80 to 0.73. The sensitizing capability of the target compound is higher than the traditional single photosensitizer and the mixture of the photosensitizer. The present invention can be used as efficient photosensitizer to sensitizing and discolour a large pi conjugated system such as substitute anthracene.
Description
The invention belongs to the photosensitizers field of chemical reaction, particularly relate to composite photosensing agnet of eosin-dipyridine ruthonium and preparation method and use thereof.
Photosensitizers is that a class can make the chemical reaction that can not carry out originally carry out, and the reaction that perhaps can make some be difficult to carry out can be carried out under comparatively gentle condition, perhaps can change the approach of reaction and result's compound.Because of its consumption seldom (0.1-1% of reactant), can act on reactant repeatedly, so in a sense, photosensitizers can be regarded as uses up the catalyzer that is energized into excited state.
Eosin (English name Eosin, its disodium salt is called Eosin Y, is code name with EO below) is a kind of village dyestuff that accounts for, and chemical structure is as follows:
The eosin of excited state has suitable singlet state and triplet state distributes, its fluorescence quantum yield Φ
F=0.48, pass through quantum yield Φ between being
ISC=0.32, the report of this respect is referring to " photochemistry and photo bio magazine, A collects ", 1989, the 47th volume, 203-212 page or leaf (Tao SHEN, Zhan-gong ZHAO, Qun YU, Hui-jun XU:Photosensitized Reduction ofBenzil by Heteroatom-Containing Anthracene Dyes, J.Photochem.Photobiol., A, 1989,47,203-212.) article, so it is a kind of widely used sensitizing agent.For example, people such as Zhao Zhangong, Shen Tao is at " Chinese chemical wall bulletin ", nineteen ninety, the first roll, 19-20 page or leaf (Zhan-gong ZHAO, Tao SHEN:Synthesis of Benzoins by DyePhotosensitization, Chinese Chem.Letters, 1990,1,19-20.) show that (benzil BL) can not be with triethylamine (Et in methyl alcohol (MeOH) for benzil in the article delivered
3N) directly reduction, but as add 0.1% eosin or other band heavy atom account for the village dyestuff, (Vis) excites photosensitizers with visible light, benzil just can by triethylamine be reduced into quantitatively st-yrax (benzoin, BN).
Research shows that also this is to carry out sensitization by the triplet state of photosensitizers.
In addition, " materials chemistry magazine ", 1998, the 8th volume, the 9th phase, the article of 2055-60 page or leaf (Bing-wen JING, Hong ZHANG, Man-hua ZHANG, Tao SHEN:Ruthenium (II) ThiocyanateComplexes containing 4 '-(4-Phosphonato-phenyl)-2,2 ': 6 ' 2 "-and terpyridine:Synthesis, photophysicsand photosensitization to nanocrystalline TiO
2Electrodes.J.Materials Chem., 1998,8 (9), 2055-60.) report, bipyridyl ruthenium class dyestuff (is code name with RU) is highly stable, and extinction haves a wide reach, quite long lifetime of excited state is at room temperature just arranged, and also is the very good photosensitizers of a class.
But the binary compound (EO-RU) of eosin (EO) and bipyridyl ruthenium class dyestuff (RU) chemical bond-linking yet there are no report as photosensitizers at present.
The object of the present invention is to provide a class composite photosensing agnet of eosin-dipyridine ruthonium and a preparation method and use thereof, the equal proportion mixture of its sensitization energy force rate eosin (EO), bipyridyl ruthenium class dyestuff (RU) itself or eosin (EO) and bipyridyl ruthenium class dyestuff (RU) all much higher (concrete data are seen advantage and effect part).
The structure of composite photosensing agnet of eosin-dipyridine ruthonium of the present invention (EO-RU) is as follows:
Wherein, R is the substituting group of lower aliphatic alkanes, as methyl, ethyl, propyl group or butyl etc.The synthetic route of composite photosensing agnet of eosin-dipyridine ruthonium of the present invention (EO-RU) is as follows:
Wherein, (I) be the general formula of intermediate, R is the substituting group of lower aliphatic alkanes, as methyl (intermediate is called I1), ethyl (I2), propyl group (I3) or butyl (I4) etc.; Ru (bp)
2.2H
2O is two hydration dichloride bipyridyl rutheniums.
The synthetic of composite photosensing agnet of eosin-dipyridine ruthonium of the present invention (EO-RU) undertaken by following step:
The first step: the preparation of eosin-alkyl bipyridyliums compound (EO-I):
With eosin disodium salt (molecular formula C
20H
6Br
4Na
2O
5Molecular weight 692, be called EO), 4-brooethyl-4 '-R base-2,2 '-dipyridyl (being called intermediate compound I) is with 1: 0.9～1: 1 mixed of mol ratio, and be that 0.72 times anhydrous sodium carbonate of eosin disodium salt (EO) weight is dissolved in an amount of solvent dimethyl formamide (DMF) to dissolving fully with weight, heat up then, reacted 5-10 hour down at 80-100 ℃, remove the dimethyl formamide (DMF) that desolvates then, obtain dark red solid, thoroughly wash with suitable quantity of water,, again the solid that obtains is separated with silica gel column chromatography to remove unreacted eosin disodium salt (EO), make leacheate with chloroform/methanol, its volume ratio is 3/1, obtains eosin-alkyl bipyridyliums compound (EO-I), and productive rate is 0.30-0.20.
Second step: the preparation of composite photosensing agnet of eosin-dipyridine ruthonium (EO-RU):
With eosin-alkyl bipyridyliums compound (EO-I) and two hydration dichloride bipyridyl ruthenium [molecular formula C
20H
16Cl
2N
4O
2Ru, molecular weight 516] etc. mixed in molar ratio, and to be dissolved in volume ratio be in 3: 1 the mixed solution of second alcohol and water, to reflux under nitrogen protection and stirred 3-4 hour; Filter then to remove insolubles, using molecular sieve type column chromatography for separation, leacheate after gained filtrate concentrates is the acetone that contains 0.1M NaCl, and its volume ratio is 3/1; Collect red effluent liquid, obtain final product composite photosensing agnet of eosin-dipyridine ruthonium (EO-RU) after further handling, along with I (substituting group is from methyl to the butyl) from I1 to I4, productive rate from 0.80 to 0.73.
Wherein, the molecular sieve type post is a Sephadex-C-25 type chromatography column.
With 9,10-diphenylanthrancene (DPA) is a probe, under the oxygen saturated conditions, uses the rayed greater than the 510nm wavelength, and under the effect of various photosensitizerss, the result of fading of DPA is compared to table 1.
Table 1: with 9,10-diphenylanthrancene (DPA) is a probe, the sensitization of the various sensitizing agents result of fading
In the table, A is illumination when beginning, the absorbancy that DPA is original, A
0Be the absorbancy of DPA after the illumination, (A
0-A) absorbancy for reducing after the illumination, (A
0-A)/A
0Be the ratio that absorbancy after the illumination reduces, the rate of promptly fading.EO-RU represents target compound composite photosensing agnet of eosin-dipyridine ruthonium of the present invention, the model compound eosin ethyl ester that EOEt representative and target compound EO-RU compare, RU represents another model compound bipyridyl ruthenium, (EOEt+RU) represent the equal proportion mixture of eosin ethyl ester and bipyridyl ruthenium dye, RB represents typical triplet state sensitizing agent rose bengal.As can be seen from Table 1, the sensitization efficient of complex photosensitizer of the present invention be single photosensitizers (comprising best rose bengal) or its mixture 4-5 doubly.
| (A 0-A)/A 0 | EOEt | EOEt+RU | RB | EO-RU |
| After 10 minutes | 0.06 | 0.06 | 0.07 | 0.32 |
| Relative ratio 1 | 1.0 | 5.3 | ||
| Relative ratio 2 | 1.0 | 5.3 | ||
| Relative ratio 3 | 1.0 | 4.6 | ||
| After 20 minutes | 0.10 | 0.12 | 0.14 | 0.54 |
| Relative ratio 1 | 1.0 | 5.4 | ||
| Relative ratio 2 | 1.0 | 4.5 | ||
| Relative ratio 3 | 1.0 | 3.9 |
Using above-mentioned working method, is photosensitizers with EO-RU, and to different compounds, the result that sensitization is faded is also different.The order of its validity is as follows:
9,10-dimethylanthracene (DMA)＞9-methyl anthracene (MA)＞9,10-diphenylanthrancene (DPA)＞anthracene (An)＞9,10-two chrloroanthracenes (DCA)～9,10-dibromoanthracene (DBA)～9-anthraldehyde (An-CHO)～9-anthroic acid (An-COOH).
Illustrate that this class complex photosensitizer also has certain range of application.Electron density on the anthracene nucleus is high more, and the effect that sensitization is faded is good more.Wherein to 9,10-dimethylanthracene (DMA), 9-methyl anthracene (MA), 9, the sensitization result of 10-diphenylanthrancene (DPA) is compared to table 2.
Table 2: with EO-RU is photosensitizers, to 9, and 10-dimethylanthracene (DMA), 9-methyl anthracene (MA), 9, the sensitization of 10-diphenylanthrancene (DPA) is faded the result relatively
| (A 0-A)/A 0 | DPA | MA | DMA |
| After 10 minutes | 0.03 | 0.07 | 0.46 |
| After 20 minutes | 0.10 | 0.15 | 0.69 |
We have also done the controlled trial of most typical triplet state photosensitizers rose bengal (Rose Bengal is called RB).One of characteristics of triplet state sensitizing agent are to form the extremely strong creating singlet oxygen by using of oxidation capacity with airborne oxygen, and this is the important channel that the oxidation of organic compounds that much has big pi-conjugated system is faded.
Formation singlet excited under ground state sensitizing agent (S) illumination (h ν) (
1S), between being, pass through (ISC), to triplet excited state (
3S), with oxygen (O
2) effect, the formation creating singlet oxygen by using (
1O
2), reactant (A) is faded.Can be schematically as follows:
In acetonitrile, use the RB sensitization, illumination 15 minutes, the rate of fading of diphenylanthrancene is 9.9%; It is 39.4% that similarity condition is used EO-RU sensitization, the rate of fading of diphenylanthrancene down, is 4 times of RB approximately.We know that the creating singlet oxygen by using quantum yield of RB is 0.76; The creating singlet oxygen by using quantum yield of EO-RU when exciting EO is that 0.54 (Wang Bojie surveys with spectrography abroad, detailed method is seen Bojie WANG, P.R.Ogiby, physical chemistry magazine (J.Phys.Chem.), 1993,97 volumes, 38 phases, the 9593-9598 page or leaf), though higher than EO itself (0.32), but not as good as RB.In view of this, the hyperreaction of EO-RU can be affirmed reason in addition.
For this reason, we have compared the photosensitive property of EO-RU in various solvent.In polar solvent, the photosensitive speed of EO-RU is than faster in non-polar solvent.As in non-polar solvent benzene, in the presence of EO-RU, use radiation of visible light 15 minutes, the rate of fading of dimethylanthracene is 42.4%; And in the polar acetonitrile, under the similarity condition, the rate of fading of dimethylanthracene can reach 96.1%, is 2.3 times in benzene.Diphenylanthrancene for another example, under the similarity condition, the rate of fading in benzene is 4.6%; And the rate of fading 39.4% in acetonitrile is 8.6 times (seeing Table 3) in benzene.
Table 3: dimethylanthracene and the diphenylanthrancene rate of fading in benzene and in acetonitrile
EO-RU is a binary compound, and transfer transport very easily takes place under illumination.Polar solvent then is the prerequisite of transfer transport.Top data have effectively been supported in the sensitizing of EO-RU, the possibility that photic transfer transport participates in.
| In benzene | In acetonitrile | |
| The rate of fading of dimethylanthracene | 42.4 | 96.1 |
| The rate of fading relatively | 1 | 2.3 |
| The rate of fading of diphenylanthrancene | 4.6 | 39.4 |
| The rate of fading relatively | 1 | 8.6 |
For example, positive ion has very strong oxidation capacity, and it also can make the reactant oxidation fade, and this understands on the other hand that also the high electron density on the anthracene nucleus why helps sensitized reaction.One photosensitizers can not have this effect.This is exactly the basic reason of the efficient sensitization of complex photosensitizer probably.
The invention provides the photosensitizers that a class has high sensitization efficient, be composite photosensing agnet of eosin-dipyridine ruthonium, the equal proportion mixture of its sensitization energy force rate eosin (EO), bipyridyl ruthenium class dyestuff (RU) itself or eosin (EO) and bipyridyl ruthenium class dyestuff (RU) is all much higher.Can be used as photosensitizers efficiently, big pi-conjugated system (as the anthracene class that replaces) sensitization is faded.
Further describe the present invention below in conjunction with embodiment:
Embodiment 1
R is that composite photosensing agnet of eosin-dipyridine ruthonium (EO-RU) synthetic method of methyl is as follows:
The first step: the method for making of eosin-alkyl bipyridyliums compound (EO-I1):
I1 (4-brooethyl-4 '-methyl-2,2 '-dipyridyl, molecular formula C
12H
11BrN
2, molecular weight 263) and 1.8mmol (474mg), eosin disodium salt (molecular formula C
20H
6Br
4Na
2O
5, molecular weight 692) and 2mmol (1384mg), the 1g anhydrous sodium carbonate, and 20mlDMF is at 90 ℃ of reactions 5 hours, pressure reducing and steaming solvent then.Gained dark red solid water thoroughly washs to remove unreacted eosin disodium salt, again with the solid silica gel column chromatography that obtains, and chloroform/methanol (volume ratio: 3/1) make leacheate, get pure products EO-I1 (molecular formula C
32H
17Br
4N
2NaO
5, molecular weight 852) and 460mg (0.54mmol), productive rate 0.30.
IR(KBr)：ν
max(C＝O)＝1720cm
-1；
1HNMR(d
6-DMSO)：2.39(s，3H)，5.22(s，2H)，6.93(s，2H)，7.25(d，1H)，7.52(d，1H)，7.82-7.94(m，3H)，8.18-8.32(m，3H)，8.50(m，2H)；
Molecular formula: C
32H
7N
2O
5Br
4Na,
Ultimate analysis: theoretical value: C:45.08%, H:2.01%, N:3.28%,
Observed value: C:44.78%, H:2.34%, N:3.14%.
Second step: the method for making of composite photosensing agnet of eosin-dipyridine ruthonium (EO-RU):
EO-I1 (molecular formula C
32H
17Br
4N
2NaO
5, molecular weight 852) and 0.2mmol (170mg), Ru (bp)
2Cl
22H
2O (molecular formula C
20H
16Cl
2N
4O
2Ru, molecular weight 516) 0.2mmol (103mg), 30ml ethanol, 10ml water, nitrogen protection refluxes down and stirs 3h.The reaction after-filtration is removed insolubles, and filtrate concentrates back Sephadex-C-25 column chromatography, and (volume ratio: 3/1) the solution ripples is washed with the acetone of the NaCl that contains 0.1M.The red effluent liquid that contains product is concentrated to 20ml, and it is saturated to be added dropwise to 20ml
NaClO
4In the aqueous solution, separate out red precipitate immediately.Filter, with cold water, ether washing, get final product composite photosensing agnet of eosin-dipyridine ruthonium (EO-RU) (molecular formula C after the drying respectively
52H
29Br
4Cl
2N
6NaO
5Ru, molecular weight 1332) 211mg (0.16mmol), productive rate 0.80.
Vis：462nm(ε＝2×10
4M
-1cm
-1)，542nm(ε＝9.5×10
4M
-1cm
-1)；
IR(KBr)：ν
max(C＝O)＝1725cm
-1；
1HNMR(CD
3CN)：2.46(s，3H)，5.16(s，2H)，7.06(s，2H)，7.18-7.21(m，1H)，7.30-7.90(m，4H)，8.00-8.15(m，4H)，8.20-8.40(m，3H)，8.47-8.70)；
Molecular formula: C
52H
33N
6O
13Br
4Cl
2RuNa2H
2O,
Ultimate analysis: theoretical value: C:41.62%, H:2.48%, N:5.60%;
Observed value: C:41.87%, H:2.62%; N:5.37%.
Embodiment 2
Because the first step is lower by the productive rate that condensation obtains EO-I1, some reaction conditions tests have been done.
Press embodiment 1, when temperature of reaction remained on 80 ℃, productive rate dropped to 0.22.
Embodiment 3
Temperature of reaction is brought up to 100 ℃, and reaction yield does not improve yet.
Embodiment 4
Press embodiment 1, the reaction times extends to 10 hours, and the productive rate of condensation does not increase.
Embodiment 5
Press embodiment 1, but I1 2mmol (474mg), remaining pharmaceutical chemicals consumption is all identical with embodiment 1 with working method, gets pure products EO-I1 383mg, productive rate 0.25.I1 has increased than embodiment 1, and the productive rate of EO-I1 has descended on the contrary.This may be because the I1 of equal proportion has also increased the chance that connects I1 on the both sides of eosin disodium salt.
Embodiment 6
Press the synthesis step of embodiment 1, (R is an ethyl to I1, molecular formula C with I2
13H
13BrN
2, molecular weight 291) and 524mg (1.8mmol) replacement, remaining pharmaceutical chemicals consumption is all identical with embodiment 1 with working method, gets pure products EO-I2 (molecular formula C
33H
19Br
4N
2NaO
5. molecular weight 880) 440mg (0.50mmol), productive rate 0.28.
Embodiment 7
Press the synthesis step of embodiment 1, (R is a propyl group to I1, molecular formula C with I3
14H
15BrN
2, molecular weight 319) and 574mg (1.8mmol) replacement, remaining pharmaceutical chemicals consumption is all identical with embodiment 1 with working method, gets pure products EO-I3 (molecular formula C
34H
21Br
4N
2NaO
5. molecular weight 908) 409mg (0.45mmol), productive rate 0.25.
Embodiment 8
Press the synthesis step of embodiment 1, (R is a butyl to I1, molecular formula C with I4
15H
17BrN
2, molecular weight 347) and 625mg (1.8mmol) replacement, remaining pharmaceutical chemicals consumption is all identical with embodiment 1 with working method, gets pure products EO-I4 (molecular formula C
35H
23Br
4N
2NaO
5. molecular weight 936) 337mg (0.36mmol), productive rate 0.20.
All appraising datums are also similar to the final compound of embodiment 1, and difference has had more three peaks on nuclear magnetic resonance map, and they are: 1.3 (m, 2H), 1.6 (m, 2H), 2.6 (t, 2H), that is respectively to belong to three methylene radical replacing butyl.
From top example as can be seen, for intermediate (I), the R group is big more, and the productive rate of condensation reaction is low more.This may be the increase of R group, has hindered the carrying out of condensation reaction.
Embodiment 9
As for the complex reaction of second step with two hydration dichloride bipyridyl rutheniums, the variation of various intermediate reactions is little, and productive rate is between 0.73-0.80.This may be that the R group is from hapto cause far away.Consider controlled step that neither be main from the angle of overall yield.
Claims (4)
1. a class composite photosensing agnet of eosin-dipyridine ruthonium is characterized in that the general structure of described photosensitizers is as follows:
Wherein, R is methyl, ethyl, propyl group or butyl.
2. the synthetic method of a class composite photosensing agnet of eosin-dipyridine ruthonium according to claim 1 is characterized in that being undertaken by following step:
(1). the preparation of eosin-alkyl Bipyridine compound:
With the eosin disodium salt, 4-brooethyl-4 '-R base-2,2 '-dipyridyl is with the mixed of mol ratio 1/0.9-1/1, and be that 0.72 times anhydrous sodium carbonate of eosin disodium salt weight is dissolved in the solvent dimethyl formamide to dissolving fully with weight, heat up then, reacted 5-10 hour down at 80-100 ℃, remove the dimethyl formamide that desolvates then, obtain dark red solid, water washs, to remove unreacted eosin disodium salt, again the solid that obtains is separated with silica gel column chromatography, be that 3: 1 chloroform/methanol is done leacheate drip washing with volume ratio, obtain eosin-alkyl Bipyridine compound
(2). the preparation of composite photosensing agnet of eosin-dipyridine ruthonium:
With mixed in molar ratio such as eosin-alkyl bipyridyl ruthenium class mixture and two hydration dichloride bipyridyl rutheniums, and be dissolved in the mixed solution that volume ratio is 3/1 second alcohol and water, under nitrogen protection, reflux and stirred 3-4 hour; Filter then to remove insolubles, using molecular sieve type column chromatography for separation, leacheate after gained filtrate concentrates is the acetone that contains 0.1MNaCl, and its volume ratio is 3/1; Collect red effluent liquid, obtain the final product composite photosensing agnet of eosin-dipyridine ruthonium after further handling.
3. the synthetic method of a class composite photosensing agnet of eosin-dipyridine ruthonium as claimed in claim 2 is characterized in that the molecular sieve type post is a Sephadex-C-25 type chromatography column.
4. the purposes of a class composite photosensing agnet of eosin-dipyridine ruthonium according to claim 1 is characterized in that: photosensitive the fading that is used for big pi-conjugated system dimethylanthracene, diphenylanthrancene etc.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99119650A CN1087745C (en) | 1999-09-24 | 1999-09-24 | Composite photosensing agnet of eosin-dipyridine ruthonium and its synthesis process and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99119650A CN1087745C (en) | 1999-09-24 | 1999-09-24 | Composite photosensing agnet of eosin-dipyridine ruthonium and its synthesis process and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1289776A CN1289776A (en) | 2001-04-04 |
| CN1087745C true CN1087745C (en) | 2002-07-17 |
Family
ID=5281014
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99119650A Expired - Fee Related CN1087745C (en) | 1999-09-24 | 1999-09-24 | Composite photosensing agnet of eosin-dipyridine ruthonium and its synthesis process and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1087745C (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105936560A (en) * | 2016-05-24 | 2016-09-14 | 安徽普氏生态环境工程有限公司 | Method for degrading sewage based on dye photooxidation and visible light catalytic oxidation |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1989002072A1 (en) * | 1987-09-03 | 1989-03-09 | Terumo Kabushiki Kaisha | Method and apparatus for optically measuring concentration of material |
-
1999
- 1999-09-24 CN CN99119650A patent/CN1087745C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1989002072A1 (en) * | 1987-09-03 | 1989-03-09 | Terumo Kabushiki Kaisha | Method and apparatus for optically measuring concentration of material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1289776A (en) | 2001-04-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111995580B (en) | Fluorescent dye with tetraphenyl ethylene imidazole ring structure and application thereof | |
| CN112592360A (en) | Amphiphilic aza-BODIPY near-infrared dye and preparation method thereof | |
| CN111825634B (en) | Novel compounds, process for their preparation and their use | |
| CN103172650A (en) | Strong fluorescence fluoro-boron dipyrrole compound containing triphenylamine structure as well as preparation method and application thereof | |
| CN110305026B (en) | Solid fluorescent dye and preparation method thereof | |
| CN105753892A (en) | Water-soluble BODIPY (boron-dipyrromethene) derivatives with different hydrophobic chains and preparation method of water-soluble BODIPY derivatives | |
| CN1087745C (en) | Composite photosensing agnet of eosin-dipyridine ruthonium and its synthesis process and application | |
| CN105837568B (en) | A kind of fluorenyl β carbolines class compound, its application and preparation method as luminous organic material and aggregation inducing Fluorescence Increasing material | |
| CN1101929A (en) | Fluorescent dye with double chromogens and preparing process thereof | |
| CN106632262B (en) | Triaryl pyridine derivate and the preparation method and application thereof of the one kind containing carbazole skelton | |
| CN101225240A (en) | Conjugated benzophenone-containing triphenylamine dyes as well as synthesis and uses thereof | |
| CN113501836A (en) | Star BODIPY near-infrared fluorescent dye and preparation method thereof | |
| CN101037392A (en) | Naphthalin-triphenylamine branch-shaped molecule with strong double-photon absorption characteristic | |
| CN108558595B (en) | P-phenylene ethylene bridged trimer indene derivative and preparation method thereof | |
| CN113480550B (en) | Bishydroxycoumarin conjugated porphyrin derivative and preparation method thereof | |
| CN111171004B (en) | (E) Preparation method of 2- (2- (9-alkyl) carbazole-3-) vinyl-benzimidazole | |
| CN101838475A (en) | P-nitryl diphenylethylene dye sensitizing agent containing bromine as well as synthesis and application thereof | |
| CN115232161B (en) | Trimerdanyl-BODIPY-perylene diimide ternary system molecule and preparation method thereof | |
| CN116102740B (en) | Photosensitive photoluminescent supermolecule nanoparticle, and preparation method and application thereof | |
| CN101624407A (en) | Benzene ligand ferrocenium salt cationic photoinitiators containing carbazole and pendant carbazole ether group and a preparation method thereof | |
| CN113292585B (en) | BODIPY-benzothiadiazole-porphyrin-carbazole quaternary system linear compound and preparation method thereof | |
| CN113968881B (en) | Mitochondrial targeting light activated fluorescence imaging compound and preparation method and application thereof | |
| CN113061128B (en) | Photosensitizer with aggregation-induced light emission and broad-spectrum absorption characteristics and preparation method and application thereof | |
| Yan et al. | Synthesis, structures, and properties of two new two-photon photopolymerization initiators | |
| CN113845915B (en) | Photosensitive material for enhancing up-conversion of rare earth doped nanometer and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| REG | Reference to a national code |
Ref country code: HK Ref legal event code: GR Ref document number: 1068667 Country of ref document: HK |