CN101402648B - Blue light emitting organic luminescent material small-substituent pyridine diimine hydrargyrum complex and method of preparing the same - Google Patents

Blue light emitting organic luminescent material small-substituent pyridine diimine hydrargyrum complex and method of preparing the same Download PDF

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CN101402648B
CN101402648B CN2008101375396A CN200810137539A CN101402648B CN 101402648 B CN101402648 B CN 101402648B CN 2008101375396 A CN2008101375396 A CN 2008101375396A CN 200810137539 A CN200810137539 A CN 200810137539A CN 101402648 B CN101402648 B CN 101402648B
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blue light
luminescent material
organic luminescent
emitting
pyridine diimine
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范瑞清
王平
杨玉林
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Harbin Institute of Technology
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Abstract

The invention relates to a small substitution group-pyridine diimine and mercury complex of blue-light emitting organic materials and a preparation method thereof, and relates to the light-emitting organic materials and the preparation method thereof. The small substitution group-pyridine diimine and mercury complex solves the problem of lower intensity in light emitting of the existing blue light-emitting organic material. The molecular formula of the pyridine diimine and mercury complex is C21H19N3HgCl2, C23H23N3HgCl2 or C23H23N3HgCl2. The preparation method is as follows: under the nitrogen protection, a ligand and anhydrous HgCl2 are dissolved in an organic solvent and then stirred, and finally recrystallized. The product prepared by the preparation method of the invention is a singlecrystal with good shape and the light emitting materials produced can emit blue fluorescence by the test and show better monochromaticity. Additionally, the preparation method is simple in operation and high in yield which can reach more than 80 percent.

Description

Organic luminescent material small-substituent pyridine diimine hydrargyrum complex of blue light-emitting and preparation method thereof
Technical field
The present invention relates to luminous organic material and preparation method thereof.
Background technology
The synthetic research with performance of luminous organic material is the focus of field of light emitting materials research always, and stable blue light compound purposes aspect organic electroluminescence device (being called for short OLED) is very big, well behavedly in the red, green, blue three-color light-emitting material of OLED present organic materials red, green glow and obtain, and the luminous organic material that presents blue light seldom, becomes the technical bottleneck of OLED development.Recently the people's attention extremely because the luminescent ligand compound of containing n-donor ligand has good performance and potential application prospect at aspects such as sensor technology, photochemistry and electroluminescent materials.Therefore in the preparation blue organic luminous material, utilize the adjustability of the metal ion of metal complexes and containing n-donor ligand to design and synthesize that blue organic luminous material is very challenging efficiently.The d of recently a large amount of containing n-donor ligands 10Family's metal complexes is synthesized in succession, and has studied their luminescent properties, but the report of research hydrargyrum complex luminescent properties is an only a few.For example: people such as H.Kunkely have studied a kind of UV spectrum and fluorescence spectrum of mercury alkylide title complex, and this compound is an excitation wavelength with 420nm in benzole soln, has obtained maximum emission wavelength in 638nm, presents red fluorescence.People such as Ren Yonghua synthesize and have characterized the diamine complexes of the multinuclear mercury of a series of novelties, have studied the luminous and chemical property of these compounds.It is rare especially to present blue-fluorescence in the hydrargyrum complex of having studied, and existing organic blue light material luminous intensity and fluorescence quantum efficiency are on the low side.
Summary of the invention
The objective of the invention is luminous intensity problem on the low side, and organic luminescent material small-substituent pyridine diimine hydrargyrum complex of blue light-emitting and preparation method thereof is provided for the luminous organic material that solves existing blue light-emitting.
The organic luminescent material small-substituent pyridine diimine hydrargyrum complex Hg of blue light-emitting among the present invention (2,6-two [1-(phenyl imine) ethyl] pyridine) Cl 2Molecular formula be C 21H 19N 3HgCl 2, its structural formula is
Figure G2008101375396D00021
The organic luminescent material small-substituent pyridine diimine hydrargyrum complex Hg of blue light-emitting (2,6-two [1-(phenyl imine) ethyl] pyridine) Cl 2Preparation method's step as follows: one, under nitrogen protection, with 2 of 100～120mg, the HgCl of 6-two [1-(phenyl imine) ethyl] pyridine and 86～104mg 2Be dissolved in the methylene dichloride of 15～25mL, stirred under the room temperature 10～15 hours, be heated to the methylene dichloride evaporate to dryness then, get pale yellow powder; Two,, promptly get the organic luminescent material small-substituent pyridine diimine hydrargyrum complex C of blue light-emitting with step 1 product recrystallization 2～3 times 21H 19N 3HgCl 2The used organic solvent of recrystallization is CH in the step 2 3CN.
The organic luminescent material small-substituent pyridine diimine hydrargyrum complex Hg of another kind of blue light-emitting among the present invention (2,6-two [1-(2-aminomethyl phenyl imines) ethyl] pyridine) Cl 2Molecular formula be C 23H2 3N 3HgCl 2, its structural formula is
Figure G2008101375396D00022
The organic luminescent material small-substituent pyridine diimine hydrargyrum complex Hg of blue light-emitting (2,6-two [1-(2-aminomethyl phenyl imines) ethyl] pyridine) Cl 2Preparation method's step as follows: one, under nitrogen protection, with 2 of 100～150mg, the HgCl of 6-two [1-(2-aminomethyl phenyl imines) ethyl] pyridine and 85～100mg 2Be dissolved in the methylene dichloride of 15～25mL, stirred under the room temperature 15～20 hours, be heated to the methylene dichloride evaporate to dryness then, get pale yellow powder; Two,, promptly get the organic luminescent material small-substituent pyridine diimine hydrargyrum complex C of blue light-emitting with step 1 product recrystallization 2～3 times 23H 23N 3HgCl 2The used organic solvent of recrystallization is CH in the step 2 3CN and CH 2Cl 2Mixing solutions, CH 3CN and CH 2Cl 2Volume ratio be 2:1.
The organic luminescent material small-substituent pyridine diimine hydrargyrum complex Hg of another kind of blue light-emitting among the present invention (2,6-two [1-(4-aminomethyl phenyl imines) ethyl] pyridine) Cl 2Molecular formula be C 23H 23N 3HgCl 2, its structural formula is
Figure G2008101375396D00031
The organic luminescent material small-substituent pyridine diimine hydrargyrum complex Hg of blue light-emitting (2,6-two [1-(4-aminomethyl phenyl imines) ethyl] pyridine) Cl 2Preparation method's step as follows: one, under nitrogen protection, with 2 of 100～130mg, the HgCl of 6-two [1-(4-aminomethyl phenyl imines) ethyl] pyridine and 85～100mg 2Be dissolved in the methylene dichloride of 15～25mL, stirred under the room temperature 12～18 hours, be heated to the methylene dichloride evaporate to dryness then, get pale yellow powder; Two,, promptly get the organic luminescent material small-substituent pyridine diimine hydrargyrum complex C of blue light-emitting with step 1 product recrystallization 2～3 times 23H 23N 3HgCl 2The used organic solvent of recrystallization is CH in the step 2 3CN.
The consumption of the organic solvent that the present invention uses does not have obviously influence to reaction.
The inventive method preparing product is the intact monocrystalline of crystal formation; The present invention makes blue light organic luminescent material and tests through luminescent properties, presents blue-fluorescence under dichloromethane solution and room temperature condition, and the monochromatic performance that is presented is relatively good, and luminous intensity has improved 2～10 times, and maximum emission wavelength is 390～430nm.And stability is strong, can place for a long time in air.The inventive method is simple to operation and productive rate is high, reaches more than 80%, than the productive rate raising 10%～20% of bibliographical information.
Description of drawings
Fig. 1 is the crystalline structure figure that the specific embodiment of the invention one method makes product.Fig. 2 is the crystalline structure figure that the specific embodiment of the invention seven methods make product.Fig. 3 is the crystalline structure figure that the specific embodiment of the invention ten cubic legal systems get product.Fig. 4 is the infrared spectrogram that the specific embodiment of the invention one method makes product.Fig. 5 is the infrared spectrogram that the specific embodiment of the invention seven methods make product.Fig. 6 is the infrared spectrogram that the specific embodiment of the invention ten cubic legal systems get product.Fig. 7 is the fluorescence spectrum figure that the specific embodiment of the invention one method makes product.Fig. 8 is the fluorescence spectrum figure that the specific embodiment of the invention seven methods make product.Fig. 9 is the fluorescence spectrum figure that the specific embodiment of the invention ten cubic legal systems get product.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the organic luminescent material small-substituent pyridine diimine hydrargyrum complex Hg of present embodiment blue light-emitting (2,6-two [1-(phenyl imine) ethyl] pyridine) Cl 2Molecular formula be C 21H 19N 3HgCl 2, its structural formula is
Figure G2008101375396D00041
The organic luminescent material small-substituent pyridine diimine hydrargyrum complex Hg of blue light-emitting (2,6-two [1-(phenyl imine) ethyl] pyridine) Cl 2Preparation method's step is as follows: one, under nitrogen protection, and with 2 of 100～120mg, the HgCl of 6-two [1-(phenyl imine) ethyl] pyridine and 86～104mg 2Be dissolved in the methylene dichloride of 15～25mL, stirred under the room temperature 10～15 hours, be heated to the methylene dichloride evaporate to dryness then, get pale yellow powder; Two,, promptly get the organic luminescent material small-substituent pyridine diimine hydrargyrum complex C of blue light-emitting with step 1 product recrystallization 2～3 times 21H 19N 3HgCl 2
The productive rate of present embodiment is 84%, and the product that present embodiment makes is the intact monocrystalline crystal of yellow crystal formation, and Fig. 4 product of making of present embodiment as can be seen is Hg (2,6-two [1-(phenyl imine) ethyl] pyridine) Cl 2, Fig. 7 product of making of present embodiment as can be seen presents blue-fluorescence, and the monochromatic performance that is presented is relatively good, and the maximum emission peak wavelength is λ Max=395nm.
The reaction equation of present embodiment is as follows
Figure G2008101375396D00042
Embodiment two: what present embodiment and embodiment one were different is that the used organic solvent of recrystallization is CH in the step 2 3CN.Other is identical with embodiment one.
Embodiment three: what present embodiment and embodiment one were different is that churning time is 11～14 hours in the step 1.Other is identical with embodiment one.
Embodiment four: what present embodiment and embodiment one were different is that churning time is 10 hours in the step 1.Other is identical with embodiment one.
Embodiment five: what present embodiment and embodiment one were different is that churning time is 15 hours in the step 1.Other is identical with embodiment one.
Embodiment six: what present embodiment and embodiment one were different is that churning time is 13 hours in the step 1.Other is identical with embodiment one.
Embodiment seven: the organic luminescent material small-substituent pyridine diimine hydrargyrum complex Hg of present embodiment blue light-emitting (2,6-two [1-(2-aminomethyl phenyl imines) ethyl] pyridine) Cl 2Molecular formula be C 23H 23N 3HgCl 2, its structural formula is
Figure G2008101375396D00051
The organic luminescent material small-substituent pyridine diimine hydrargyrum complex Hg of blue light-emitting (2,6-two [1-(2-aminomethyl phenyl imines) ethyl] pyridine) Cl 2Preparation method's step is as follows: one, under nitrogen protection, and with 2 of 100～150mg, the HgCl of 6-two [1-(2-aminomethyl phenyl imines) ethyl] pyridine and 85～100mg 2Be dissolved in the methylene dichloride of 15～25mL, stirred under the room temperature 15～20 hours, be heated to the methylene dichloride evaporate to dryness then, get pale yellow powder; Two,, promptly get the organic luminescent material small-substituent pyridine diimine hydrargyrum complex C of blue light-emitting with step 1 product recrystallization 2～3 times 23H 23N 3HgCl 2
The productive rate of present embodiment is 84%, and the product that present embodiment makes is the intact monocrystalline crystal of glassy yellow crystal formation, and Fig. 6 product of making of present embodiment as can be seen is Hg (2,6-two [1-(2-aminomethyl phenyl imines) ethyl] pyridine) Cl 2, Fig. 8 product of making of present embodiment as can be seen presents blue-fluorescence, and the monochromatic performance that is presented is relatively good, and the maximum emission peak wavelength is λ Max=403nm.
The reaction equation of present embodiment is as follows:
Figure G2008101375396D00052
Embodiment eight: what present embodiment and embodiment seven were different is that the used organic solvent of recrystallization is CH in the step 2 3CN and CH 2Cl 2Mixing solutions.Other is identical with embodiment seven.
Embodiment nine: that present embodiment and embodiment eight are different is CH 3CN and CH 2Cl 2Volume ratio be 2:1.Other is identical with embodiment eight.
Embodiment ten: what present embodiment and embodiment seven were different is that churning time is 16～18 hours in the step 1.Other is identical with embodiment seven.
Embodiment 11: what present embodiment and embodiment seven were different is that churning time is 15 hours in the step 1.Other is identical with embodiment seven.
Embodiment 12: what present embodiment and embodiment seven were different is that churning time is 20 hours in the step 1.Other is identical with embodiment seven.
Embodiment 13: what present embodiment and embodiment seven were different is that churning time is 17 hours in the step 1.Other is identical with embodiment seven.
Embodiment 14: the organic luminescent material small-substituent pyridine diimine hydrargyrum complex Hg of present embodiment blue light-emitting (2,6-two [1-(4-aminomethyl phenyl imines) ethyl] pyridine) Cl 2Molecular formula be C 23H 23N 3HgCl 2, its structural formula is
Figure G2008101375396D00061
The organic luminescent material small-substituent pyridine diimine hydrargyrum complex Hg of blue light-emitting (2,6-two [1-(4-aminomethyl phenyl imines) ethyl] pyridine) Cl 2Preparation method's step is as follows: one, under nitrogen protection, and with 2 of 100～130mg, the HgCl of 6-two [1-(4-aminomethyl phenyl imines) ethyl] pyridine and 85～100mg 2Be dissolved in the methylene dichloride of 15～25mL, stirred under the room temperature 12～18 hours, be heated to the methylene dichloride evaporate to dryness then, get pale yellow powder; Two,, promptly get the organic luminescent material small-substituent pyridine diimine hydrargyrum complex C of blue light-emitting with step 1 product recrystallization 2～3 times 23H 23N 3HgCl 2
The productive rate of present embodiment is 86%, and the product that present embodiment makes is the intact monocrystalline crystal of faint yellow crystal formation, and Fig. 6 product of making of present embodiment as can be seen is Hg (2,6-two [1-(4-aminomethyl phenyl imines) ethyl] pyridine) Cl 2, Fig. 9 product of making of present embodiment as can be seen presents blue-fluorescence, and the monochromatic performance that is presented is relatively good, and the maximum emission peak wavelength is λ Max=427nm.
The reaction equation of present embodiment is as follows:
Figure G2008101375396D00071
Embodiment 15: what present embodiment and embodiment 14 were different is that the used organic solvent of recrystallization is CH in the step 2 3CN.Other is identical with embodiment 14.
Embodiment 16: what present embodiment and embodiment 14 were different is that churning time is 13～17 hours in the step 1.Other is identical with embodiment 14.
Embodiment 17: what present embodiment and embodiment 14 were different is that churning time is 15 hours in the step 1.Other is identical with embodiment 14.
Embodiment 18: what present embodiment and embodiment 14 were different is that churning time is 12 hours in the step 1.Other is identical with embodiment 14.
Embodiment 19: what present embodiment and embodiment 14 were different is that churning time is 18 hours in the step 1.Other is identical with embodiment 14.

Claims (2)

1. the organic luminescent material small-substituent pyridine diimine hydrargyrum complex of blue light-emitting is characterized in that organic luminescent material small-substituent pyridine diimine hydrargyrum complex Hg (2,6-two [1-(the 4-aminomethyl phenyl imines) ethyl] pyridine) Cl of blue light-emitting 2Molecular formula be C 23H 23N 3HgCl 2, its structural formula is
Figure FA20190551200810137539601C00011
2. the preparation method of the organic luminescent material small-substituent pyridine diimine hydrargyrum complex of blue light-emitting according to claim 1; the organic luminescent material small-substituent pyridine diimine hydrargyrum complex that it is characterized in that blue light-emitting prepares according to the following steps: one, under nitrogen protection; with 2 of 100～130mg, the HgCl of 6-two [1-(4-aminomethyl phenyl imines) ethyl] pyridine and 85～100mg 2Be dissolved in the methylene dichloride of 15～25mL, stirred under the room temperature 12～18 hours, be heated to the methylene dichloride evaporate to dryness then, get pale yellow powder; Two,, promptly get the organic luminescent material small-substituent pyridine diimine hydrargyrum complex C of blue light-emitting with step 1 product recrystallization 2～3 times 23H 23N 3HgCl 2The used organic solvent of recrystallization is CH in the step 2 3CN.
CN2008101375396A 2008-11-14 2008-11-14 Blue light emitting organic luminescent material small-substituent pyridine diimine hydrargyrum complex and method of preparing the same Expired - Fee Related CN101402648B (en)

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范瑞清.吡啶二亚胺金属配合物的合成、表征及发光性能的研究.吉林大学2004 年博士论文.2005,200475-88. *

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