CN111825603B - Ruthenium polypyridine complex and preparation method and application thereof - Google Patents
Ruthenium polypyridine complex and preparation method and application thereof Download PDFInfo
- Publication number
- CN111825603B CN111825603B CN201910313344.0A CN201910313344A CN111825603B CN 111825603 B CN111825603 B CN 111825603B CN 201910313344 A CN201910313344 A CN 201910313344A CN 111825603 B CN111825603 B CN 111825603B
- Authority
- CN
- China
- Prior art keywords
- ruthenium
- complex
- bipyridine ligand
- preparation
- rucl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 229910052707 ruthenium Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000010668 complexation reaction Methods 0.000 title description 2
- 239000002253 acid Substances 0.000 claims abstract description 21
- 125000004424 polypyridyl Polymers 0.000 claims abstract description 13
- 239000003446 ligand Substances 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- 238000005286 illumination Methods 0.000 claims description 16
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 16
- 238000010992 reflux Methods 0.000 claims description 15
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- 229910052736 halogen Inorganic materials 0.000 claims description 9
- 150000002367 halogens Chemical class 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 5
- 150000001450 anions Chemical class 0.000 claims description 4
- 229910020366 ClO 4 Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 abstract description 7
- 239000002994 raw material Substances 0.000 abstract description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 229920002120 photoresistant polymer Polymers 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- HLLSOEKIMZEGFV-UHFFFAOYSA-N 4-(dibutylsulfamoyl)benzoic acid Chemical compound CCCCN(CCCC)S(=O)(=O)C1=CC=C(C(O)=O)C=C1 HLLSOEKIMZEGFV-UHFFFAOYSA-N 0.000 description 1
- UBSRTSGCWBPLQF-UHFFFAOYSA-N 4-chloro-2-(4-chloropyridin-2-yl)pyridine Chemical compound ClC1=CC=NC(C=2N=CC=C(Cl)C=2)=C1 UBSRTSGCWBPLQF-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002114 high-resolution electrospray ionisation mass spectrometry Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000003586 protic polar solvent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/26—Radicals substituted by halogen atoms or nitro radicals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0046—Ruthenium compounds
- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Pyridine Compounds (AREA)
Abstract
The invention discloses a ruthenium polypyridine complex, the structure of which is shown in a formula 1, and the ruthenium polypyridine complex is used as a photoacid generator, so that the problems that the existing photoacid generator needs to generate acid through ultraviolet irradiation, the acid generation reaction time is long, the required raw material dosage is large, and the efficiency is low can be solved. The invention also discloses a preparation method and application of the ruthenium polypyridyl complex.
Description
Technical Field
The invention relates to the technical field of photoacid generators. More particularly, relates to a ruthenium polypyridine complex, a preparation method and application thereof.
Background
Photoacid generators (Photoacid generator, PAGs) are a class of molecules capable of generating acids under certain wavelengths of light. The photoacid generator is widely applied in the field of Photoresist (Photorisist), the principle of the Photoresist is that after the Photoresist is irradiated by the light source, the solubility is changed, and the photoacid generator can improve the photosensitivity of a Photoresist system and the imaging quality in an integrated circuit and a semiconductor accessory. There are a great number of documents and patents related to the photoacid generator, for example, the publication of the Chinese patent application with publication number of CN108496113A and the publication of the Chinese patent application with publication number of CN107129448A, the photoacid generator is disclosed, the most widely used photoacid generators are sulfonium salts and sulfonate, however, the photoacid generator is limited in application by acid generation through ultraviolet illumination, and the reaction system is organic solvents of chloroform, acetonitrile and the like, so that the reaction time is long, the reaction time is required to be tens of hours, and the raw material amount required for the reaction is large.
In view of the above, it is desirable to provide a novel photoacid generator.
Disclosure of Invention
The first object of the present invention is to provide a ruthenium polypyridine complex, which is used as a photoacid generator, and can solve the problems of long acid production reaction time, large required raw material dosage and low efficiency of the existing photoacid generator that acid is produced by ultraviolet irradiation.
The second object of the present invention is to provide a method for preparing ruthenium polypyridyl complex.
The third object of the present invention is to provide a photoacid generator which can solve the problems of the existing photoacid generator that the acid is generated by ultraviolet irradiation, the acid generation reaction time is long, the required raw material metering is large, and the efficiency is low.
A fourth object of the present invention is to provide the use of the ruthenium polypyridyl complex provided in the first object above in the preparation of halogen acid.
In order to achieve the first object, the present invention adopts the following technical scheme:
a ruthenium polypyridine complex having the structure set forth in formula I below:
wherein,,
R 1 、R 2 、R 3 each independently selected from H or-CH 2 X and at least one is-CH 2 X, said X being selected from halogen;
the A-represents a charge-balancing monovalent anion.
Optionally, the halogen is selected from one of Cl and Br.
Alternatively, the monovalent anion is selected from PF 6 - 、Cl - 、NO 3 - 、ClO 4 - 、BF 4 - One of them.
In order to achieve the second object, the present invention adopts the following technical scheme:
a preparation method of ruthenium polypyridine complex,
when R is 1 、R 2 、R 3 Only one of them is-CH 2 In the X process, the preparation method comprises the following steps:
RuCl is to be processed 3 ·xH 2 Dissolving O and lithium chloride in DMF, adding 2,2' -bipyridine ligand, wherein RuCl 3 ·xH 2 The molar ratio of O to 2,2' -bipyridine ligand is 1:2, in N 2 Refluxing in atmosphere, spin-drying the solvent, separating and purifying to obtain an intermediate 1, dissolving the intermediate 1 in DMF, adding 4,4 '-dihalomethyl-2, 2' -bipyridine ligand, wherein the molar ratio of the intermediate 1 to the 4,4 '-dihalomethyl-2, 2' -bipyridine ligand is 1:1, refluxing, separating and purifying to obtain the ruthenium polypyridine complex; or alternatively, the first and second heat exchangers may be,
when R is 1 、R 2 、R 3 Two of them are-CH 2 In the X process, the preparation method comprises the following steps:
RuCl is to be processed 3 ·xH 2 O and lithium chloride are dissolved in DMF, 4 '-dihalomethyl-2, 2' -bipyridine ligand is added, wherein RuCl 3 ·xH 2 The molar ratio of O to 4,4 '-dihalomethyl-2, 2' -bipyridine ligand is 1:2, in N 2 Reflux is carried out under atmosphere, the solvent is dried by spinning,obtaining an intermediate 2 through separation and purification, dissolving the intermediate 2 in DMF, adding a 2,2 '-bipyridine ligand, wherein the molar ratio of the intermediate 2 to the 2,2' -bipyridine ligand is 1:1, refluxing, and separating and purifying to obtain the ruthenium polypyridine complex;
when R is 1 、R 2 、R 3 Are all-CH 2 In the X process, the preparation method comprises the following steps:
RuCl is to be processed 3 ·xH 2 O and lithium chloride are dissolved in DMF, 4 '-dihalomethyl-2, 2' -bipyridine ligand is added, wherein RuCl 3 ·xH 2 The molar ratio of O to 4,4 '-dihalomethyl-2, 2' -bipyridine ligand is 1:3, in N 2 Refluxing under atmosphere, spin-drying the solvent, and separating and purifying to obtain the ruthenium polypyridyl complex.
In order to achieve the third object, the present invention adopts the following technical scheme:
a photoacid generator comprising the ruthenium polypyridine complex provided in the first object above.
In order to achieve the fourth object, the present invention also provides the use of the photoacid generator as described in the third object above in the preparation of a halogen acid.
Alternatively, the photoacid generator is used for the preparation of hydrohalic acid by illumination.
Optionally, the light used for illumination is visible light or ultraviolet light.
Optionally, the method of application comprises the steps of:
dissolving the ruthenium polypyridine complex in a water phase or a protonic solvent, and uniformly mixing to obtain a solution A;
and (3) carrying out illumination on the solution A to prepare the halogen acid.
Preferably, the illumination time is 1s-10min.
Alternatively, the concentration of solution A is 1. Mu.M-1 mM.
Optionally, the protic solvent is selected from one or more of water, methanol, ethanol and ethylene glycol.
The beneficial effects of the invention are as follows:
according to one object of the invention, the ruthenium polypyridyl complex provided by the invention can generate acid by using visible light or ultraviolet light irradiation due to the specific structure, and has the advantages of short acid generation reaction time, small required raw material metering and high efficiency. According to another object of the present invention, the photoacid generator provided by the present invention can generate halogen acid by visible light, and the whole acid generation process has short reaction time, high efficiency, acid generation efficiency up to more than 40%, and small required raw material dosage. According to still another object of the present invention, the present invention provides an application that also has the effects of the photoacid generator, which is not described herein.
Drawings
The following describes the embodiments of the present invention in further detail with reference to the drawings.
FIG. 1 shows a nuclear magnetic resonance hydrogen spectrum of the ruthenium polypyridyl complex prepared in example 1.
FIG. 2 shows a mass spectrum of the ruthenium polypyridyl complex prepared in example 1.
FIG. 3 shows the pH of the ruthenium polypyridyl complex (10. Mu.M) prepared in example 1 in an aqueous solution as a function of the time of irradiation.
Detailed Description
In order to more clearly illustrate the present invention, the present invention will be further described with reference to preferred embodiments and the accompanying drawings. Like parts in the drawings are denoted by the same reference numerals. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and that this invention is not limited to the details given herein.
Example 1
Ruthenium polypyridine complexes of the formula,
the preparation method comprises the following steps:
RuCl 3 ·xH 2 o (50 mg,0.19 mmol) and 4,4 '-dichloro-2, 2' -bipyridine (bcm-bpy) (152 mg,0.6 mmol) inN in DMF solvent 2 Reflux overnight under atmosphere and spin-dry the solvent. Purifying compound 3 by silica gel column with eluting solvent CH 3 CN/H 2 O/KNO 3 (10:4:1), the product was dissolved in water and treated with NH 4 PF 6 And precipitating out. Reference is made to figures 1 and 2. 1 H NMR(400MHz,CD 3 CN)δ8.49(s,6H),7.61(d,J＝5.8Hz,6H),7.37(d,J＝5.9Hz,6H),4.73(s,12H).HR ESI-MS:m/z＝429.9834for(M-2PF 6 - ) 2+ 。
Dissolving the prepared ruthenium polypyridine complex into water to obtain visible light with a concentration of 10 μm and an illumination wavelength of 520nm, and illuminating with an illumination intensity of 10mW/cm 2 The illumination time is 50s, and the photoacid efficiency is 50%. As shown in fig. 3, the pH of the solution decreased with increasing time.
Example 2
Ruthenium polypyridine complexes of the formula,
the preparation method comprises the following steps:
RuCl 3 ·xH 2 o (100 mg,0.38 mmol) and LiCl (106 mg), bpy (113 mg,0.8mmol) N in DMF solvent 2 Reflux overnight under atmosphere and spin-dry the solvent. Acetone was added to the obtained product, which was left overnight at 4℃in a refrigerator, and the solid (intermediate, ru (bpy)) was obtained by filtration 2 Cl 2 )，100mg Ru(bpy) 2 Cl 2 (0.19 mmol) and bcm-bpy (50.6 mg, 0.2)mmol) N in DMF solvent 2 Reflux overnight under atmosphere and spin-dry the solvent. Purifying compound 1 by silica gel column, eluting with CH 3 CN/H 2 O/KNO 3 (10:4:1), the product was dissolved in water and treated with NH 4 PF 6 And (5) sinking out.
Dissolving the prepared ruthenium polypyridine complex into water to obtain visible light with a concentration of 10 μm and an illumination wavelength of 520nm, and illuminating with an illumination intensity of 10mW/cm 2 The light time was 50s and the acid production was similar to example 1.
Example 3
Ruthenium polypyridine complexes of the formula,
the preparation method comprises the following steps:
RuCl 3 ·xH 2 o (100 mg,0.38 mmol) and LiCl (106 mg), bcm-bpy (204 mg,0.8 mmol) N in DMF solvent 2 Reflux overnight under atmosphere and spin-dry the solvent. Acetone was added to the obtained product, which was left overnight at 4℃in a refrigerator, and the solid (intermediate, ru (bcm-bpy)) was obtained by filtration 2 Cl 2 )，100mg Ru(bcm-bpy) 2 Cl 2 (0.15 mmol) and bpy (22.7 mg, 0.16)mmol) N in DMF solvent 2 Reflux overnight under atmosphere and spin-dry the solvent. Purifying compound 3 by silica gel column with eluting solvent CH 3 CN/H 2 O/KNO 3 (10:4:1), the product was dissolved in water and treated with NH 4 PF 6 And (5) sinking out.
Dissolving the prepared ruthenium polypyridine complex into water to obtain visible light with a concentration of 10 μm and an illumination wavelength of 520nm, and illuminating with an illumination intensity of 10mW/cm 2 The light time was 50s and the acid production was similar to example 1.
It should be understood that the foregoing examples of the present invention are provided merely for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention, and that various other changes and modifications may be made therein by one skilled in the art without departing from the spirit and scope of the present invention as defined by the appended claims.
Claims (8)
1. Use of a photoacid generator in the preparation of a hydrohalic acid, characterized in that the photoacid generator comprises a ruthenium polypyridine complex;
the ruthenium polypyridyl complex has a structure as shown in the following formula I:
wherein,,
R 1 、R 2 、R 3 each independently selected from H or-CH 2 X and at least one is-CH 2 X, said X being selected from halogen;
the A is - Representing a monovalent anion that balances the charge.
2. The use according to claim 1, wherein the halogen is selected from one of Cl, br.
3. The use according to claim 1, wherein the monovalent anion is selected from the group consisting of PF 6 - 、Cl - 、NO 3 - 、ClO 4 - 、BF 4 - One of them.
4. The use according to claim 1, wherein,
when R is 1 、R 2 、R 3 Only one of them is-CH 2 In the X process, the preparation method of the ruthenium polypyridyl complex comprises the following steps:
RuCl is to be processed 3 ·xH 2 Dissolving O and lithium chloride in DMF, adding 2,2' -bipyridine ligand, wherein RuCl 3 ·xH 2 The molar ratio of O to 2,2' -bipyridine ligand is 1:2, in N 2 Refluxing in atmosphere, spin-drying the solvent, separating and purifying to obtain an intermediate 1, dissolving the intermediate 1 in DMF, adding 4,4 '-dihalomethyl-2, 2' -bipyridine ligand, wherein the molar ratio of the intermediate 1 to the 4,4 '-dihalomethyl-2, 2' -bipyridine ligand is 1:1, refluxing, separating and purifying to obtain the ruthenium polypyridine complex; or alternatively, the first and second heat exchangers may be,
when R is 1 、R 2 、R 3 Two of them are-CH 2 The preparation method of the ruthenium polypyridyl complex comprises the following steps ofThe method comprises the following steps:
RuCl is to be processed 3 ·xH 2 O and lithium chloride are dissolved in DMF, 4 '-dihalomethyl-2, 2' -bipyridine ligand is added, wherein RuCl 3 ·xH 2 The molar ratio of O to 4,4 '-dihalomethyl-2, 2' -bipyridine ligand is 1:2, in N 2 Refluxing under atmosphere, spin-drying the solvent, separating and purifying to obtain an intermediate 2, dissolving the intermediate 2 in DMF, adding a 2,2 '-bipyridine ligand, wherein the molar ratio of the intermediate 2 to the 2,2' -bipyridine ligand is 1:1, refluxing, separating and purifying to obtain the ruthenium polypyridine complex;
when R is 1 、R 2 、R 3 Are all-CH 2 In the X process, the preparation method of the ruthenium polypyridyl complex comprises the following steps:
RuCl is to be processed 3 ·xH 2 O and lithium chloride are dissolved in DMF, 4 '-dihalomethyl-2, 2' -bipyridine ligand is added, wherein RuCl 3 ·xH 2 The molar ratio of O to 4,4 '-dihalomethyl-2, 2' -bipyridine ligand is 1:3, in N 2 Refluxing under atmosphere, spin-drying the solvent, and separating and purifying to obtain the ruthenium polypyridyl complex.
5. The use according to claim 1, characterized in that the photoacid generator is used for the preparation of hydrohalic acid by illumination.
6. The use according to claim 5, wherein the light used for illumination is visible or ultraviolet light.
7. The use according to any of claims 1-6, characterized in that the method of the use comprises the steps of:
dissolving the ruthenium polypyridine complex in a water phase or a protonic solvent, and uniformly mixing to obtain a solution A;
and (3) carrying out illumination on the solution A to prepare the halogen acid.
8. The use according to claim 7, wherein the illumination time is 1s-10min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910313344.0A CN111825603B (en) | 2019-04-18 | 2019-04-18 | Ruthenium polypyridine complex and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910313344.0A CN111825603B (en) | 2019-04-18 | 2019-04-18 | Ruthenium polypyridine complex and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111825603A CN111825603A (en) | 2020-10-27 |
| CN111825603B true CN111825603B (en) | 2023-04-28 |
Family
ID=72915572
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910313344.0A Active CN111825603B (en) | 2019-04-18 | 2019-04-18 | Ruthenium polypyridine complex and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111825603B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709202A (en) * | 2013-12-26 | 2014-04-09 | 广东药学院 | Ruthenium (II) complex, preparation method thereof, and application of complex as cell fluorescent dye |
| CN107129448A (en) * | 2016-02-29 | 2017-09-05 | 罗门哈斯电子材料有限责任公司 | Light acid produces monomer, includes the photo-corrosion-resisting agent composition of the polymer from its derivative polymer |
| CN107602619A (en) * | 2017-08-28 | 2018-01-19 | 常州大学 | A kind of Ru-polypyridine complex sensitising agent and preparation method thereof |
| CN108496113A (en) * | 2016-04-27 | 2018-09-04 | 三亚普罗股份有限公司 | Photoacid generator and photoetching resin combination |
-
2019
- 2019-04-18 CN CN201910313344.0A patent/CN111825603B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103709202A (en) * | 2013-12-26 | 2014-04-09 | 广东药学院 | Ruthenium (II) complex, preparation method thereof, and application of complex as cell fluorescent dye |
| CN107129448A (en) * | 2016-02-29 | 2017-09-05 | 罗门哈斯电子材料有限责任公司 | Light acid produces monomer, includes the photo-corrosion-resisting agent composition of the polymer from its derivative polymer |
| CN108496113A (en) * | 2016-04-27 | 2018-09-04 | 三亚普罗股份有限公司 | Photoacid generator and photoetching resin combination |
| CN107602619A (en) * | 2017-08-28 | 2018-01-19 | 常州大学 | A kind of Ru-polypyridine complex sensitising agent and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| Formation of Thin Polymeric Films by Electropolymerization. Reduction of Metal Complexes Containing Bromomethyl-Substituted Derivatives of 2,2’-Bipyridine;Sharon Gould等;《Inorganic Chemistry》;19911231;第30卷(第14期);第2944页表1 * |
| Mitochondria targeted and NADH triggered photodynamic activity of chloromethyl modified Ru(II) complexes under hypoxic conditions;Na Tian等;《Chemical Communications》;20190212;第55卷(第18期);第2676页方案1，supporting information第3页 * |
| Na Tian等.Mitochondria targeted and NADH triggered photodynamic activity of chloromethyl modified Ru(II) complexes under hypoxic conditions.《Chemical Communications》.2019,第55卷(第18期),第2676页方案1 supporting information第3页. * |
| Ruthenium Tris(bipyridine)-Centered Linear and Star-Shaped Polystyrenes: Making Atom Transfer Radical Polymerization and Metal Complex Initiators Compatible;Xufeng Wu等;《Macromolecules》;20010327;第34卷(第9期);第2818页 * |
| Ruthenium Tris(bipyridine)-Centered Linear and Star-Shaped Polystyrenes: Making Atom Transfer Radical Polymerization and Metal Complex Initiators CompatibleMacromolecules;Xufeng Wu等;《Macromolecules》;20010327;第34卷(第9期);第2813页 * |
| Sharon Gould等.Formation of Thin Polymeric Films by Electropolymerization. Reduction of Metal Complexes Containing Bromomethyl-Substituted Derivatives of 2,2’-Bipyridine.《Inorganic Chemistry》.1991,第30卷(第14期),第2944页表1. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111825603A (en) | 2020-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI400236B (en) | Photosensitizer dye | |
| CN109942831B (en) | Two photochromic viologen host-guest MOFs materials and preparation and application thereof | |
| CN106883207B (en) | A kind of preparation method of trimeric indenyl bicoumarin fluorescent dye | |
| CN112592360A (en) | Amphiphilic aza-BODIPY near-infrared dye and preparation method thereof | |
| CN114573622B (en) | Linear type fluoroborodipyrrole electron donor with 180-degree coordination included angle, supermolecule metal macrocycle, synthesis process and application | |
| CN110148672B (en) | Hole transport material, preparation method and application thereof, and perovskite solar cell comprising hole transport material | |
| CN112279856B (en) | Non-peripherally-substituted soluble metal phthalocyanine, synthesis method and application thereof, and perovskite solar cell | |
| CN111686821A (en) | Ruthenium complex and molybdenum-sulfur cluster dye-sensitized photocatalytic hydrogen production system reaction liquid | |
| CN115215901A (en) | Self-assembly hole transport material based on 7H-dibenzocarbazole and synthetic method | |
| CN111825603B (en) | Ruthenium polypyridine complex and preparation method and application thereof | |
| Murata et al. | Photocatalytic Styrene Polymerization by Novel Bichromophoric Pd Catalyst Having Long Excited-state Lifetime | |
| CN104231007A (en) | Amphiphilic benzimidazole ruthenium complex for dye-sensitized solar cell and preparation method of amphiphilic benzimidazole ruthenium complex | |
| CN113480528B (en) | Imidazole photosensitizer specifically targeting mitochondria and efficiently generating singlet oxygen and preparation method thereof | |
| EP2646450A1 (en) | Process for the synthesis of precursor complexes of titanium dioxide sensitization dyes based on ruthenium polypyridine complexes | |
| CN113292607B (en) | Ionic luminescent platinum complex based on benzimidazole phosphine ligand and preparation method thereof | |
| CN109232586A (en) | A kind of synthetic method of the more imidazole salts cage compounds of three-dimensional | |
| CN109111392B (en) | Synthetic method of cyclobutane derivative | |
| CN114437136A (en) | Preparation method and application of thiourea functionalized multi-chiral dual-core Ir (III) metal-organic double helix structure | |
| JP2012007084A (en) | New photosensitizer | |
| Anbalagan et al. | Spectral and photochemical behaviour of newly synthesized 2, 2′-dipyridylamine complexes of Pt (II) and Pd (II) with various dioxolenes | |
| CN112679541B (en) | Preparation method and application of metal organic ternary cyclic compound | |
| CN115043856B (en) | Pyrene condensed ring nucleus non-fullerene organic small molecule receptor material and preparation method and application thereof | |
| CN114907383B (en) | Di (benzopyrrole) phenothiazine organic dye, and preparation method and application thereof | |
| CN115286620B (en) | Calixarene compound, composite material, preparation method and application thereof | |
| CN111423595B (en) | Three-dimensional supramolecular polymer based on spirofluorene four-site column [ n ] arene and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |