CN108047211B - Bipyrazole acetic acid coumarin derivative laser material and application thereof - Google Patents

Bipyrazole acetic acid coumarin derivative laser material and application thereof Download PDF

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CN108047211B
CN108047211B CN201810015621.5A CN201810015621A CN108047211B CN 108047211 B CN108047211 B CN 108047211B CN 201810015621 A CN201810015621 A CN 201810015621A CN 108047211 B CN108047211 B CN 108047211B
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coumarin derivative
bipyrazolylacetic
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laser material
acid coumarin
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陆知纬
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Wuxi Dade Optoelectronic Technology Co ltd
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
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Abstract

The invention provides a bipyrazolylacetic acid coumarin derivative laser material, which has the structural formula:

Description

Bipyrazole acetic acid coumarin derivative laser material and application thereof
Technical Field
The invention belongs to the field of laser materials, and particularly relates to a bipyrazole acetic acid coumarin derivative laser material.
Background
The traditional laser has a plurality of problems, such as difficult crystal growth, high technical requirement, high price and the like for the solid laser; the laser glass is generally required to be melted under high temperature, OH groups and gas protection are also required to be removed for different matrix materials and different laser working wave bands, the process conditions are severe, and the production cost is high. At present, more carbon dioxide gas lasers are used, and the device is heavy and huge although the power is high, so that a plurality of inconveniences are brought to occasions needing a miniaturized laser. In recent years, inorganic semiconductor lasers have been rapidly developed and widely used, but have a problem of high production cost. In view of these limitations in laser performance, scientists have long been striving to develop new laser materials in an effort to achieve a more perfect laser. The exploration and development of novel laser working substances and materials are not only the precondition and basis for developing novel high-efficiency lasers and laser systems in the future, but also have great potential application value.
Organic semiconductor materials have been widely used in the fields of Organic Light Emitting Diodes (OLEDs), organic Field Effect Transistors (OFETs), organic solar cells (OPVs), organic lasers (organic lasers) and the like because of their good optical and electrical properties, simple preparation processes and structural and performance modulatability, and have become an important content for research on organic electronics. In recent years, research and development of organic lasers which are compact in structure and low in price (even can be abandoned) are very rapid. Compared with dye lasers, the organic semiconductor material has the advantages of organic laser dyes (high luminous efficiency, wide adjustable spectrum range, four-energy-level system and the like), high solid state luminous efficiency, good carrier transmission, good film forming property and the like, and is widely focused on laser application. However, the high laser threshold of the organic laser under the electric pumping makes the electric pumping of the organic laser difficult to realize, which is also a bottleneck problem which plagues the development of the organic laser. In order to reduce the laser threshold, organic semiconductor materials including small molecular materials, polymer materials, high molecular materials and the like are synthesized by optimizing molecular structure design. The polymer has a multidimensional space topological structure, is monodisperse and can be purified by using conventional silica gel column chromatography like small molecules, and has good film forming performance similar to polymers. In addition, because of the space multidimensional structure, the interaction among molecules is weakened, so that the materials have better solubility in polar solvents to form a film with regular and uniform surface morphology, and meanwhile, the materials have isotropic photoelectric properties.
Disclosure of Invention
Technical problems: in order to solve the defects in the prior art, the invention provides a bipyrazolylacetic acid coumarin derivative laser material.
The technical scheme is as follows: the invention provides a bipyrazolylacetic acid coumarin derivative laser material, which has the structural formula:
Figure BDA0001541843830000021
the melting point of the bipyrazolylacetic acid coumarin derivative laser material is above 170.1.
The laser material of the bipyrazolylacetic acid coumarin derivative is between 449 and 453 nm.
The full width at half maximum of PL emission peak of the bipyrazolylacetic acid coumarin derivative laser material is below 4.1 nm.
The bipyrazole acetic acid coumarin derivative laser materialThe gain coefficient of the material is 97-101cm -1 Between them.
The invention also provides a preparation method of the bipyrazolylacetic acid coumarin derivative laser material, which is characterized by comprising the following steps of: the method comprises the following steps:
(1) Preparation of 4-phenyl-7-hydroxycoumarin: in the presence of sodium bisulfate monohydrate, carrying out reflux reaction on resorcinol and ethyl benzoylacetate to obtain 4-phenyl-7-hydroxycoumarin;
the reaction formula is:
Figure BDA0001541843830000022
(2) Preparation of bipyrazole acetic acid coumarin derivatives: reacting 4-phenyl-7-hydroxycoumarin with bis (1-pyrazole) acetic acid in the presence of triethylamine to obtain a bipyrazole acetic acid coumarin derivative; the reaction formula is:
Figure BDA0001541843830000031
in the step (1), the molar ratio of sodium bisulfate monohydrate, resorcinol and ethyl benzoylacetate is (0.10-0.20): 1: (1-2), the reaction time is 10-20min.
In the step (2), the molar ratio of the bis (1-pyrazole) to the 4-phenyl-7-hydroxycoumarin to the triethylamine is (1-1.2): 1: (2-4), the reaction temperature is room temperature, and the reaction time is 3-5h.
The invention also provides application of the bipyrazolylacetic acid coumarin derivative laser material in a laser.
The beneficial effects are that: the bipyrazolylacetic acid coumarin derivative laser material provided by the invention has the advantages of low preparation cost, simple and controllable synthesis, high yield, good solubility and better thermal stability. The material has excellent thermal stability, film forming stability, low threshold characteristic, low water oxygen sensitivity and high luminous intensity in the application of an organic laser device. The high luminous efficiency and mobility of the organic light-emitting diode lead the organic light-emitting diode to have potential application value in the aspects of electrically pumping organic semiconductor laser, organic electroluminescence and organic field effect transistors.
Detailed Description
The present invention will be further described below.
Example 1
The preparation method of the bipyrazolylacetic acid coumarin derivative laser material comprises the following steps of:
(1) Preparation of 4-phenyl-7-hydroxycoumarin: 40.0mmol of resorcinol, 60.0mmol of ethyl benzoylacetate and 4.0mmol of sodium bisulfate monohydrate are added into a round-bottomed flask, uniformly mixed, placed into a microwave chemical reactor, provided with a reflux device, intermittently heated under the condition of 400W of power, monitored by TLC for reaction progress, after heating for 8min, resorcinol disappears, and microwave heating is stopped. After cooling, 80mL of ice water was added to the reaction flask, stirred, dispersed with ultrasonic waves, a large amount of bulk solid was precipitated, filtered off with suction to remove water, and then recrystallized with 95% ethanol to give 7.08g of dark green solid with a yield of 70.9%.
MS(m/z):238.2(M+，92.1％)，210.1(100％)，181.2(34.2％)，152.1(26.3％)，76.1(9.2％)。R f (0.55, ethyl acetate: petroleum ether=2:1)
The reaction formula is:
Figure BDA0001541843830000041
(2) Preparation of bipyrazole acetic acid coumarin derivatives: adding 3mmol of triethylamine into a round-bottom flask, stirring, and simultaneously adding 1mmol of 4-phenyl-7-hydroxycoumarin and 1.1mmol of bis (1-pyrazole) acetic acid to react for 4 hours at room temperature to obtain a bipyrazole coumarin acetate derivative; the yield thereof was found to be 84.1%.
The reaction formula is:
Figure BDA0001541843830000042
MS(m/z):412.4(M+)。
example 2
The preparation method of the bipyrazolylacetic acid coumarin derivative laser material comprises the following steps of:
(1) Preparation of 4-phenyl-7-hydroxycoumarin: in the presence of sodium bisulfate monohydrate, carrying out reflux reaction on resorcinol and ethyl benzoylacetate to obtain 4-phenyl-7-hydroxycoumarin; wherein, the mole ratio of sodium bisulfate monohydrate, resorcinol and ethyl benzoylacetate is 0.15:1:1.5, the reaction time is 15min; yield 69.8%;
(2) Preparation of bipyrazole acetic acid coumarin derivatives: reacting 4-phenyl-7-hydroxycoumarin with bis (1-pyrazole) acetic acid in the presence of triethylamine to obtain a bipyrazole acetic acid coumarin derivative; wherein, the mol ratio of the bis (1-pyrazole) to the 4-phenyl-7-hydroxycoumarin to the triethylamine is 1.1:1:3, the reaction temperature is room temperature, and the reaction time is 4 hours; the yield thereof was found to be 82.6%.
Example 3
The preparation method of the bipyrazolylacetic acid coumarin derivative laser material comprises the following steps of:
(1) Preparation of 4-phenyl-7-hydroxycoumarin: in the presence of sodium bisulfate monohydrate, carrying out reflux reaction on resorcinol and ethyl benzoylacetate to obtain 4-phenyl-7-hydroxycoumarin; wherein, the mole ratio of sodium bisulfate monohydrate, resorcinol and ethyl benzoylacetate is 0.10:1:2, the reaction time is 20min; yield 69.4%;
(2) Preparation of bipyrazole acetic acid coumarin derivatives: reacting 4-phenyl-7-hydroxycoumarin with bis (1-pyrazole) acetic acid in the presence of triethylamine to obtain a bipyrazole acetic acid coumarin derivative; wherein, the mol ratio of the bis (1-pyrazole) to the 4-phenyl-7-hydroxycoumarin to the triethylamine is 1:1:2, the reaction temperature is room temperature, and the reaction time is 5 hours; the yield thereof was found to be 81.9%. .
Example 4
The preparation method of the bipyrazolylacetic acid coumarin derivative laser material is characterized by comprising the following steps of: the method comprises the following steps:
(1) Preparation of 4-phenyl-7-hydroxycoumarin: in the presence of sodium bisulfate monohydrate, carrying out reflux reaction on resorcinol and ethyl benzoylacetate to obtain 4-phenyl-7-hydroxycoumarin; wherein, the mole ratio of sodium bisulfate monohydrate, resorcinol and ethyl benzoylacetate is 0.20:1:1, the reaction time is 10min; yield 69.2%;
(2) Preparation of bipyrazole acetic acid coumarin derivatives: reacting 4-phenyl-7-hydroxycoumarin with bis (1-pyrazole) acetic acid in the presence of triethylamine to obtain a bipyrazole acetic acid coumarin derivative; wherein, the mol ratio of the bis (1-pyrazole) to the 4-phenyl-7-hydroxycoumarin to the triethylamine is 1.2:1:4, the reaction temperature is room temperature, and the reaction time is 3 hours; the yield thereof was found to be 82.0%. .
Example 5
The solubility of the bipyrazolylacetic acid coumarin derivative laser materials of examples 1 to 4 was measured, and the results are shown in Table 1.
TABLE 1
Example 1 Example 2 Example 3 Example 4
Melting point DEG C 172.6-173.8 171.1-172.3 170.1-171.8 170.3-171.0
The solubility of the bipyrazolylacetic acid coumarin derivative laser materials of examples 1 to 4 was measured, and the results are shown in Table 2.
TABLE 2
Solvent(s) Example 1 Example 2 Example 3 Example 4
Methanol △ △ △ △
Ethanol △ △ △ △
Acetone (acetone) √ √ √ √
Dichloromethane (dichloromethane) √ √ √ √
Tetrahydrofuran (THF) √ √ √ √
DMF √ √ √ √
DMSO √ √ √ √
Toluene (toluene) △ △ △ △
Cyclohexane × × × ×
And (2) the following steps: completely dissolving; delta: partially dissolving; x, insoluble.
THF is used as a solvent, and the dipyrazolylacetic acid coumarin derivative laser materials of examples 1 to 4 are adopted as a luminous main body to prepare 20mg/mL solutions respectively. The quartz plate is cleaned by ultrasonic wave, and the organic laser device is prepared by adopting a spin coating mode, wherein the spin coating condition is 2000rpm, and the film thickness is about 100 nm. The properties were measured and the results are shown in Table 3.
TABLE 3 Table 3
Figure BDA0001541843830000061
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Claims (5)

1. A bipyrazolylacetic acid coumarin derivative laser material has a structural formula as follows:
Figure FDA0004106033540000011
2. the bipyrazolylacetic acid coumarin derivative laser material according to claim 1, wherein the laser material is characterized in that: the melting point of the bipyrazolylacetic acid coumarin derivative laser material is above 170.1.
3. The bipyrazolylacetic acid coumarin derivative laser material according to claim 1, wherein the laser material is characterized in that: the full width at half maximum of PL emission peak of the bipyrazolylacetic acid coumarin derivative laser material is below 4.1 nm.
4. The bipyrazolylacetic acid coumarin derivative laser material according to claim 1, wherein the laser material is characterized in that: the gain coefficient of the bipyrazolylacetic acid coumarin derivative laser material is 97-101cm -1 Between them.
5. The use of a bipyrazolylacetic acid coumarin derivative laser material according to claim 1 in a laser.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB991202A (en) * 1961-04-27 1965-05-05 Geigy Ag J R Improvements relating to 3-phenyl-7-pyrazolyl coumarins and their use as optical brightening agents
US3521187A (en) * 1967-09-18 1970-07-21 Eastman Kodak Co Laser media containing coumarin dye solutions
EP1041074A1 (en) * 1999-03-09 2000-10-04 Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo Light-sensitive 4-cyanocoumarin derivatives
CN101525497A (en) * 2008-03-06 2009-09-09 中国科学院理化技术研究所 Pyrazoline naphthyridine benzocoumarin fluorescent dye derivatives, synthesis method of same, and application of same
CN104788279A (en) * 2015-04-02 2015-07-22 南京邮电大学 Organic semiconductor laser material as well as preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB991202A (en) * 1961-04-27 1965-05-05 Geigy Ag J R Improvements relating to 3-phenyl-7-pyrazolyl coumarins and their use as optical brightening agents
US3521187A (en) * 1967-09-18 1970-07-21 Eastman Kodak Co Laser media containing coumarin dye solutions
EP1041074A1 (en) * 1999-03-09 2000-10-04 Kabushiki Kaisha Hayashibara Seibutsu Kagaku Kenkyujo Light-sensitive 4-cyanocoumarin derivatives
CN101525497A (en) * 2008-03-06 2009-09-09 中国科学院理化技术研究所 Pyrazoline naphthyridine benzocoumarin fluorescent dye derivatives, synthesis method of same, and application of same
CN104788279A (en) * 2015-04-02 2015-07-22 南京邮电大学 Organic semiconductor laser material as well as preparation method and application thereof

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