CN104876825B - A kind of derivant of pyrene and its preparation method and application - Google Patents
A kind of derivant of pyrene and its preparation method and application Download PDFInfo
- Publication number
- CN104876825B CN104876825B CN201510219480.5A CN201510219480A CN104876825B CN 104876825 B CN104876825 B CN 104876825B CN 201510219480 A CN201510219480 A CN 201510219480A CN 104876825 B CN104876825 B CN 104876825B
- Authority
- CN
- China
- Prior art keywords
- pyrene
- group
- preparation
- carbon atoms
- substituent group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Electroluminescent Light Sources (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to field of organic electroluminescent materials, in particular to a kind of derivant of pyrene and its preparation method and application.The derivant of the pyrene that the present invention provides, it is the 1 of pyrene, 3 and 6,8 introducings have the large-substituent unit of different electronic properties, rigid structure, the destruction of molecule coplanarity will suppress its intermolecular π pi accumulation, make it be difficult to form exciplex, and suppress its crystallization process, improve its film property；And then reach the purpose improving device performance；By introducing electron donor and electron acceptor in specific position, realize asymmetric functionalization pyrene ring, construct push-pull type molecule, induction occurs Intramolecular electron transfer, improve the charge transport ability of material, preparation has blue light property and the luminous organic material of high fluorescence quantum yield.Compared to existing luminescent material, the luminous efficiency of this material, excitation and stability all have larger lifting.
Description
Technical field
The present invention relates to field of organic electroluminescent materials, in particular to a kind of derivant of pyrene and its preparation side
Method and application.
Background technology
Development with multimedia technology and the arriving of information-intensive society, the requirement more and more higher to flat faced display performance.
Organic Light Emitting Diode (Organic Light-Emitting Diodes, OLED) device communication, information, display, illumination and
Novel full color shows high-tech areas such as luminous (Full-Color Flat-Panel Displays), shows huge business
Application prospect, becomes a study hotspot at this stage.Many scientists are devoted to the research of OLED, and obtain proud one-tenth
Really.
Currently, the research of OLED is concentrated mainly on to the making of device and exploitation two aspect of functional material, and develops
The luminous organic material of unique electronic structure and luminescent properties becomes one of research emphasis.Organic material is because having high lighting
Efficiency, the wide glow color range of choice, the superiority of easy large area film forming, be widely used in functional material and device it
In.In the evolution of OLED, in order to realize full-color EL display (Full-Color Flat-Panel Displays), preparation
Blue light emitting material is most important.Blue light material not only can realize efficient, stable blue emission, meets full-color EL display
Require, and because its energy gap is relatively wide, using it as material of main part, using chemical modification techniques, shift the methods such as energy, permissible
Obtain corresponding red light material and green light material.At present, HONGGUANG, green light material are with fastest developing speed, have basically reached commercialization practical
Stage, and it is challenging to prepare air-stable, high efficiency and the high blue light material of excitation.Therefore explore the tool of synthesizing new
The navy blue luminescent material having premium properties becomes current top priority.
Pyrene is the polycyclic aromatic compounds that a class has big conjugatedπbond, and it has good heat stability, strong electronics passes
Lead, navy blue photoluminescent property and high quantum yield, be widely used in the research of the aspects such as fluorescent probe.But, in high concentration (＞
10-4Mol/L, under solution) or solid state, pyrene easily forms bimolecular exciplex, thus reducing fluorescence quantum efficiency, pole
Big limits pyrene application as luminescent material in the opto-electronic device.Therefore, pyrene ring is modified, preparation is with pyrene as parent
The high-performance luminescent material of (or containing pyrenyl group), is increasingly becoming study hotspot.
With the progress of OLED technology, the research of OLED material obtains tremendous expansion, the active position (1,3,6,8- of pyrene
Position) and K- region (4,5,9,10- position) obtain widely studied.But great majority research is concentrated mainly on the symmetrical pyrene that replaces prepares pyrenyl
Luminescent material, this kind of one maximum shortcoming of material is exactly the problem of poor solubility and excitation.Light currently for pyrenyl class
Material, more tends to explore the performance study of the luminescent material of the synthetic route of asymmetric functionalization pyrene and asymmetric pyrene.
Main cause is to introduce asymmetric electron donor-acceptor structure unit in pyrene ring, builds the molecular structure of big conjugation, by Molecular regulator
Interior electric charge transfer (intramolecular charge-transfer, ICT), increases intramolecular charge coupling, is conducive to
Adjust the electronic structure of material, reduce intramolecular energy level, improve the quantum yield of compound.With M ü llen seminar as representative,
Take the lead in reporting the 4- in pyrene ring, 5- position and 9-, 10- position carries out asymmetric modification, be prepared for D-A type pyrenyl derivant, push away electricity
Subbase group and electron withdraw group are simultaneously introduced the K- region of pyrene ring, by Intramolecular electron transfer, effectively reduce molecule
Energy level, by Molecular regulator energy level, is prepared for green, Huang Hehong pyrenyl luminescent material, but but can not obtain one of three primary colours
Blue light material.And, the derivant of existing asymmetric pyrene suffers from the drawback that：
1st, preparation method is complex；
2nd, pyrenyl class blue light material fluorescence quantum yield is relatively low；
3rd, the luminous efficiency of pyrenyl class blue light material, excitation and stability need to be lifted further.
In view of this, the special proposition present invention.
Content of the invention
The first object of the present invention is to provide a kind of derivant of pyrene, and the derivant of described pyrene has asymmetric
Chain structure, compared to existing luminescent material, the luminous efficiency of this material, excitation and stability all have larger lifting.
The second object of the present invention is to provide a kind of preparation method of the derivant of described pyrene, and the method is simply easy
OK, high income.
The third object of the present invention is to provide a kind of derivant of described pyrene as luminescent material in photoluminescent emitter
Application in part.
In order to realize the above-mentioned purpose of the present invention, spy employs the following technical solutions：
A kind of derivant of pyrene is it is characterised in that have following structure：
Wherein：
R1Substituent group be selected from have 5 to 30 carbon atoms substituted aroma hydrocarbon, have 6 to 50 carbon atoms aryloxy group,
The aromatic amine with 5 to 30 carbon atoms, the boron aromatic hydrocarbons with 6-20 carbon atom, there is the fragrant aromatics of 5 to 40 annular atoms
One of heterocyclic group or cyano group；
R1' substituent group be selected from have 5 to 30 carbon atoms substituted aroma hydrocarbon, have 6 to 50 carbon atoms aryloxy group,
The aromatic amine with 5 to 30 carbon atoms, the boron aromatic hydrocarbons with 6-20 carbon atom, the aromatic series with 5 to 40 annular atoms
One of heterocyclic group, cyano group or hydrogen；
R2Substituent group be selected from have 5 to 30 carbon atoms substituted aroma hydrocarbon, have 6 to 50 carbon atoms aryloxy group,
The aromatic amine with 5 to 30 carbon atoms, the boron aromatic hydrocarbons with 6-20 carbon atom, the aromatic series with 5 to 40 annular atoms
One of heterocyclic group or cyano group；
R1Substituent group and R2Substituent group is different；
R1' substituent group and R2Substituent group is different.
The derivant of the pyrene that the present invention provides, is 1-, 3- and the 6- in pyrene, and 8- position introduces has different electronic properties, just
Property structure large-substituent unit, the destruction of molecule coplanarity will suppress its intermolecular pi-pi accumulation so as to be difficult formed swash
Base complex, and suppress its crystallization process, improve its film property；And then reach the purpose improving device performance；By specific
Position introduce electron donor and electron acceptor, realize asymmetric functionalization pyrene ring, construct push-pull type molecule, induction occurs molecule
Interior electric charge transfer, improves the charge transport ability of material, and preparation has organic of blue light property and high fluorescence quantum yield
Luminescent material.Compared to existing luminescent material, the luminous efficiency of this material, excitation and stability all have larger lifting.
Preferably, described R1' substituent group be hydrogen.
I.e. the derivant of pyrene has following structure：
The derivant of such pyrene, is 1- and 6- in pyrene, and 8- position introduces has different electronic properties, the taking greatly of rigid structure
For base unit so as to be difficult to form exciplex, and suppress its crystallization process, improve its film property, improve the transmission of its electric charge
Performance；Meanwhile, the destruction of molecule public affairs flatness will be destroyed its emission peak blue shift and then reached the purpose improving device performance, realizes
Asymmetric functionalization pyrene, preparation has blue light property and the luminous organic material of high fluorescence quantum yield.Compared to existing
Luminescent material, the luminous efficiency of this material, excitation and stability all have larger lifting.
Preferably, described R1' substituent group and described R1Substituent group is identical.I.e. the derivant of Asymmetrical substitute pyrene have following
Structure：
Wherein：
R1Substituent group be selected from have 5 to 30 carbon atoms substituted aroma hydrocarbon, have 6 to 50 carbon atoms aryloxy group,
There is the aromatic amine of 5 to 30 carbon atoms, the virtue having the boron aromatic hydrocarbons containing 6-20 carbon atom, having 5 to 40 annular atoms
One of fragrant race heterocyclic group or cyano group；
R2Substituent group be selected from have 5 to 30 carbon atoms substituted aroma hydrocarbon, have 6 to 50 carbon atoms aryloxy group,
There is the aromatic amine of 5 to 30 carbon atoms, the virtue having the boron aromatic hydrocarbons containing 6-20 carbon atom, having 5 to 40 annular atoms
One of fragrant race heterocyclic group or cyano group；
R1Substituent group and R2Substituent group is different.
The derivant of this pyrene, is 1-, 3- and the 6- in pyrene, 8- position introduce have different electronic properties, rigid structure big
Substituent group unit, the destruction of molecule coplanarity will suppress its intermolecular pi-pi accumulation so as to be difficult to form exciplex,
And suppress its crystallization process, improve its film property；And then reach the purpose improving device performance；By introducing in specific position
Electron donor and electron acceptor, realize asymmetric functionalization pyrene ring, construct push-pull type molecule, and induction occurs intramolecular charge to turn
Move, improve the charge transport ability of material, preparation has blue light property and the luminous organic material of high fluorescence quantum yield.Phase
In existing luminescent material, the luminous efficiency of this material, excitation and stability all have larger lifting to ratio.
Derivant as the Asymmetrical substitute pyrene of present invention offer can be any one of following structural formula：
R therein1And R2For end-capping group, it is selected from as hydrogen, fluorine, alkyl, alkoxyl, aldehyde radical, amido, cyano group, C6-C30
Aryl, the heteroaryl of C2-C30, the aralkyl of C6-C30, the heteroarylalkyl of C2-C30, the aryloxy group of C5-C30, C2-C30
Any one in the Heterocyclylalkyl of heteroaryloxy, the cycloalkyl of C3-C30 or C2-C30.
Present invention also offers the preparation method of the derivant of described pyrene, comprise the following steps：
(a)、With bromating agent in organic solvent, reaction obtains
(b)、By crosslinked coupling reaction, obtain
(c)、With bromating agent in organic solvent, reaction obtains
(d)、By crosslinked coupling reaction, obtain
The preparation method of the derivant of pyrene that the present invention provides, is with pyrene, bromating agent etc. as raw material, by chemistry progressively
Synthesis, method is simple, prepares the novel bromine pyrene derivatives intermediate of a class, then passes through classical crosslinked coupling anti-
Should, prepare Asymmetrical substitute pyrene derivatives, this pyrenyl analog derivative is to have having of blue light property and high fluorescence quantum yield
Machine luminescent material.
Synthetic route is：
Preferably, in step (a) and (c), described bromating agent is selected from N- bromo-succinimide, benzyl trimethyl tribromo
Change any one or more in ammonium and bromine water.Empirical tests, the bromating agent reactivity of this species is higher, and selectivity is preferably it is easy to obtain
To product.
Preferably, in step (a) and (c), described organic solvent is dichloromethane, in chloroform, tetrachloromethane
Any one.The organic solvent of this species is easy to the carrying out of bromination reaction, it is to avoid the generation of other by-products.
Preferably, in step (b) and (d), described crosslinking coupling reaction is Suzuki reaction, Sonogashira reacts,
Any one in Buchwald Hartwig coupling reaction.Above-mentioned crosslinking coupling reaction is classical crosslinked coupling reaction, technology
, it is easy to apply, product is stable for maturation.
In order to reach more preferable reaction effect it is preferable that in step (c), under inert gas shielding,With
Bromating agent is with mol ratio for 1：2.5-4 is mixed in dichloromethane, reacts 4-5 hour at normal temperatures, is filtrated to get product, described
Product, through column chromatography chromatogram or recrystallization, obtains
Present invention also offers the preparation method of the derivant of another kind of asymmetric functionalization pyrene, comprise the following steps：
(a)、With isobutyl chloride in dichloromethane solution, with AlCl3It is catalyzed, reaction obtains
(b)、In the presence of bromating agent benzyl trimethyl tribromide ammonium, reaction obtains
(c)、By crosslinked coupling reaction, obtain
(d)、With catalyst in organic solvent, generate after reaction
(e)、With bromating agent in organic solvent, generate after reaction
(f)、By crosslinked coupling reaction, obtain
The preparation method of this Asymmetrical substitute pyrene, by chemosynthesis progressively, method is simple, prepares a class
Novel bromine pyrene derivatives intermediate, then passes through classical crosslinked coupling reaction, prepares the pyrene class of Asymmetrical substitute, such pyrene
Based luminescent material has the features such as efficient blue light property, high fluorescence quantum yield and good heat stability.
Synthetic route is：
Preferably, in step (d), described catalyst is Nafion-H.Perfluorinated sulfonic resin (Nafion-H) is present
The known super acids of strong solid, have that heat resistance is good, a chemical stability and the features such as high mechanical strength.Nafion-H is used as
It is easy to separate during catalyst, can Reusability；And corrosivity are little, cause public hazards few, selectivity good it is easy in industrialized production
Middle application.
Preferably, in step (d), described organic solvent is in toluene, o-Dimethylbenzene, meta-xylene and xylol
One or more.
Preferably, in step (e), described bromating agent be N- bromo-succinimide, benzyl trimethyl tribromide ammonium and
One or more of bromine water.
Preferably, in step (c) and (f), described crosslinking coupling reaction is Suzuki reaction, Sonogashira reacts,
Any one in Buchwald Hartwig coupling reaction.Above-mentioned crosslinking coupling reaction is classical crosslinked coupling reaction, technology
, it is easy to apply, product is stable for maturation.
In order to preferably react, specific product is obtained it is preferable that in step (e), protecting in noble gases with more efficient
Under shield,With bromating agent with mol ratio for 1：2.5～4 are mixed in dichloromethane, and reaction 4～5 is little at normal temperatures
When, it is filtrated to get product, described product, through column chromatography chromatogram or recrystallization, obtainsAsWith bromine
The mol ratio of agent can be 1：2.5、1：3、1：3.5 and 1：4 etc..
Present invention also offers the application in the opto-electronic device as luminescent material of the derivant of described pyrene.
Compared with prior art, beneficial effects of the present invention are：
(1) derivant of the pyrene that the present invention provides is 1- and 6-, 8- position or 1-, 3- and the 6- in pyrene in pyrene, and 8- draws position
Enter to have the large-substituent unit of different electronic properties, rigid structure, the destruction of molecule coplanarity will suppress it intermolecular
Pi-pi accumulation is so as to be difficult to form exciplex, and suppresses its crystallization process, improves its film property；And then reach and improve device
The purpose of performance；By introducing electron donor and electron acceptor in specific position, realize Asymmetrical substitute pyrene ring, construct push-and-pull
Type molecule, there is Intramolecular electron transfer in induction, improve the charge transport ability of material, and preparation has blue light property and high glimmering
The luminous organic material of quantum yield, compared to existing luminescent material, the luminous efficiency of this luminescent material, excitation and steady
Qualitative all have larger lifting；
(2) preparation method of the derivant of pyrene that the present invention provides, by chemosynthesis progressively, method is simple,
Prepare the novel bromine pyrene derivatives intermediate of a class, then pass through classical crosslinked coupling reaction, prepare asymmetric function
Change pyrenyl derivant, such pyrenyl derivant is to have the luminous organic material of blue light property and high fluorescence quantum yield.
(3) present invention passes through to select specific bromating agent, organic solvent and catalyst etc. so that preparation process is simply easy
OK, yield is high, and pollution is few.
Brief description
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
The accompanying drawing having required use in technology description is briefly described.
Fig. 1 is 1- phenyl -6 in the embodiment of the present invention 1, the fluorescence emission of 8- bis--(4,4,-two fluorine-based diphenylamines bases) pyrene
Spectrogram；
Fig. 2 is 1- phenyl -6 in the embodiment of the present invention 2, the fluorescence emission spectrogram of compound of 8- dicyan pyrene；
Fig. 3 is the fluorescence emission spectrogram of compound of 1- phenyl -6- two-(4- ethynylbiphenyl) pyrene in the embodiment of the present invention 3.
Specific embodiment
Below in conjunction with embodiment, embodiment of the present invention is described in detail, but those skilled in the art will
Understand, the following example is merely to illustrate the present invention, and be not construed as limiting the scope of the present invention.Unreceipted concrete in embodiment
Condition person, the condition according to normal condition or manufacturer's suggestion is carried out.Agents useful for same or the unreceipted production firm person of instrument, are
Can be by the conventional products of commercially available acquisition.
Embodiment 1
1- phenyl -6, the preparation of 8- bis--(4,4,-two fluorine-based diphenylamines bases) pyrene
1- phenyl -6, the molecular structural formula of 8- bis--(4,4,-two fluorine-based diphenylamines bases) pyrene is as follows：
Concrete preparation process is as follows：
The first step：Under conditions of nitrogen protection, take pyrene 1g (4.9mmol) and benzyl trimethyl tribromide ammonium (NBS)
974mg (5.5mmol), is dissolved in 50ml dichloromethane, is stirred at room temperature 5 hours, filters, weight in dichloromethane and normal hexane
Crystallization, obtains 1- bromine pyrene (1.08g), and yield is 78%；
Second step：Under conditions of nitrogen protection, by first step product 1- bromine pyrene 500mg (1.78mmol), phenylboric acid
270mg (2.2mmol), tetrakis triphenylphosphine palladium 70mg (0.06mmol), potassium carbonate 300mg (2.2mmol) add in single neck bottle,
It is subsequently adding toluene (10ml) and ethanol (4ml), strong stirring, keeping temperature is 90 DEG C, flow back 24 hours, filter out product,
Through column chromatography chromatogram or recrystallization, obtain highly purified 1- phenyl pyrene (109mg), yield about 70%；
3rd step：Under conditions of nitrogen protection, by second step product 1- phenyl pyrene 350mg (1.26mmol) and
BTMABr31.72g (4.4mmol) is raw material, is stirred at room temperature 5 hours, filters, ties in dichloromethane and normal hexane again
Crystalline substance, obtains final product 1- phenyl -6,8- dibromo pyrene (328mg), and yield is 75%；
4th step：Under conditions of nitrogen protection, by the 3rd step product 1- phenyl -6,8- dibromo pyrene 110mg
(0.25mmol), 4,4 ,-two fluorine-based diphenylamines 130mg (0.63mmol), tert-butyl group phosphine 30mg (1mmol), palladium 30mg
(0.13mmol), cesium carbonate 200mg (0.61mmol) adds in single neck bottle, is subsequently adding o-Dimethylbenzene (10ml), strong stirring,
Keeping temperature is 120 DEG C, flows back 48 hours, filters out product, through column chromatography chromatogram or recrystallization, obtains highly purified target and produces
Thing (97mg), yield about 56%.
In mass spectrum, m/z:684.22 (100.0%), 685.22 (50.5%), 686.23 (12.3%), 687.23
(2.0%).
Maximum emission peak under solution state for the target product is 481nm, specifically as shown in Figure 1.
Embodiment 2
1- phenyl -6, the preparation of 8- dicyan pyrene
1- phenyl -6, the molecular structural formula of 8- dicyan pyrene is as follows：
Concrete preparation process is as follows：
The first step：Under conditions of nitrogen protection, take pyrene 1g (4.9mmol) and NBS974mg (5.5mmol), be dissolved in 50ml
Dichloromethane, is stirred at room temperature 5 hours, filters, recrystallization in dichloromethane and normal hexane, obtains 1- bromine pyrene (1.08g),
Yield is 78%；
Second step：Under conditions of nitrogen protection, by first step product 1- bromine pyrene 500mg (1.78mmol), phenylboric acid
270mg (2.2mmol), tetrakis triphenylphosphine palladium 70mg (0.06mmol), potassium carbonate 300mg (2.2mmol) add in single neck bottle,
It is subsequently adding toluene (10ml) and ethanol (4ml), strong stirring, keeping temperature is 90 DEG C, flow back 24 hours, filter out product,
Through column chromatography chromatogram or recrystallization, obtain highly purified 1- phenyl pyrene (109mg), yield about 70%；
3rd step：Under conditions of nitrogen protection, by second step product 1- phenyl pyrene 1.76mmol and BTMABr31.72g
(4.4mmol) be raw material, be stirred at room temperature 4 hours, filter, recrystallization in dichloromethane and normal hexane, obtain final product 1- phenyl-
6,8- dibromo pyrenes (328mg), yield is 72%；
4th step：Under conditions of nitrogen protection, by 1- phenyl -6,8- dibromo pyrene 110mg (0.25mmol), CuCN
50mg (0.55mmol) and N-Methyl pyrrolidone 10ml adds in single neck bottle, strong stirring, and keeping temperature is 100 DEG C, backflow
24 hours, filter out product, through column chromatography chromatogram or recrystallization, obtain highly purified target product 1- phenyl -6,8- dicyan pyrene
46mg, yield about 56%.
In mass spectrum, m/z:328.10 (100.0%), 329.10 (26.7%), 330.11 (3.3%)
Target product 1- phenyl -6, maximum emission peak under solution state for the 8- dicyan pyrene is 432nm, is specifically shown in 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 conditions of nitrogen protection, the pyrene 1g (4.9mmol) and different tertiary butyl chloride 450mg (4.9mmol) is taken to be
Raw material, in AlCl3Under the catalysis of 1.4g (9mmol), in dichloromethane solution (50ml), stir 5 hours under room temperature, filter,
Recrystallization in normal hexane, obtains final product 2- tert-butyl group pyrene (1.9g), and yield is 83%；
Second step：Under conditions of nitrogen protection, take 2- tert-butyl group pyrene 2.58g (1mmol), BTMABr34.41g
(3.5mmol) it is raw material, is dissolved in dichloromethane solution (30ml), stir 12 hours under room temperature, filter, in dichloromethane with just
Recrystallization in hexane, obtains the 7- tert-butyl group -1,3- dibromo pyrene 3.02g, and yield is 78%；
3rd step：By the second step product 7- tert-butyl group -1,3- dibromo pyrene 200mg (0.5mmol), phenylboric acid 250mg
(2.0mmol), tetrakis triphenylphosphine palladium 70mg (0.06mmol) and potassium carbonate 250mg (1.8mmol) adds in single neck bottle, then
Add toluene (12ml) and ethanol (4ml), strong stirring, keeping temperature is 90 DEG C, flow back 24 hours, filter out product, through post
Thin layer chromatography or recrystallization, obtain the highly purified 7- tert-butyl group -1,3- diphenyl pyrene (124mg), yield about 63%；
4th step：Under conditions of nitrogen protection, by the 3rd step product 7- tert-butyl group -1st, 3- diphenyl pyrene 410mg
(0.09mmoL) closed reactor, strong stirring are added with Nafion-H (400mg), keeping temperature is 150 DEG C, reaction 24 is little
When, filter out product, through column chromatography chromatogram or recrystallization, obtain highly purified 1,3- diphenyl pyrene (300mg), yield is about
85%；
5th step：Under conditions of nitrogen protection, with the 4th step product 1,3- diphenyl pyrene 0.48mmol and
BTMABr3480mg (1.2mmol) is raw material, is dissolved in dichloromethane (10ml), is stirred at room temperature 5 hours, filters, in dichloro
Recrystallization in methane and normal hexane, obtains 1,3- diphenyl -6- bromine pyrene (270g), and yield is 75%；
6th step：Under conditions of nitrogen protection, by the 5th step product 1,3- diphenyl -6- bromine pyrene 100mg
(0.23mmol), 4- acetenyl biphenyl 55mg (0.3mmol), two (triphenylphosphine) palladium chloride 21mg (0.03mmol), triphen
Base phosphine 20mg (0.08mmol), triethylamine (5ml) and DMF (5ml) add in single neck bottle, and strong stirring is protected
Hold temperature and be 110 DEG C, flow back 48 hours, filter out product, through column chromatography chromatogram or recrystallization, obtain highly purified target product
(68mg), yield about 56%.
In mass spectrum, m/z:530.20 (100.0%), 531.21 (45.7%), 532.21 (10.2%), 533.21
(1.5%)
Target product 1- phenyl -6- two-(4- ethynylbiphenyl) maximum emission peak under solution state for the pyrene is
434nm, is specifically shown in Fig. 3.
Embodiment 4
1,3- phenyl -6, the preparation of 8- bis--(4,4,-two fluorine-based diphenylamines bases) pyrene
1,3- phenyl -6, the molecular structural formula of 8- bis--(4,4,-two fluorine-based diphenylamines bases) pyrene is as follows：
Concrete preparation method is as follows：
The first step：Under conditions of nitrogen protection, with by 1, the 3- diphenyl pyrene preparing in embodiment 3
0.875mmol and BTMABr31.4g (3.5mmol) is raw material, is dissolved in dichloromethane (10ml), is stirred at room temperature 5 hours, mistake
Filter, recrystallization in dichloromethane and normal hexane, obtain 1,3- diphenyl -6,8- dibromo pyrene (270g), yield is 79%；
Second step：Under conditions of nitrogen protection, by 1,3- diphenyl -6,8- dibromo pyrene 150mg (0.29mmol), 4,
4 ,-two fluorine-based diphenylamines 180mg (0.87mmol), tert-butyl group phosphine 0.05ml, palladium 40mg (0.18mmol), cesium carbonate 51mg
(0.2mmol) add in single neck bottle, be subsequently adding o-Dimethylbenzene (12ml), strong stirring, keeping temperature is 120 DEG C, backflow 48
Hour, 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 diphenylamines bases) pyrene (125mg), yield about 56%.
In addition, the application is also prepared forWithThis two kinds of compounds and reality
The spectroscopic data applying the end-product that a 1-4 is obtained is as shown in table 1.
The spectroscopic data of the derivant of table 1 pyrene
As it can be seen from table 1 the derivant of the Asymmetrical substitute pyrene of present invention synthesis, decomposition temperature is all higher than 300 DEG C, molten
Point is all higher, illustrates there is good heat stability；Maximum emission wavelength and quantum efficiency as shown by data：This Asymmetrical substitute pyrene
Derivant display navy blue photoluminescent property (411nm<λem max<437nm), high quantum efficiency (>86%), illustrate this not
The luminous efficiency of the symmetrical derivant replacing pyrene is high.
The present invention synthesis pyrene class blue light material, selected by solid, 1, the 3- position of pyrene, 6,8- position or 1- position, 6,8-
Position introduces the substituted radical with different electronic effects respectively, builds D-A system, and adjust importing pushes away electronics/electron-withdrawing power,
Electric charge transfer in inducing molecule, prepares the luminophor of high-fluorescence quantum yield；Improve the luminescent properties of material.By suitable
When molecule cutting, the accumulation mode under condensed state of degree and molecule of regulation and control conjugated system, with reduce intermolecular mutually
Effect, and then improve luminosity under condensed state for the luminous organic material, so that material emission performance is significantly improved,
This pyrene class material with dissymmetrical structure can be widely applied to Blue OLED device.
Although illustrate and describing the present invention with specific embodiment, but it will be appreciated that without departing substantially from the present invention's
Many other changes can be made in the case of spirit and scope and change.It is, therefore, intended that in the following claims
Including all such changes and modifications belonging in the scope of the invention.
Claims (11)
1. a kind of preparation method of the derivant of pyrene is it is characterised in that comprise the following steps：
(a)、With bromating agent in organic solvent, reaction obtains
(b)、By crosslinked coupling reaction, obtain
(c)、With bromating agent in organic solvent, reaction obtains
(d)、By crosslinked coupling reaction, obtain
The derivant of described pyrene has following structure：
Wherein：
R1Substituent group is selected to be had the substituted aroma hydrocarbon of 5 to 30 carbon atoms, has the aryloxy group of 6 to 50 carbon atoms, has 5
To 30 carbon atoms aromatic amine, there is the boron aromatic hydrocarbons of 6-20 carbon atom, there is the aromatic heterocycle of 5 to 40 annular atoms
One of group or cyano group；
R1' substituent group be hydrogen；
R2Substituent group is selected to be had the substituted aroma hydrocarbon of 5 to 30 carbon atoms, has the aryloxy group of 6 to 50 carbon atoms, has 5
To 30 carbon atoms aromatic amine, there is the boron aromatic hydrocarbons of 6-20 carbon atom, there is the aromatic heterocycle of 5 to 40 annular atoms
One of group or cyano group；
R1Substituent group and R2Substituent group is different；
R1' substituent group and R2Substituent group is different.
2. preparation method according to claim 1 is it is characterised in that in step (a) and (c), described bromating agent is selected from
Any one or more in N- bromo-succinimide, benzyl trimethyl tribromide ammonium and bromine water.
3. preparation method according to claim 1 is it is characterised in that in step (a) and (c), described organic solvent is
Any one in dichloromethane, chloroform, tetrachloromethane.
4. preparation method according to claim 1 is it is characterised in that in step (b) and (d), described crosslinking coupling is anti-
Should be Suzuki reaction, Sonogashira reaction, any one in Buchwald Hartwig coupling reaction.
5. preparation method according to claim 1 is it is characterised in that in step (c), under inert gas shielding,With bromating agent with mol ratio for 1：2.5～4 are mixed in dichloromethane, react 4～5 hours at normal temperatures, filter
Obtain product, described product, through column chromatography chromatogram or recrystallization, obtains
6. a kind of preparation method of the derivant of pyrene is it is characterised in that comprise the following steps：
(a)、With isobutyl chloride in dichloromethane solution, with AlCl3It is catalyzed, reaction obtains
(b)、In the presence of bromating agent benzyl trimethyl tribromide ammonium, reaction obtains
(c)、By crosslinked coupling reaction, obtain
(d)、With catalyst in organic solvent, generate after reaction
(e)、With bromating agent in organic solvent, generate after reaction
(f)、By crosslinked coupling reaction, obtain
The derivant of described pyrene has following structure：
Wherein：
R1Substituent group is selected to be had the substituted aroma hydrocarbon of 5 to 30 carbon atoms, has the aryloxy group of 6 to 50 carbon atoms, has 5
To 30 carbon atoms aromatic amine, there is the boron aromatic hydrocarbons of 6-20 carbon atom, there is the aromatic heterocycle of 5 to 40 annular atoms
One of group or cyano group；
R1' substituent group be selected from there is the substituted aroma hydrocarbon of 5 to 30 carbon atoms, there is the aryloxy group of 6 to 50 carbon atoms, have 5
To 30 carbon atoms aromatic amine, there is the boron aromatic hydrocarbons of 6-20 carbon atom, there is the aromatic heterocycle of 5 to 40 annular atoms
One of group or cyano group；
R2Substituent group is selected to be had the substituted aroma hydrocarbon of 5 to 30 carbon atoms, has the aryloxy group of 6 to 50 carbon atoms, has 5
To 30 carbon atoms aromatic amine, there is the boron aromatic hydrocarbons of 6-20 carbon atom, there is the aromatic heterocycle of 5 to 40 annular atoms
One of group or cyano group；
R1Substituent group and R2Substituent group is different；
R1' substituent group and R2Substituent group is different；
Described R1 ' substituent group and described R1Substituent group is identical.
7. preparation method according to claim 6 is it is characterised in that in step (d), described catalyst is Nafion-
H.
8. preparation method according to claim 6 is it is characterised in that in step (d), described organic solvent is toluene,
One or more of o-Dimethylbenzene, meta-xylene and xylol.
9. preparation method according to claim 6 is it is characterised in that in step (e), described bromating agent is N- bromo fourth
One or more of imidodicarbonic diamide, benzyl trimethyl tribromide ammonium and bromine water.
10. preparation method according to claim 6 is it is characterised in that in step (c) and (f), described crosslinking coupling is anti-
Should be Suzuki reaction, Sonogashira reaction, any one in Buchwald Hartwig coupling reaction.
11. preparation methoies according to claim 6 it is characterised in that in step (e), under inert gas shielding,With bromating agent with mol ratio for 1：2.5～4 are mixed in dichloromethane, react 4～5 hours at normal temperatures, filter
Obtain product, described product, through column chromatography chromatogram or recrystallization, obtains
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510219480.5A CN104876825B (en) | 2015-04-30 | 2015-04-30 | A kind of derivant of pyrene and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510219480.5A CN104876825B (en) | 2015-04-30 | 2015-04-30 | A kind of derivant of pyrene and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104876825A CN104876825A (en) | 2015-09-02 |
| CN104876825B true CN104876825B (en) | 2017-03-01 |
Family
ID=53944544
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510219480.5A Expired - Fee Related CN104876825B (en) | 2015-04-30 | 2015-04-30 | A kind of derivant of pyrene and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104876825B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107434758B (en) * | 2017-05-23 | 2021-05-11 | 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 |
| CN110183315B (en) * | 2019-06-10 | 2022-02-01 | 南京邮电大学 | Pyrene derivative 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 |
| CN114516779B (en) * | 2022-02-21 | 2023-03-31 | 中国科学院化学研究所 | Selective functionalization method of bicycloheptatriene-rubine (DHR) and derivatization application thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4060669B2 (en) * | 2002-08-28 | 2008-03-12 | 富士フイルム株式会社 | 1,3,6,8-tetrasubstituted pyrene compound, organic EL device and organic EL display |
| US7888856B2 (en) * | 2004-03-29 | 2011-02-15 | Fujifilm Corporation | Organic electroluminescence device and display apparatus containing the same, method for making organic electroluminescence device and method for making display apparatus |
| JP2010015785A (en) * | 2008-07-02 | 2010-01-21 | Fujifilm Corp | Light-emitting element, multicolor display device, and light-emitting element manufacturing method |
-
2015
- 2015-04-30 CN CN201510219480.5A patent/CN104876825B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104876825A (en) | 2015-09-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104876825B (en) | A kind of derivant of pyrene and its preparation method and application | |
| CN105778891B (en) | Organic photoelectrical material, preparation method and the organic electroluminescence device including the organic material | |
| CN105340101A (en) | Light-emitting material, long-persistent phosphor, organic light-emitting element and compound | |
| CN115073464B (en) | Organic compound, application thereof and organic electroluminescent device comprising same | |
| Yuan et al. | The electron inductive effect of CF3 on penta-carbazole containing blue emitters: Trade-off between color purity and luminescent efficiency in TADF OLEDs | |
| TW201105609A (en) | Organic electroluminescent device using organic electroluminescent compounds | |
| Huang et al. | Thermally activated delayed fluorescence of N-phenylcarbazole and triphenylamine functionalised tris (aryl) triazines | |
| CN109535131A (en) | It is a kind of using cyanopyridine as the compound of receptor and its application | |
| Wang et al. | An efficient guest/host fluorescent energy transfer pair based on the naphthalimide skeleton, and its application in heavily-doped red organic light-emitting diodes | |
| CN107573925B (en) | Organic electroluminescent compound | |
| CN113698436A (en) | Organic electrophosphorescent luminescent material and application thereof | |
| CN113773349A (en) | Organic electrophosphorescent luminescent material and application thereof in OLED (organic light emitting diode) device | |
| CN109608453A (en) | One kind is with the compound that 4,7- phenanthroline is receptor and its application | |
| CN107602542A (en) | A kind of organic compound containing dibenzo hexatomic ring and its application | |
| Lee et al. | Asymmetric indolylmaleimides as non-dopant type red color emitting dyes | |
| Yao et al. | Triphenylamine or carbazole-containing dibenzothiophene sulfones: Color-tunable solid-state fluorescence and hypso-or bathochromic mechanofluorochromic behaviors | |
| CN102617466A (en) | Top-bottom asymmetrical tert-butyl spirobifluorene compound | |
| CN103232472A (en) | Bipolar bisthieno[3,2-b:2',3'-d] thiophene derivatives and applications thereof | |
| Li et al. | Novel red-emitting thieno-[3, 4-b]-pyrazine derivatives suitable for vacuum evaporation and solution method to fabricate non-doped OLEDs | |
| CN111777614B (en) | Organic electroluminescent compound and application thereof | |
| CN111454265B (en) | Fused heterocyclic compound and preparation method and application thereof | |
| CN110183476B (en) | Biboroxadibenzo [ A, J ] anthracene derivatives and application thereof | |
| CN110272441B (en) | Biboroxadibenzo [ A, H ] anthracene derivatives and application thereof | |
| JP2014208602A (en) | New imidazole compound, material for electronic device, light emitting element, electronic device and method for producing thereof | |
| Wang et al. | An efficient blue emitter based on a naphthalene indenofluorene core |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170301 Termination date: 20180430 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |