Ruthenium polypyridine complex and preparation method and application thereof
阅读说明：本技术 一种钌多吡啶配合物及其制备方法和应用 (Ruthenium polypyridine complex and preparation method and application thereof ) 是由 王雪松 田纳 周前雄 于 2019-04-18 设计创作，主要内容包括：本发明公开一种钌多吡啶配合物,结构如式1所示,该钌多吡啶配合物作为光酸产生剂使用,可解决现有的光酸产生剂需经紫外光照产酸,且产酸反应时间长,需要的原料剂量大,效率低的问题。本发明还公开了该钌多吡啶配合物的制备方法和应用。(The invention discloses a ruthenium polypyridine complex, the structure of which is shown as formula 1, the ruthenium polypyridine complex is used as a photoacid generator, and can solve the problems that the conventional photoacid generator needs to generate acid by ultraviolet illumination, the acid generation reaction time is long, the required raw material dosage is large, and the efficiency is low. The invention also discloses a preparation method and application of the ruthenium polypyridine complex.)
1. A ruthenium polypyridine complex having the structure of formula I:
wherein the content of the first and second substances,
R1、R2、R3each independently selected from H or-CH2X and at least one is-CH2X, said X is selected from halogen;
a is described-Represents a charge-balancing monovalent anion.
2. A ruthenium polypyridine complex according to claim 1 in which the halogen is selected from the group consisting of Cl and Br.
3. A ruthenium polypyridine complex in accordance with claim 1, wherein the monovalent anion is selected from the group consisting of PF6 -、Cl-、NO3 -、ClO4 -、BF4 -One kind of (1).
4. A process for preparing a ruthenium polypyridine complex according to any one of claims 1 to 3, wherein,
when R is1、R2、R3Only one of them is-CH2X, the preparation method comprises the following steps:
adding RuCl3·xH2Dissolving O and lithium chloride in DMF, adding 2, 2' -bipyridyl ligand, wherein RuCl3·xH2The molar ratio of O to 2, 2' -bipyridine ligand is 1:2 in N2Refluxing under the 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 the like, or, alternatively,
when R is1、R2、R3Two of them are-CH2X, the preparation method comprises the following steps:
adding RuCl3·xH2Dissolving O and lithium chloride in DMF, adding 4,4 '-dihalomethyl-2, 2' -bipyridine ligand, wherein RuCl3·xH2The molar ratio of O to 4,4 '-dihalomethyl-2, 2' -bipyridine ligand is 1:2 in N2Refluxing under the atmosphere, spin-drying the solvent, separating and purifying to obtain an intermediate 2, dissolving the intermediate 2 in DMF, adding a 2,2 '-bipyridyl ligand, refluxing, separating and purifying to obtain the ruthenium polypyridine complex, wherein the molar ratio of the intermediate 2 to the 2, 2' -bipyridyl ligand is 1: 1;
when R is1、R2、R3Are all-CH2X, the preparation method comprises the following steps:
ru is mixedCl3·xH2Dissolving O and lithium chloride in DMF, adding 4,4 '-dihalomethyl-2, 2' -bipyridine ligand, wherein RuCl3·xH2The molar ratio of O to 4,4 '-dihalomethyl-2, 2' -bipyridine ligand is 1:3 in N2Refluxing under the atmosphere, spin-drying the solvent, and separating and purifying to obtain the ruthenium polypyridine complex.
5. A photoacid generator comprising the ruthenium polypyridine complex according to any one of claims 1 to 3.
6. Use of the photoacid generator of claim 5 in the production of a hydrohalic acid.
7. Use according to claim 6, wherein the photoacid generator is used for the preparation of hydrohalic acid by irradiation with light.
8. The use according to claim 7, wherein the light used for the illumination is visible or ultraviolet light.
9. Use according to any of claims 6-8, characterized in that the method of application comprises the steps of:
dissolving the ruthenium polypyridine complex in a water phase or a protic solvent, and uniformly mixing to obtain a solution A;
illuminating the solution A to prepare halogen acid;
preferably, the illumination time is 1s-10 min.
Technical Field
The invention relates to the technical field of photoacid generators. More particularly, relates to a ruthenium polypyridine complex and a preparation method and application thereof.
Background
Photo Acid Generators (PAGs) are a class of molecules that generate acid under a certain wavelength of light. The photoacid generator has wide application in the field of Photoresist (photo resist), 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 light sensitivity of a Photoresist system and improve the imaging quality in an integrated circuit and a semiconductor accessory. Many documents and patents have reported on photoacid generators, for example, chinese patent application publication No. CN108496113A and chinese patent application publication No. CN107129448A both disclose photoacid generators, and the most commonly used photoacid generators are sulfonium salts and sulfonates at present, however, the use of such photoacid generators is limited by the production of acid by ultraviolet light irradiation, and the reaction system is organic solvents such as chloroform and acetonitrile, so the reaction time is long, and sometimes it takes several tens of hours, and the amount of raw materials required for the reaction is large.
In view of the above problems, it is desirable to provide a novel photoacid generator.
Disclosure of Invention
The invention aims to provide a ruthenium polypyridine complex, which is used as a photoacid generator and can solve the problems that the conventional photoacid generator needs to generate acid by ultraviolet irradiation, the acid generation reaction time is long, the required raw material dosage is large, and the efficiency is low.
The second purpose of the invention is to provide a preparation method of the ruthenium polypyridine complex.
The third purpose of the invention is to provide a photoacid generator, which can solve the problems that the existing photoacid generator needs to generate acid by ultraviolet irradiation, the reaction time of acid generation is long, the required raw material amount is large, and the efficiency is low.
A fourth object of the present invention is to provide the use of the ruthenium polypyridine complex provided in the first object above for the preparation of hydrohalic acid.
In order to achieve the first purpose, the invention adopts the following technical scheme:
a ruthenium polypyridine complex having the structure of formula I:
wherein the content of the first and second substances,
R1、R2、R3each independently selected from H or-CH2X and at least one is-CH2X, said X is selected from halogen;
the A-represents a charge-balancing monovalent anion.
Optionally, the halogen is selected from one of Cl and Br.
Optionally, the monovalent anion is selected from PF6 -、Cl-、NO3 -、ClO4 -、BF4 -One kind of (1).
In order to achieve the second purpose, the invention adopts the following technical scheme:
a preparation method of a ruthenium polypyridine complex,
when R is1、R2、R3Only one of them is-CH2X, the preparation method comprises the following steps:
adding RuCl3·xH2Dissolving O and lithium chloride in DMF, adding 2, 2' -bipyridyl ligand, wherein RuCl3·xH2The molar ratio of O to 2, 2' -bipyridine ligand is 1:2 in N2Refluxing under the atmosphere, spin-drying the solvent, separating and purifying to obtain an
when R is1、R2、R3Two of them are-CH2X, the preparation method comprises the following steps:
adding RuCl3·xH2Dissolving O and lithium chloride in DMF, adding 4,4 '-dihalomethyl-2, 2' -bipyridine ligand, wherein RuCl3·xH2The molar ratio of O to 4,4 '-dihalomethyl-2, 2' -bipyridine ligand is 1:2 in N2Refluxing under the atmosphere, spin-drying the solvent, separating and purifying to obtain an intermediate 2, dissolving the intermediate 2 in DMF, adding a 2,2 '-bipyridyl ligand, refluxing, separating and purifying to obtain the ruthenium polypyridine complex, wherein the molar ratio of the
when R is1、R2、R3Are all-CH2X, the preparation method comprises the following steps:
adding RuCl3·xH2Dissolving O and lithium chloride in DMF, adding 4,4 '-dihalomethyl-2, 2' -bipyridine compoundBody, wherein RuCl3·xH2The molar ratio of O to 4,4 '-dihalomethyl-2, 2' -bipyridine ligand is 1:3 in N2Refluxing under the atmosphere, spin-drying the solvent, and separating and purifying to obtain the ruthenium polypyridine complex.
In order to achieve the third purpose, the invention adopts the following technical scheme:
a photoacid generator comprising a ruthenium polypyridine complex as provided above for the first object.
To achieve the fourth object, the present invention also provides the use of the photoacid generator described above for the third object in the production of a hydrohalic acid.
Optionally, the photoacid generator is used in light irradiation to produce a hydrohalic acid.
Optionally, the light used for the illumination is visible light or ultraviolet light.
Optionally, the method of applying comprises the steps of:
dissolving the ruthenium polypyridine complex in a water phase or a protic solvent, and uniformly mixing to obtain a solution A;
and (4) illuminating the solution A to prepare the halogen acid.
Preferably, the illumination time is 1s-10 min.
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 invention has the following beneficial effects:
according to an object of the invention, due to the specific structure of the ruthenium polypyridine complex, when the ruthenium polypyridine complex is used as a photoacid generator, visible light or ultraviolet light can be used for generating acid, the acid generation reaction time is short, the required raw material amount is small, and the efficiency is high. According to another object of the invention, the photoacid generator provided by the invention can produce halogen acid through visible light, and has the advantages of short reaction time, high efficiency, acid production efficiency of more than 40% and small required raw material dosage in the whole acid production process. According to another object of the present invention, the application provided in the present invention also has the effect brought by the photoacid generator, which is not described herein.
Drawings
The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.
FIG. 1 shows a nuclear magnetic hydrogen spectrum of a ruthenium polypyridine complex prepared in example 1.
FIG. 2 shows a mass spectrum of a ruthenium polypyridine complex prepared in example 1.
FIG. 3 shows the pH of ruthenium polypyridine complex (10. mu.M) prepared in example 1 in aqueous solution as a function of the time of light irradiation.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below with reference to preferred embodiments and the accompanying drawings. Similar parts in the figures 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 is not to be taken as limiting the scope of the invention.
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