CN110283124B - Pyridoindene compound and preparation method and application thereof - Google Patents

Pyridoindene compound and preparation method and application thereof Download PDF

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CN110283124B
CN110283124B CN201910507401.9A CN201910507401A CN110283124B CN 110283124 B CN110283124 B CN 110283124B CN 201910507401 A CN201910507401 A CN 201910507401A CN 110283124 B CN110283124 B CN 110283124B
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pyridoindene
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吴学峰
饶建行
霍延平
籍少敏
李先纬
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Guangdong University of Technology
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    • C—CHEMISTRY; METALLURGY
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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Abstract

The invention discloses a pyridoindene compound which has a molecular structure shown in a formula (III):
Figure DDA0002092277690000011
is named as N- (4- (5-indeno [1,2-b ]]Pyridine-7-yl) phenyl) -4-methoxy-N- (4-methoxyphenyl) aniline is a novel luminescent molecule which is never discovered, has strong absorption and emission, and has high fluorescence quantum yield, high fluorescence efficiency, higher luminescent intensity, good color purity, good thermal stability, long service life and good solubility. The invention also provides a preparation method of the pyridoindene compound and application of the pyridoindene compound in luminescent materials and devices.

Description

Pyridoindene compound and preparation method and application thereof
Technical Field
The invention relates to the technical field of organic luminescent materials, in particular to a pyridoindene compound and a preparation method and application thereof.
Background
Electroluminescence refers to a light emission phenomenon in which a light emitting material is excited by an electric field or current to generate an excited state, and then radiatively transits back to a ground state in the form of light. Inorganic luminescent materials have been studied more recently, but they have some drawbacks in terms of manufacturing and performance when used as host materials for light emitting devices, which limits their further development.
In recent years, organic compounds have been focused on organic light-emitting materials due to their advantages of high light-emitting efficiency, fast response speed, and the like, and thus organic light-emitting materials have been the hot point of research and development recently. Electronic devices, which are composed of multiple layers of Organic thin films and electrode thin films and are applied to flat panel displays or illumination, are called Organic Light-Emitting diodes (Organic Light-Emitting diodes), or Organic Light-Emitting diodes (OLEDs). The OLED has the advantages of wide visual angle, self-luminescence, low working voltage, thin panel, flexibility and the like, and has the potential of low cost, so the OLED has wide application prospect in the fields of flat panel display and solid light sources.
Organic light-emitting materials are the most core part in the OLED, and people hope to find a light-emitting material which can have the action effect of various functional layers in a multilayer device structure, can simplify the device structure and approach the simplest device structure; but also can greatly reduce the production cost and realize large-scale industrial production. Chinese patent application CN109134372A discloses a novel synthesis method of pyridine indene compounds, but the prior art does not disclose that the pyridine indene compounds can be used for organic luminescent materials.
The existing organic light emitting materials have not yet fully satisfied the requirements, and research and development personnel are required to continuously make efforts to develop new organic compounds that can be used for the organic light emitting materials.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides the pyridoindene compounds, which can be used for organic luminescent materials, have high fluorescence quantum yield, high fluorescence efficiency, higher luminescent intensity, good color purity, good thermal stability, long service life and good solubility, and have great potential in the preparation of luminescent devices.
The invention also aims to provide a preparation method of the pyridoindene compounds.
The invention also aims to provide application of the pyridoindene compounds in organic luminescent materials.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows:
a pyridoindene compound has a molecular structure shown in a formula (III):
Figure BDA0002092277670000021
the compound in the formula (III) is N- (4- (5-indeno [1,2-b ] pyridine-7-yl) phenyl) -4-methoxy-N- (4-methoxyphenyl) aniline. It is abbreviated as NIPP-MNA.
The pyridoindene compounds are a brand new luminescent material. The compound shown in the formula (III) is a novel luminescent molecule which is not discovered in reports, has strong absorption and emission, has high fluorescence quantum yield, high fluorescence efficiency, high luminescent intensity, good color purity, good thermal stability, long service life and good solubility, and has great potential in the preparation of luminescent devices.
The invention also provides a preparation method of the pyridoindene compound, which comprises the following steps:
s1, reacting 4,4 '-dimethoxy-4' -triphenylamine borate with bromoxynil through Suzuki to generate a compound shown in a formula (I);
s2, carrying out addition reaction on the compound shown in the formula (I) and absolute ethyl alcohol in acetyl chloride to obtain a compound shown in a formula (II);
s3, reacting the compound shown in the formula (II) with acrolein under the action of a catalyst to obtain a compound shown in a formula (III);
Figure BDA0002092277670000031
the preparation method provides a new synthesis method for the research and development of the luminescent material, and brings great revolution to the development of the luminescent material in the future.
Preferably, step S1. is carried out in a solvent under the action of a catalyst of tetrakis (triphenylphosphine) palladium.
Preferably, in the step s1, the solvent is a mixture of toluene, ethanol and potassium carbonate solution.
Preferably, step s1. is carried out in an inert atmosphere. The inert atmosphere is one or the combination of more than two of nitrogen atmosphere, argon atmosphere or helium atmosphere.
The reaction condition of the step S1 is heating reflux.
Preferably, the reaction temperature in the step S1 is 90-110 ℃, and the reaction time is 15-18 h.
More preferably, the reaction temperature of the step S1 is 100 ℃ and the reaction time is 16 h.
Preferably, the reaction temperature in the step S2 is-10 ℃, and the reaction time is 9-11 h.
More preferably, the reaction temperature of step S2. is 0 ℃ and the reaction time is 10 h.
And S2, using acetyl chloride as a catalyst and a solvent.
Preferably, in step s3. the catalyst comprises silver bis (trifluoromethanesulphonimide), bis (pentamethylcyclopentadienyl) rhodium (III) dichloride, sodium ions and copper ions.
Preferably, step S3. the reaction is carried out in the solvent 1, 2-dichloroethane.
Preferably, the reaction temperature in the step S3 is 90-110 ℃, and the reaction time is 3-5 h.
More preferably, the reaction temperature of step S3. is 100 ℃ and the reaction time is 4 h.
The invention also protects the application of the pyridine indene compounds in organic luminescent materials.
The application of the pyridindeno compound in preparing a light-emitting device is also within the protection scope of the application.
Compared with the prior art, the invention has the beneficial effects that:
the invention provides a novel luminescent molecule N- (4- (5-indeno [1,2-b ] pyridine-7-yl) phenyl) -4-methoxyl-N- (4-methoxyl phenyl) aniline which is not reported to be discovered, has strong absorption and emission, high fluorescence quantum yield, high fluorescence efficiency, higher luminescent intensity, good color purity, good thermal stability, longer service life and good solubility, and has great potential in the preparation of luminescent devices.
In addition, the preparation method of the molecule provides a new synthetic method for the research and development of luminescent materials, and brings great revolution to the development of the luminescent materials in the future.
Drawings
FIG. 1 shows a compound of formula (III) 1 H-NMR chart.
FIG. 2 shows a compound of formula (III) 13 C-NMR chart.
FIG. 3 shows 4,4 '-dimethoxy-4' -triphenylamine borate as a raw materialIs 13 C-NMR chart.
FIG. 4 is a diagram showing the absorption spectrum of a solution of a compound of the formula (III).
FIG. 5 shows fluorescence emission spectra of the solution of the compound of formula (III).
FIG. 6 is a solvation effect diagram of a solution of a compound of formula (III).
FIG. 7 is a time-resolved fluorescence spectrum of the compound of formula (III). In the figure, N-hex represents N-hexane; DCM represents dichloromethane; THF represents tetrahydrofuran; EA represents ethyl acetate; diox1,4 dioxane; DMF represents N-N-dimethylamide; CAN represents acetonitrile.
Detailed Description
The present invention will be further described with reference to the following embodiments.
The raw materials in the examples are all commercially available;
the reagents, methods and apparatus employed in the present invention are conventional in the art, except as otherwise indicated.
Example 1
The preparation of N- (4- (5-indeno [1,2-b ] pyridin-7-yl) phenyl) -4-methoxy-N- (4-methoxyphenyl) aniline comprises the following steps,
s1, preparing a compound of formula (I):
1g of p-bromobenzonitrile, 0.4g of 4,4 '-dimethoxy-4' -triphenylamine borate and 0.1g of tetrakis (triphenylphosphine palladium) were weighed into a round-bottomed flask, 20mL of each of toluene and an oxygen-free solution of ethanol were added, and 0.5g of K was weighed 2 CO 3 In 6mL of H 2 O, performing magnetic stirring at 100 ℃ under the protection of nitrogen for 16 hours, performing extraction and column chromatography purification after reaction, and separating 1.8g of a yellow solid intermediate, namely the compound of the formula (I), wherein an eluent is petroleum ether/dichloromethane; the reaction formula is as follows,
Figure BDA0002092277670000051
s2, preparing a compound of a formula (II):
weighing 1.4g of a compound of formula (I), 12mL of absolute ethyl alcohol and 8mL of acetyl chloride in a 250mL round-bottom flask without oxygen, carrying out magnetic stirring at the temperature of 0 ℃, reacting for 10 hours, and purifying by extraction and column chromatography after the reaction, wherein an eluent is petroleum ether/dichloromethane, and separating 1.2g of a gray yellow solid compound of formula (II); the reaction formula is as follows,
Figure BDA0002092277670000052
s3, preparing a compound shown in a formula (III),
weighing 0.09g of the compound of formula (II), 4 drops of acrolein and 30mg of sodium acetate, 50mg of copper acetate, 1 mg of dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer, 2mg of bis (trifluoromethanesulfonimide) silver, 1 mL of 1, 2-dichloroethane liquid in a 20mL reaction tube, covering the reaction tube with a cover, reacting at 100 ℃ for 4 hours, purifying by column chromatography after the reaction, and separating 0.07g of the final product of the compound of formula (III), namely 4 '-dimethoxy-4' -triphenylamine borate pyridoindene molecule (NIPP-MNA); the reaction formula is as follows,
Figure BDA0002092277670000061
structure and performance testing
(1) Nuclear magnetic testing
Bruk 400MHz superconducting NMR spectrometer, deuterated reagent: deuterated chloroform.
(2) Photophysical property testing
Absorption spectrum, fluorescence emission spectrum, solvation effect and time-resolved fluorescence spectrum.
Fluorescence emission spectrum, solvation effect and time-resolved fluorescence spectrum test, namely Edinburgh FLS-980; the absorption spectrum is Shimadzu UVVIS-2700; test solvent, tetrahydrofuran; concentration 10 -5 mol/L。
Test results
The NMR spectrum of the compound of formula (III) is shown in FIG. 1, and the characteristic wavenumbers are 7.81, 7.73, 7.67, 7.49, 7.48 and 7.26,7,09,6.87,6.85,3.9,3.8. The nuclear magnetic resonance carbon spectrum of the compound of the formula (III) is shown in FIG. 2, and the characteristic peaks are 155.90, 144.26, 140.73, 127.57, 125.89, 120.57, 114.68, 77.32, 77.00, 76.68, 55.41 and 34.63. Measuring molecules of triphenylamine 4,4 '-dimethoxy-4' -borate 13 C-NMR chart as shown in FIG. 3. As can be seen from fig. 3, the characteristic peaks are 55.519, 76.768, 77.086, 77.404, 82.002, 115.828, 122.270, 126.736, 137.694, 148.639, and 156.167. The control product, a compound of formula (III), can confirm the formation of N- (4- (5-indeno [1,2-b ]]Pyridin-7-yl) phenyl) -4-methoxy-N- (4-methoxyphenyl) aniline (NIPP-MNA) molecules.
The photophysical properties of the compounds of formula (III) are shown in FIGS. 4 to 7. As is clear from FIG. 4, the absorption peak of the compound of the formula (III) is mainly around 365 nm. As is clear from FIG. 5, the compound of formula (III) has an emission peak at an emission wavelength around 480nm, and the electron-donating ability of the donor of the molecule is increased due to the presence of the methoxy group, resulting in enhancement of luminescence to some extent. The solvation effect of the compound of formula (III) in the solution with different polarities at a concentration of 10-5M is shown in FIG. 6, which shows that the luminescence of the solution gradually red-shifts with the increase of the polarity of the solvent. FIG. 7 shows the fluorescence emission lifetime of the compound of formula (III) in tetrahydrofuran, which was fitted to FIG. 7 and the fluorescence decay of the compound of formula (III) was 3.58 ns.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.

Claims (6)

1. A pyridoindene compound organic luminescent material is characterized by having a molecular structure shown in a formula (III):
Figure FDA0003774191680000011
2. the method for preparing the pyridoindene compounds in the claim 1, characterized by comprising the following steps:
s1, reacting 4,4 '-dimethoxy-4' -triphenylamine borate with bromoxynil through Suzuki to generate a compound shown in a formula (I), wherein the reaction temperature is 90-110 ℃, and the reaction time is 15-18 h;
s2, carrying out addition reaction on the compound of the formula (I) and absolute ethyl alcohol in acetyl chloride to obtain a compound of a formula (II), wherein the reaction temperature of S2 is-10 ℃, and the reaction time is 9-11 h;
s3, reacting the compound of the formula (II) with acrolein under the action of a catalyst to obtain a compound of a formula (III), wherein the reaction temperature is 90-110 ℃, and the reaction time is 3-5 h;
Figure FDA0003774191680000012
3. the process according to claim 2, wherein step S1. is carried out in a solvent under the action of a catalyst of tetrakis (triphenylphosphine) palladium.
4. The process according to claim 3, wherein step S1. is carried out in an inert atmosphere.
5. The method according to claim 2, wherein the catalyst in step S3 comprises bis (trifluoromethanesulfonimide) silver and bis (pentamethylcyclopentadienyl) rhodium (III) dichloride dimer.
6. Use of the pyridoindene compound of claim 1 in the preparation of a light-emitting device.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109134372A (en) * 2018-10-24 2019-01-04 广东工业大学 A kind of preparation method of pyrido indene compounds
WO2019084157A1 (en) * 2017-10-24 2019-05-02 Yumanity Therapeutics, Inc. Compounds and uses thereof

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JP6655870B2 (en) * 2014-10-22 2020-03-04 三星ディスプレイ株式會社Ｓａｍｓｕｎｇ Ｄｉｓｐｌａｙ Ｃｏ．，Ｌｔｄ． Organic electroluminescent element material and organic electroluminescent element using the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019084157A1 (en) * 2017-10-24 2019-05-02 Yumanity Therapeutics, Inc. Compounds and uses thereof
CN109134372A (en) * 2018-10-24 2019-01-04 广东工业大学 A kind of preparation method of pyrido indene compounds

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