CN104876825A - Pyrene derivative as well as preparation method and application thereof - Google Patents
Pyrene derivative as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to the field of organic electroluminescent materials, and in particular relates to a pyrene derivative as well as a preparation method and application thereof; the pyrene derivative provided by the invention is that large substituent group units having different electronic properties and rigid structures are introduced at the positions of 1-, 3-, 6- and 8- of pyrene; intermolecular phi-phi stacking can be inhibited through molecular coplanar damage; therefore, an exciplex is difficult to form; the crystallization process is inhibited; the film-forming property is improved; therefore, the purpose of improving device properties is achieved; because an electron donor and an electron acceptor are introduced at special positions, a pyrene ring is asymmetrically functionalized; push-pull type molecular is constructed; intramolecular charge transfer is induced to generate; the charge transmission capability of the material is increased; and an organic light-emitting material having blue light property and high fluorescence quantum yield can be prepared. Compared with the existing light-emitting material, the light-emitting efficiency, the colour purity and the stability of the material are greatly improved.
Description
Technical field
The present invention relates to field of organic electroluminescent materials, in particular to a kind of derivative and its preparation method and application of pyrene.
Background technology
Along with the development of Multimedia technology and the arriving of information society, more and more higher to the requirement of flat-panel monitor performance.Organic Light Emitting Diode (Organic Light-Emitting Diodes, OLED) device is in high-tech areas such as communication, information, display, illumination and Novel full color displays luminous (Full-Color Flat-Panel Displays), show huge commercial application prospect, become a study hotspot of present stage.Many scientists are devoted to the research of OLED, and obtain proud achievement.
Current, the research for OLED mainly concentrates on the making of device and exploitation two aspect of functional materials, and the luminous organic material developing unique electronic structure and luminescent properties becomes one of research emphasis.Organic materials is because having high luminous efficiency, wide glow color range of choice, and the superiority of easy big area film forming, is widely used among functional materials and device.In the evolution of OLED, in order to realize full-color EL display (Full-ColorFlat-Panel Displays), prepare blue light emitting material most important.Blue light material not only can realize efficient, stable blue emission, meets the requirement of full-color EL display, and because of its energy gap wider, using it as material of main part, utilize chemical modification techniques, the methods such as transfer energy, can obtain corresponding red light material and green light material.At present, ruddiness, green light material are with fastest developing speed, substantially reach the commercialization practical stage, and the blue light material preparing air-stable, high-level efficiency and purity of color high are challenging.Therefore the mazarine luminescent material with premium properties exploring synthesizing new becomes current top priority.
Pyrene is the polycyclic aromatic compounds that a class has large conjugatedπbond, and it has good thermostability, strong electronic conduction, mazarine photoluminescent property and high quantum yield, is widely used in the research of the aspects such as fluorescent probe.But, at high density (> 10
-4mol/L) under solution or solid state, pyrene easily forms bimolecular exciplex, thus reduces fluorescence quantum efficiency, significantly limit pyrene as luminescent material application in the opto-electronic device.Therefore, modified pyrene ring, preparing with pyrene is the high-performance luminescent material of parent (or containing pyrenyl group), becomes study hotspot gradually.
Along with the progress of OLED technology, the research of OLED material obtains tremendous expansion, and the activity site (1,3,6,8-position) of pyrene and K-region (4,5,9,10-position) obtain extensively to be studied.But great majority research mainly concentrates on the symmetrical pyrene that replaces prepares pyrenyl luminescent material, the maximum shortcoming of this kind of material one is exactly the problem of poor solubility and purity of color.At present, for pyrenyl class luminescent material, more tends to the performance study exploring the synthetic route of asymmetric functionalization pyrene and the luminescent material of asymmetric pyrene.Major cause is, asymmetric electron donor-acceptor structure unit is introduced at pyrene ring, build the molecular structure of large conjugation, by (the intramolecular charge-transfer of charge transfer in Molecular regulator, ICT), increase intramolecular charge coupling, be conducive to the electronic structure regulating material, reduce internal energy of molecular level, improve the quantum yield of compound.With M ü llen seminar for representative, take the lead in reporting the 4-at pyrene ring, asymmetric modification is carried out in 5-position and 9-, 10-position, has prepared D-A type pyrenyl derivative, electron donating group and electron-withdrawing group introduce the K-region of pyrene ring simultaneously, by Intramolecular electron transfer, effectively reduce molecular energy level, by Molecular regulator energy level, prepare pyrenyl luminescent material that is green, Huang Hehong, but but can not obtain the blue light material of one of three primary colours.And there is following shortcoming in the derivative of existing asymmetric pyrene:
1, preparation method is comparatively complicated;
2, pyrenyl class blue light material fluorescence quantum yield is lower;
3, the luminous efficiency of pyrenyl class blue light material, purity of color and stability need to promote further.
In view of this, special proposition the present invention.
Summary of the invention
The first object of the present invention is the derivative providing a kind of pyrene, and the derivative of described pyrene has asymmetric branched structure, and compared to existing luminescent material, the luminous efficiency of this material, purity of color and stability all have larger lifting.
The second object of the present invention is the preparation method of the derivative providing a kind of described pyrene, and the method is simple, and yield is high.
The third object of the present invention is to provide a kind of derivative of described pyrene as the application of luminescent material in photo luminescent devices.
In order to realize above-mentioned purpose of the present invention, spy by the following technical solutions:
A derivative for pyrene, is characterized in that, has following structure:
Wherein:
R
1substituting group be selected from the substituted aroma hydrocarbon with 5 to 30 carbon atoms, the aryloxy with 6 to 50 carbon atoms, have 5 to 30 carbon atoms aromatic amine, have 6-20 carbon atom boron aromatic hydrocarbons, there is one in the fragrant aromatic heterocyclic group of 5 to 40 annular atomses or cyano group;
R
1' substituting group is selected from the substituted aroma hydrocarbon with 5 to 30 carbon atoms, the aryloxy with 6 to 50 carbon atoms, the aromatic amine with 5 to 30 carbon atoms, the boron aromatic hydrocarbons with 6-20 carbon atom, the one had in the aromatic heterocyclic group of 5 to 40 annular atomses, cyano group or hydrogen;
R
2substituting group be selected from the substituted aroma hydrocarbon with 5 to 30 carbon atoms, the aryloxy with 6 to 50 carbon atoms, have 5 to 30 carbon atoms aromatic amine, have 6-20 carbon atom boron aromatic hydrocarbons, there is one in the aromatic heterocyclic group of 5 to 40 annular atomses or cyano group;
R
1substituting group and R
2substituting group is different;
R
1' substituting group and R
2substituting group is different.
The derivative of pyrene provided by the invention, the 1-at pyrene, 3-and 6-, the large-substituent unit with different electronic property, rigid structure is introduced in 8-position, the destruction of molecule coplanarity will suppress its intermolecular pi-pi accumulation, make it not easily form exciplex, and suppress its crystallisation process, improve its film-forming properties; And then reach the object improving device performance; By introducing electron donor(ED) and electron acceptor(EA) in specific position, realizing asymmetric functionalization pyrene ring, construct push-pull type molecule, there is Intramolecular electron transfer in induction, improve the charge transport ability of material, preparation has the luminous organic material of blue light character and high fluorescence quantum yield.Compared to existing luminescent material, the luminous efficiency of this material, purity of color and stability all have larger lifting.
Preferably, described R
1' substituting group is hydrogen.
Namely the derivative of pyrene has following structure:
The derivative of such pyrene, is that the large-substituent unit with different electronic property, rigid structure is introduced in 1-and 6-at pyrene, 8-position, makes it not easily form exciplex, and suppress its crystallisation process, improve its film-forming properties, improve its charge transport properties; Meanwhile, the destruction of the public planarity of molecule is by its emission peak blue shift of destruction and then reach the object improving device performance, and realize asymmetric functionalization pyrene, preparation has the luminous organic material of blue light character and high fluorescence quantum yield.Compared to existing luminescent material, the luminous efficiency of this material, purity of color and stability all have larger lifting.
Preferably, described R
1' substituting group and described R
1substituting group is identical.Namely the derivative of Asymmetrical substitute pyrene has following structure:
Wherein:
R
1substituting group be selected from the substituted aroma hydrocarbon with 5 to 30 carbon atoms, the aryloxy with 6 to 50 carbon atoms, have 5 to 30 carbon atoms aromatic amine, there is boron aromatic hydrocarbons containing 6-20 carbon atom, there is one in the aromatic heterocyclic group of 5 to 40 annular atomses or cyano group;
R
2substituting group be selected from the substituted aroma hydrocarbon with 5 to 30 carbon atoms, the aryloxy with 6 to 50 carbon atoms, have 5 to 30 carbon atoms aromatic amine, there is boron aromatic hydrocarbons containing 6-20 carbon atom, there is one in the aromatic heterocyclic group of 5 to 40 annular atomses or cyano group;
R
1substituting group and R
2substituting group is different.
The derivative of this pyrene is the 1-at pyrene, 3-and 6-, the large-substituent unit with different electronic property, rigid structure is introduced in 8-position, and the destruction of molecule coplanarity will suppress its intermolecular pi-pi accumulation, make it not easily form exciplex, and suppress its crystallisation process, improve its film-forming properties; And then reach the object improving device performance; By introducing electron donor(ED) and electron acceptor(EA) in specific position, realizing asymmetric functionalization pyrene ring, construct push-pull type molecule, there is Intramolecular electron transfer in induction, improve the charge transport ability of material, preparation has the luminous organic material of blue light character and high fluorescence quantum yield.Compared to existing luminescent material, the luminous efficiency of this material, purity of color and stability all have larger lifting.
Derivative as Asymmetrical substitute pyrene provided by the invention can be any one of following structural formula:
R wherein
1and R
2for capping group, can be selected from as any one in the Heterocyclylalkyl of the aryloxy of the heteroaralkyl of the aralkyl of the heteroaryl of the aryl of hydrogen, fluorine, alkyl, alkoxyl group, aldehyde radical, amido, cyano group, C6-C30, C2-C30, C6-C30, C2-C30, C5-C30, the heteroaryloxy of C2-C30, the cycloalkyl of C3-C30 or C2-C30.
Present invention also offers the preparation method of the derivative of described pyrene, comprise the following steps:
(a),
with bromizating agent in organic solvent, be obtained by reacting
(b),
by crosslinked coupled reaction, obtain
(c),
with bromizating agent in organic solvent, be obtained by reacting
(d),
by crosslinked coupled reaction, obtain
The preparation method of the derivative of pyrene provided by the invention, for raw material with pyrene, bromizating agent etc., by chemosynthesis progressively, method is simple, prepare the bromine pyrene derivatives intermediate of a class novelty, then by classical crosslinked coupled reaction, prepare Asymmetrical substitute pyrene derivatives, this pyrenyl analog derivative is the luminous organic material with blue light character and high fluorescence quantum yield.
Synthetic route is:
Preferably, in step (a) and (c), described bromizating agent is selected from any one or more in N-bromo-succinimide, benzyl trimethyl tribromide ammonium and bromine water.Empirical tests, the bromizating agent reactivity of this kind is higher, and selectivity is better, is easy to obtain product.
Preferably, in step (a) and (c), described organic solvent is any one in methylene dichloride, trichloromethane, tetrachloromethane.The organic solvent of this kind is easy to the carrying out of bromination reaction, avoids the generation of other by products.
Preferably, in step (b) and (d), described crosslinked coupled reaction is any one in Suzuki reaction, Sonogashira reaction, Buchwald – Hartwig linked reaction.Above-mentioned crosslinked coupled reaction is classical crosslinked coupled reaction, and technology maturation is easy to application, product stable.
In order to reach better reaction effect, preferably, in step (c), under protection of inert gas,
be that 1:2.5-4 is mixed in methylene dichloride with bromizating agent with mol ratio, react 4-5 hour at normal temperatures, filter and obtain product, described product, through column chromatography chromatogram or recrystallization, obtains
Present invention also offers the preparation method of the derivative of another kind of asymmetric functionalization pyrene, comprise the following steps:
(a),
with isobutyl chloride in dichloromethane solution, with AlCl
3carry out catalysis, be obtained by reacting
(b),
under the effect of bromizating agent benzyl trimethyl tribromide ammonium, be obtained by reacting
(c),
by crosslinked coupled reaction, obtain
(d),
with catalyzer in organic solvent, reaction after generate
(e),
with bromizating agent in organic solvent, reaction after generate
(f),
by crosslinked coupled reaction, obtain
The preparation method of this Asymmetrical substitute pyrene, by chemosynthesis progressively, method is simple, prepare the bromine pyrene derivatives intermediate of a class novelty, then by classical crosslinked coupled reaction, prepare the pyrene class of Asymmetrical substitute, such pyrenyl luminescent material has the features such as efficient blue light character, high fluorescence quantum yield and good thermostability.
Synthetic route is:
Preferably, in step (d), described catalyzer is Nafion-H.Perfluorinated sulfonic resin (Nafion-H) is now known most strong solid super acids, has that resistance toheat is good, chemical stability and a physical strength high.When Nafion-H is used as catalyzer, be easy to be separated, can Reusability; And corrodibility is little, cause public hazards few, selectivity is good, is easy to apply in suitability for industrialized production.
Preferably, in step (d), described organic solvent is one or more in toluene, o-Xylol, m-xylene and p-Xylol.
Preferably, in step (e), described bromizating agent is one or more in N-bromo-succinimide, benzyl trimethyl tribromide ammonium and bromine water.
Preferably, in step (c) and (f), described crosslinked coupled reaction is any one in Suzuki reaction, Sonogashira reaction, Buchwald – Hartwig linked reaction.Above-mentioned crosslinked coupled reaction is classical crosslinked coupled reaction, and technology maturation is easy to application, product stable.
In order to better reaction, to obtain specific product more efficiently, preferably, in step (e), under protection of inert gas,
be that 1:2.5 ~ 4 are mixed in methylene dichloride with bromizating agent with mol ratio, react 4 ~ 5 hours at normal temperatures, filter and obtain product, described product, through column chromatography chromatogram or recrystallization, obtains
as
can be 1:2.5,1:3,1:3.5 and 1:4 etc. with the mol ratio of bromizating agent.
Present invention also offers the derivative of described pyrene as luminescent material application in the opto-electronic device.
Compared with prior art, beneficial effect of the present invention is:
(1) derivative of pyrene provided by the invention is 1-and 6-at pyrene, 8-position or the 1-at pyrene, 3-and 6-, the large-substituent unit with different electronic property, rigid structure is introduced in 8-position, the destruction of molecule coplanarity will suppress its intermolecular pi-pi accumulation, make it not easily form exciplex, and suppress its crystallisation process, improve its film-forming properties; And then reach the object improving device performance; By introducing electron donor(ED) and electron acceptor(EA) in specific position, realize Asymmetrical substitute pyrene ring, construct push-pull type molecule, there is Intramolecular electron transfer in induction, improve the charge transport ability of material, preparation has the luminous organic material of blue light character and high fluorescence quantum yield, and compared to existing luminescent material, the luminous efficiency of this luminescent material, purity of color and stability all have larger lifting;
(2) preparation method of the derivative of pyrene provided by the invention, by chemosynthesis progressively, method is simple, prepare the bromine pyrene derivatives intermediate of a class novelty, then by classical crosslinked coupled reaction, prepare asymmetric functionalization pyrenyl derivative, such pyrenyl derivative is the luminous organic material with blue light character and high fluorescence quantum yield.
(3) the present invention is by selecting specific bromizating agent, organic solvent and catalyzer etc., and make preparation process simple, yield is high, pollutes few.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below.
Fig. 1 is the fluorescence emission spectrogram of 1-phenyl-6,8-bis--(4,4 ,-two fluorine-based pentanoic bases) pyrene in the embodiment of the present invention 1;
Fig. 2 is the fluorescence emission spectrogram of 1-phenyl-6,8-dicyan pyrene in the embodiment of the present invention 2;
Fig. 3 is the fluorescence emission spectrogram of 1-phenyl-6-two-(4-ethynylbiphenyl) pyrene in the embodiment of the present invention 3.
Embodiment
Below in conjunction with embodiment, embodiment of the present invention are described in detail, but it will be understood to those of skill in the art that the following example only for illustration of the present invention, and should not be considered as limiting the scope of the invention.Unreceipted actual conditions person in embodiment, the condition of conveniently conditioned disjunction manufacturers suggestion is carried out.Agents useful for same or the unreceipted production firm person of instrument, being can by the conventional products of commercially available acquisition.
Embodiment 1
The preparation of 1-phenyl-6,8-bis--(4,4 ,-two fluorine-based pentanoic bases) pyrene
The molecular structural formula of 1-phenyl-6,8-bis--(4,4 ,-two fluorine-based pentanoic bases) pyrene is as follows:
Concrete preparation process is as follows:
The first step: under the condition of nitrogen protection, get pyrene 1g (4.9mmol) and benzyl trimethyl tribromide ammonium (NBS) 974mg (5.5mmol), be dissolved in 50ml methylene dichloride, at room temperature stir 5 hours, filter, recrystallization in methylene dichloride and normal hexane, obtains 1-bromine pyrene (1.08g), and productive rate is 78%;
Second step: under the condition of nitrogen protection, the first step product 1-bromine pyrene 500mg (1.78mmol), phenylo boric acid 270mg (2.2mmol), tetrakis triphenylphosphine palladium 70mg (0.06mmol), salt of wormwood 300mg (2.2mmol) are added in single neck bottle, then toluene (10ml) and ethanol (4ml) is added, strong stirring, temperature is kept to be 90 DEG C, reflux 24 hours, filter out product, through column chromatography chromatogram or recrystallization, obtain highly purified 1-phenyl pyrene (109mg), productive rate about 70%;
3rd step: under the condition of nitrogen protection, by second step product 1-phenyl pyrene 350mg (1.26mmol) and BTMABr
31.72g (4.4mmol) is raw material, at room temperature stirs 5 hours, and filter, recrystallization in methylene dichloride and normal hexane, obtains 1-phenyl-6,8-dibromo pyrene (328mg), and productive rate is 75%;
4th step: under the condition of nitrogen protection, by the 3rd step product 1-phenyl-6, 8-dibromo pyrene 110mg (0.25mmol), 4, 4,-two fluorine-based pentanoic 130mg (0.63mmol), tertiary butyl phosphine 30mg (1mmol), palladium 30mg (0.13mmol), cesium carbonate 200mg (0.61mmol) adds in single neck bottle, then o-Xylol (10ml) is added, strong stirring, temperature is kept to be 120 DEG C, reflux 48 hours, filter out product, through column chromatography chromatogram or recrystallization, obtain highly purified target product (97mg), productive rate about 56%.
In mass spectrum, m/z:684.22 (100.0%), 685.22 (50.5%), 686.23 (12.3%), 687.23 (2.0%).
The maximum emission peak of target product under solution state is 481nm, specifically as shown in Figure 1.
Embodiment 2
The preparation of 1-phenyl-6,8-dicyan pyrene
The molecular structural formula of 1-phenyl-6,8-dicyan pyrene is as follows:
Concrete preparation process is as follows:
The first step: under the condition of nitrogen protection, get pyrene 1g (4.9mmol) and NBS974mg (5.5mmol), be dissolved in 50ml methylene dichloride, at room temperature stir 5 hours, filter, recrystallization in methylene dichloride and normal hexane, obtains 1-bromine pyrene (1.08g), and productive rate is 78%;
Second step: under the condition of nitrogen protection, the first step product 1-bromine pyrene 500mg (1.78mmol), phenylo boric acid 270mg (2.2mmol), tetrakis triphenylphosphine palladium 70mg (0.06mmol), salt of wormwood 300mg (2.2mmol) are added in single neck bottle, then toluene (10ml) and ethanol (4ml) is added, strong stirring, temperature is kept to be 90 DEG C, reflux 24 hours, filter out product, through column chromatography chromatogram or recrystallization, obtain highly purified 1-phenyl pyrene (109mg), productive rate about 70%;
3rd step: under the condition of nitrogen protection, by second step product 1-phenyl pyrene 1.76mmol and BTMABr
31.72g (4.4mmol) is raw material, at room temperature stirs 4 hours, and filter, recrystallization in methylene dichloride and normal hexane, obtains 1-phenyl-6,8-dibromo pyrene (328mg), and productive rate is 72%;
4th step: under the condition of nitrogen protection; by 1-phenyl-6; 8-dibromo pyrene 110mg (0.25mmol), CuCN 50mg (0.55mmol) and N-Methyl pyrrolidone 10ml add in single neck bottle, strong stirring, keep temperature to be 100 DEG C; reflux 24 hours; filter out product, through column chromatography chromatogram or recrystallization, obtain highly purified target product 1-phenyl-6; 8-dicyan pyrene 46mg, productive rate about 56%.
In mass spectrum, m/z:328.10 (100.0%), 329.10 (26.7%), 330.11 (3.3%)
The maximum emission peak of target product 1-phenyl-6,8-dicyan pyrene under solution state is 432nm, specifically sees Fig. 2.
Embodiment 3
The preparation of 1-phenyl-6-two-(4-ethynylbiphenyl) pyrene
The molecular structural formula of 1-phenyl-6-two-(4-ethynylbiphenyl) pyrene is as follows:
Concrete preparation method is as follows:
The first step: under the condition of nitrogen protection, gets pyrene 1g (4.9mmol) and different tertiary butyl chloride 450mg (4.9mmol) is raw material, at AlCl
3under the catalysis of 1.4g (9mmol), in dichloromethane solution (50ml), stirred at ambient temperature 5 hours, filter, recrystallization in normal hexane, obtains 2-tertiary butyl pyrene (1.9g), and productive rate is 83%;
Second step: under the condition of nitrogen protection, gets 2-tertiary butyl pyrene 2.58g (1mmol), BTMABr
34.41g (3.5mmol) is raw material, is dissolved in dichloromethane solution (30ml), stirred at ambient temperature 12 hours, and filter, recrystallization in methylene dichloride and normal hexane, obtain the 7-tertiary butyl-1,3-dibromo pyrene 3.02g, productive rate is 78%;
3rd step: by the second step product 7-tertiary butyl-1,3-dibromo pyrene 200mg (0.5mmol), phenylo boric acid 250mg (2.0mmol), tetrakis triphenylphosphine palladium 70mg (0.06mmol) and salt of wormwood 250mg (1.8mmol) add in single neck bottle, then toluene (12ml) and ethanol (4ml) is added, strong stirring, temperature is kept to be 90 DEG C, reflux 24 hours, filter out product, through column chromatography chromatogram or recrystallization, obtain the highly purified 7-tertiary butyl-1,3-phenylbenzene pyrene (124mg), productive rate about 63%;
4th step: under the condition of nitrogen protection, by the 3rd step product 7-tertiary butyl-1,3-phenylbenzene pyrene 410mg (0.09mmoL) and Nafion-H (400mg) add closed reactor, strong stirring, keep temperature to be 150 DEG C, react 24 hours, filter out product, through column chromatography chromatogram or recrystallization, obtain highly purified 1,3-phenylbenzene pyrene (300mg), productive rate about 85%;
5th step: under the condition of nitrogen protection, with the 4th step product 1,3-phenylbenzene pyrene 0.48mmol and BTMABr3480mg (1.2mmol) is raw material, be dissolved in methylene dichloride (10ml), at room temperature stir 5 hours, filter, recrystallization in methylene dichloride and normal hexane, obtain 1,3-phenylbenzene-6-bromine pyrene (270g), productive rate is 75%;
6th step: under the condition of nitrogen protection, by the 5th step product 1, 3-phenylbenzene-6-bromine pyrene 100mg (0.23mmol), 4-ethynyl biphenyl 55mg (0.3mmol), two (triphenylphosphine) palladium chloride 21mg (0.03mmol), triphenylphosphine 20mg (0.08mmol), triethylamine (5ml) and N, dinethylformamide (5ml) adds in single neck bottle, strong stirring, temperature is kept to be 110 DEG C, reflux 48 hours, filter out product, through column chromatography chromatogram or recrystallization, obtain highly purified target product (68mg), productive rate about 56%.
In mass spectrum, m/z:530.20 (100.0%), 531.21 (45.7%), 532.21 (10.2%), 533.21 (1.5%)
The maximum emission peak of target product 1-phenyl-6-two-(4-ethynylbiphenyl) pyrene under solution state is 434nm, specifically sees Fig. 3.
Embodiment 4
The preparation of 1,3-phenyl-6,8-bis--(4,4 ,-two fluorine-based pentanoic bases) pyrene
The molecular structural formula of 1,3-phenyl-6,8-bis--(4,4 ,-two fluorine-based pentanoic bases) pyrene is as follows:
Concrete preparation method is as follows:
The first step: under the condition of nitrogen protection, with by 1,3-phenylbenzene pyrene 0.875mmol and BTMABr prepared in embodiment 3
31.4g (3.5mmol) is raw material, is dissolved in methylene dichloride (10ml), at room temperature stirs 5 hours, and filter, recrystallization in methylene dichloride and normal hexane, obtains 1,3-phenylbenzene-6,8-dibromo pyrene (270g), and productive rate is 79%;
Second step: under the condition of nitrogen protection, by 1, 3-phenylbenzene-6, 8-dibromo pyrene 150mg (0.29mmol), 4, 4,-two fluorine-based pentanoic 180mg (0.87mmol), tertiary butyl phosphine 0.05ml, palladium 40mg (0.18mmol), cesium carbonate 51mg (0.2mmol) adds in single neck bottle, then o-Xylol (12ml) is added, strong stirring, temperature is kept to be 120 DEG C, reflux 48 hours, filter out product, through column chromatography chromatogram or recrystallization, obtain highly purified target product 1, 3-phenyl-6, 8-bis--(4, 4,-two fluorine-based pentanoic bases) pyrene (125mg), productive rate about 56%.
In addition, the application has also been prepared
with
the spectroscopic data of the end product that these two kinds of compounds and embodiment 1-4 obtain is as shown in table 1.
The spectroscopic data of the derivative of table 1 pyrene
As can be seen from Table 1, the derivative of the Asymmetrical substitute pyrene of the present invention's synthesis, decomposition temperature is all greater than 300 DEG C, and fusing point is all higher, illustrates to have good thermostability; Maximum emission wavelength and quantum yield data show: derivative display mazarine photoluminescent property (the 411nm< λ of this Asymmetrical substitute pyrene
em max<437nm), high quantum yield (>86%), the luminous efficiency describing the derivative of this Asymmetrical substitute pyrene is high.
The pyrene class blue light material of the present invention's synthesis, selected by solid, at 1 of pyrene, 3-position, 6,8-positions or 1-position, 6,8-positions introduce the substituted radical with different electronic effect respectively, build D-A system, what regulate importing pushes away electronics/electron-withdrawing power, charge transfer in inducing molecule, prepares the luminophor of high-fluorescence quantum yield; Improve the luminescent properties of material.By suitable molecule cutting, the degree of regulation and control conjugated system and the accumulation mode of molecule under condensed state, to reduce intermolecular interaction, and then improve the luminosity of luminous organic material under condensed state, thus material emission performance is significantly improved, this pyrene class material with unsymmetrical structure can be widely used in Blue OLED device.
Although illustrate and describe the present invention with specific embodiment, however it will be appreciated that can to make when not deviating from the spirit and scope of the present invention many other change and amendment.Therefore, this means to comprise all such changes and modifications belonged in the scope of the invention in the following claims.
Claims (10)
1. a derivative for pyrene, is characterized in that, has following structure:
Wherein:
R
1substituting group be selected from the substituted aroma hydrocarbon with 5 to 30 carbon atoms, the aryloxy with 6 to 50 carbon atoms, have 5 to 30 carbon atoms aromatic amine, have 6-20 carbon atom boron aromatic hydrocarbons, there is one in the aromatic heterocyclic group of 5 to 40 annular atomses or cyano group;
R
1' substituting group is selected from the substituted aroma hydrocarbon with 5 to 30 carbon atoms, the aryloxy with 6 to 50 carbon atoms, the aromatic amine with 5 to 30 carbon atoms, the boron aromatic hydrocarbons with 6-20 carbon atom, the one had in the aromatic heterocyclic group of 5 to 40 annular atomses, cyano group or hydrogen;
R
2substituting group be selected from the substituted aroma hydrocarbon with 5 to 30 carbon atoms, the aryloxy with 6 to 50 carbon atoms, have 5 to 30 carbon atoms aromatic amine, have 6-20 carbon atom boron aromatic hydrocarbons, there is one in the aromatic heterocyclic group of 5 to 40 annular atomses or cyano group;
R
1substituting group and R
2substituting group is different;
R
1' substituting group and R
2substituting group is different.
2. the derivative of pyrene according to claim 1, is characterized in that, described R1 ' substituting group is hydrogen.
3. the derivative of pyrene according to claim 1, is characterized in that, described R1 ' substituting group and described R
1substituting group is identical.
4. the preparation method of the derivative of pyrene according to claim 2, is characterized in that, comprises the following steps:
(a),
with bromizating agent in organic solvent, be obtained by reacting
(b),
by crosslinked coupled reaction, obtain
(c),
with bromizating agent in organic solvent, be obtained by reacting
(d),
by crosslinked coupled reaction, obtain
5. preparation method according to claim 4, is characterized in that, in step (a) and (c), described bromizating agent is selected from any one or more in N-bromo-succinimide, benzyl trimethyl tribromide ammonium and bromine water;
Preferably, in step (a) and (c), described organic solvent is any one in methylene dichloride, trichloromethane, tetrachloromethane.
6. preparation method according to claim 4, it is characterized in that, in step (b) and (d), described crosslinked coupled reaction is any one in Suzuki reaction, Sonogashira reaction, Buchwald – Hartwig linked reaction;
Preferably, in step (c), under protection of inert gas,
be that 1:2.5 ~ 4 are mixed in methylene dichloride with bromizating agent with mol ratio, react 4 ~ 5 hours at normal temperatures, filter and obtain product, described product, through column chromatography chromatogram or recrystallization, obtains
7. the preparation method of the derivative of pyrene according to claim 3, is characterized in that, comprises the following steps:
(a),
with isobutyl chloride in dichloromethane solution, with AlCl
3carry out catalysis, be obtained by reacting
(b),
under the effect of bromizating agent benzyl trimethyl tribromide ammonium, be obtained by reacting
(c),
by crosslinked coupled reaction, obtain
(d),
with catalyzer in organic solvent, reaction after generate
(e),
with bromizating agent in organic solvent, reaction after generate
(f),
by crosslinked coupled reaction, obtain
8. preparation method according to claim 7, is characterized in that, in step (d), described catalyzer is Nafion-H;
In step (d), described organic solvent be preferably in toluene, o-Xylol, m-xylene and p-Xylol one or more.
9. preparation method according to claim 7, is characterized in that, in step (e), described bromizating agent is one or more in N-bromo-succinimide, benzyl trimethyl tribromide ammonium and bromine water;
Preferably, in step (c) and (f), described crosslinked coupled reaction is any one in Suzuki reaction, Sonogashira reaction, Buchwald – Hartwig linked reaction;
Preferably, in step (e), under protection of inert gas,
be that 1:2.5 ~ 4 are mixed in methylene dichloride with bromizating agent with mol ratio, react 4 ~ 5 hours at normal temperatures, filter and obtain product, described product, through column chromatography chromatogram or recrystallization, obtains
10. the derivative of the pyrene described in any one of claim 1-3 is as the application of luminescent material in photo luminescent devices.
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| CN107434758A (en) * | 2017-05-23 | 2017-12-05 | 浙江工业大学 | Method for synthesizing monobromo condensed ring aromatic hydrocarbon compound |
| CN108059583A (en) * | 2018-01-19 | 2018-05-22 | 李现伟 | A kind of biphenyl compound and its application in 1- bromine pyrenes are prepared |
| CN110183315A (en) * | 2019-06-10 | 2019-08-30 | 南京邮电大学 | A kind of pyrene derivatives material and the preparation method and application thereof |
| CN111333483A (en) * | 2020-03-13 | 2020-06-26 | 陕西师范大学 | Pyrene blue organic fluorescent material and preparation method and application thereof |
| CN114516779A (en) * | 2022-02-21 | 2022-05-20 | 中国科学院化学研究所 | Method for selective functionalization of bicycloheptatriene-rubine (DHR) and derivatization application thereof |
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Cited By (7)
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| CN107434758A (en) * | 2017-05-23 | 2017-12-05 | 浙江工业大学 | Method for synthesizing monobromo condensed ring aromatic hydrocarbon compound |
| CN108059583A (en) * | 2018-01-19 | 2018-05-22 | 李现伟 | A kind of biphenyl compound and its application in 1- bromine pyrenes are prepared |
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| CN111333483A (en) * | 2020-03-13 | 2020-06-26 | 陕西师范大学 | Pyrene blue organic fluorescent material and preparation method and application thereof |
| CN111333483B (en) * | 2020-03-13 | 2024-01-26 | 陕西师范大学 | Pyrene blue organic fluorescent material and preparation method and application thereof |
| CN114516779A (en) * | 2022-02-21 | 2022-05-20 | 中国科学院化学研究所 | Method for selective functionalization of bicycloheptatriene-rubine (DHR) and derivatization application thereof |
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