CN109705108A - A kind of anthryl heterocyclic compound and its application - Google Patents
A kind of anthryl heterocyclic compound and its application Download PDFInfo
- Publication number
- CN109705108A CN109705108A CN201811650626.1A CN201811650626A CN109705108A CN 109705108 A CN109705108 A CN 109705108A CN 201811650626 A CN201811650626 A CN 201811650626A CN 109705108 A CN109705108 A CN 109705108A
- Authority
- CN
- China
- Prior art keywords
- anthryl
- heterocyclic compound
- compound according
- hydrogen
- aryl
- 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.)
- Withdrawn
Links
Abstract
The invention belongs to field of organic electroluminescent materials, a kind of anthryl heterocyclic compound and its application are disclosed.Anthryl heterocyclic compound provided by the present invention has structure shown in formula (I).Such compound is with good stability, prepares organic electroluminescence device with anthryl heterocyclic compound provided by the invention, such as the electron transport layer materials in Organic Light Emitting Diode, the luminescent lifetime of device can be made significantly to be extended.
Description
Technical field
The invention belongs to field of organic electroluminescent materials, in particular to a kind of anthryl heterocyclic compound and its application.
Background technique
Organic electroluminescence device is to realize that power-up shines by introducing one or more layers organic film in cathode and anode
A kind of device technology, can be realized ultra-thin, flexible and transparent performance, FPD and illuminating industry application year by year
It improves.Organic electroluminescence device has diversified structure.For luminescent layer, the mode that host-guest system can be used is realized
Promotion to device efficiency and service life.Material of main part receives energy and passes to object, and guest materials emits phase after receiving energy
The spectrum answered.
In order to promote efficiency and the service life of organic electroluminescence device, also need to introduce not into its structure in addition to the light emitting layer
Luminous functional layer, such as hole transmission layer and electron transfer layer." hole transmission layer " refers at least thering is cavity transmission ability
Functional layer, " hole transmission layer " in addition to that can also have other one or more abilities, such as with cavity transmission ability simultaneously
Hole injection capacity or electron-blocking capability." electron transfer layer " refers to functional layer at least with electron transport ability, " electricity
Sub- transport layer " in addition to that can also have other one or more abilities, such as electron injection ability with electron transport ability simultaneously
Or hole blocking ability.In the prior art, the material of hole transmission layer includes various aromatic amine structural compounds, electron-transport
The material of layer includes various metal complexs or nitrogen-containing heterocycle compound.
In above two aid functional material, electron transport material relative shortage, no matter in type, quantity or quality
All it is not so good as hole mobile material.Metal complex, such as common AlQ3, can be used as emitting layer material also can be used as electron-transport
Layer material, but there is unstability.The electron transport material of organic aromatic heterocyclic, such as Chinese patent literature CN101384560
Disclosed TPBI and ZADN, due to containing benzimidazole structure, the film formed is also unstable in use.In addition, beautiful
State patent document US8415031 discloses a kind of anthracene-based compounds (ET-1) of azepine dibenzothiophenes, however its disclosed device
Part performance is much the same with AlQ3 with the service life.
Therefore, in order to obtain stable luminescent property and with the organic electroluminescence device of long-life, it is badly in need of the property developed
It can good electron transport material.
Summary of the invention
The purpose of the present invention is to provide a kind of anthryl heterocyclic compound and its applications, are passed using this kind of compound as electronics
Further organic electroluminescence device obtained has more stable luminescent properties and longer service life to defeated material.
The purpose of the present invention is achieved through the following technical solutions:
Embodiments of the present invention provide a kind of anthryl heterocyclic compound, with structure shown in formula (I):
Wherein,
L1、L2Each independently represent phenyl, naphthalene or anthryl；M, n each independently represents 0 or 1；
Py1、Py2It is each independently selected from such as one of flowering structure:
Ar1、Ar2Each independently represent C1-C12 alkyl, C6-C24 aryl or C3-C24 heteroaryl；P, q is each independently
Indicate 0,1,2,3 or 4；
Ar3Structure shown in expression hydrogen, deuterium, fluorine, C6-C24 aryl or formula (Ia):
X indicates oxygen or sulphur；
X1-X8Each independently represent nitrogen or CRa, the Ra indicate hydrogen, deuterium, fluorine, C1-C24 alkyl, C6-C36 aryl or
C3-C36 heteroaryl；
Ar4Structure shown in expression (Ib):
Y indicates oxygen atom or sulphur atom, Y1-Y8Expression nitrogen-atoms or CRb independent, the Rb indicate hydrogen, deuterium,
Fluorine, the alkyl of C1-C24, the aryl of C6-C36 or C3-C36 heteroaryl；K indicates 1 or 2；
The anthryl of structure shown in G expression (Ic):
Work as L1、L2In the presence of, the L1、L29,10 of anthryl are connected to, L is worked as1、L2In the absence of, Py1、Py2Point
It is not connected to 9,10 of anthryl；；Ar3It is connected to 6 or 7 of anthryl；Ar4It is connected to the two or three-digit of anthryl.
Optionally, in anthryl heterocyclic compound structure provided by embodiments of the present invention, formula (Ia) or formula (Ib) are each
From independently selected from one of such as flowering structure:
Wherein,
R1、R2Each independently represent hydrogen, deuterium, C1-C24 alkyl, C6-C36 aryl or C3-C36 heteroaryl.
Optionally, in anthryl heterocyclic compound structure provided by embodiments of the present invention, Py1、Py2It is pyridyl group.
Optionally, in anthryl heterocyclic compound structure provided by embodiments of the present invention, L1With L2For identical group；
Ar1With Ar2For identical group；And m is equal with n, p is equal with q.
Optionally, anthryl heterocyclic compound provided by embodiments of the present invention is by four kinds of carbon, hydrogen, nitrogen, oxygen element groups
At.
Optionally, in anthryl heterocyclic compound structure provided by embodiments of the present invention, Ar3Indicate phenyl, toluene
Base, ethylbenzene, propyl phenyl, butylbenzene base, naphthalene, xenyl, triphenylene or 9- phenyl anthryl.
Optionally, in anthryl heterocyclic compound structure provided by embodiments of the present invention, Ar3With Ar4For identical base
Group, k 1.
Optionally, in anthryl heterocyclic compound structure provided by embodiments of the present invention, Ar3For hydrogen.
Optionally, anthryl heterocyclic compound provided by embodiments of the present invention has selected from one of following structure:
Embodiments of the present invention also provide application of the above-mentioned anthryl heterocyclic compound in organic electroluminescence device.
Embodiments of the present invention also provide a kind of Organic Light Emitting Diode, the electron-transport in the Organic Light Emitting Diode
Layer material includes above-mentioned anthryl heterocyclic compound.
In terms of existing technologies, anthryl heterocyclic compound provided by embodiments of the present invention, in its structure
The benzofuran or benzothiophene or azabenzofuran or azepine benzothiophene of introducing, the thermal stability of these groups
Be high, while also mentioning high molecular electronic transmission performance, be introduced into structure such as Py in logical formula (I)1And Py2What is indicated is nitrogenous
Heterocycle also can be improved the electronic transmission performance of molecule, and when connecting with anthryl group, the lumo energy of molecule is reduced, and improve electricity
Sub- injection efficiency.Using anthryl heterocyclic compound provided by embodiments of the present invention as organic electroluminescence device (such as
Organic Light Emitting Diode) in electron transport layer materials, the luminescent lifetime of device significantly extended, and voltage decline is obvious.
Specific embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with embodiment to of the invention each
Specific embodiment is explained in detail.However, it will be understood by those skilled in the art that in each embodiment party of the present invention
In formula, many technical details are proposed in order to make reader more fully understand the present invention.But even if without these technical details
And various changes and modifications based on the following respective embodiments, each claim skill claimed of the present invention also may be implemented
Art scheme.
Compound
In certain specific embodiments of the invention, a kind of anthryl heterocyclic compound is provided, with shown in formula (I)
Structure:
Wherein,
L1、L2Each independently represent phenyl, naphthalene or anthryl；M, n each independently represents 0 or 1；
Py1、Py2It is each independently selected from such as one of flowering structure:
Ar1、Ar2Each independently represent C1-C12 alkyl, C6-C24 aryl or C3-C24 heteroaryl；P, q is each independently
Indicate 0,1,2,3 or 4；
Ar3Structure shown in expression hydrogen, deuterium, fluorine, C6-C24 aryl or formula (Ia):
X indicates oxygen or sulphur,
X1-X8Each independently represent nitrogen or CRa, the Ra indicate hydrogen, deuterium, fluorine, C1-C24 alkyl, C6-C36 aryl or
C3-C36 heteroaryl；
Ar4Structure shown in expression (Ib):
Y indicates oxygen atom or sulphur atom, Y1-Y8Expression nitrogen-atoms or CRb independent, the Rb indicate hydrogen, deuterium,
Fluorine, the alkyl of C1-C24, the aryl of C6-C36 or C3-C36 heteroaryl；K indicates 1 or 2；
The anthryl of structure shown in G expression (Ic):
Work as L1、L2In the presence of, the L1、L29,10 of anthryl are connected to, L is worked as1、L2In the absence of, Py1、Py2Point
It is not connected to 9,10 of anthryl；；Ar3It is connected to 6 or 7 of anthryl；Ar4It is connected to the two or three-digit of anthryl.
In certain specific embodiments of the invention, formula (Ia) or formula (Ib) be each independently selected from as flowering structure it
One:
Wherein,
R1、R2Each independently represent hydrogen, deuterium, C1-C24 alkyl, C6-C36 aryl or C3-C36 heteroaryl.
In certain specific embodiments of the invention, Py1、Py2It is pyridyl group.
In certain specific embodiments of the invention, L1With L2For identical group；Ar1With Ar2For identical group；And m with
N is equal, and p is equal with q.
In certain specific embodiments of the invention, the anthryl heterocyclic compound is by four kinds of carbon, hydrogen, nitrogen, oxygen elements
Composition.
In certain specific embodiments of the invention, Ar3Indicate phenyl, tolyl, ethylbenzene, propyl phenyl, butylbenzene base,
Naphthalene, xenyl, triphenylene or 9- phenyl anthryl.
In certain specific embodiments of the invention, Ar3With Ar4For identical group, k 1.
In certain specific embodiments of the invention, Ar3For hydrogen.
In certain specific embodiments of the invention, provided anthryl heterocyclic compound has selected from one of following
Structure:
General synthetic routes:
The synthetic method of the compound of the present invention is referred to universal synthesis method reported in the literature, using halogenated anthraquinone
Or the derivative of halogenated anthracene, it is prepared, can also be spread out using the boric acid of anthracene by Suzuki coupling reaction with corresponding organic boronic
Biological to wait for that object reacts with organic halogen, halogen can be chlorine, bromine or iodine.The specific method of synthetic method is not limited, citing
Be referred to patent JP2009173642A, US8415031, CN102137829A, EP1734038, EP1925618A1,
WO2008133459、US200646097A1、US2015333277A1、US20120187381A1、CN100505963C、
CN101679337A、CN104744346A、CN105143186A、TWI370838B、CN104744347A、
US20080152950A1, CN106187963A, are also referred to document Chem.Lett., 2011,40,1092-1094,
Chem.Lett.,2008,37,1150-1151、J.Mater.Chem.,2008,18,3376-3384、
Chem.Commun.2009,6961-6963、Angew.Chem.Int.Ed.,2009,48,9300-9303、ACS Omega
2017,2,3144-3156、Angew.Chem.Int.Ed.,2017,56,5598-5602。
Synthesize example:
The preparation method of disclosed compound of present invention provided below.But present disclosure is not intended to be limited to institute herein
The method of narration it is any.Those skilled in the art can easily modify described method or utilize different sides
Method prepares the one or more of disclosed compound.Following aspect is merely exemplary, and is not intended to limit in the disclosure
The range of appearance.Temperature, catalyst, concentration, reactant composition and other process conditions are changeable, and match for desired
Object is closed, present disclosure those skilled in the art can readily select suitable reactant and condition.
In following embodiment used reaction raw materials be commercially available or existing technical literature in its synthesis side is disclosed
The conventional raw material compound of method.
Embodiment 1: the synthesis of compound (A-1)
2- bromopyridine (0.8g, 5.3mmol) is dissolved into anhydrous tetrahydro furan (10mL), displacement oxygen is vacuumized, in nitrogen
Compression ring cools to -78 DEG C under border, and tert-butyl lithium (4.7mL, 1.7M pentane solution) is slowly added dropwise, the temperature is kept to continue stirring 1
Hour, it is added compound (S-2) (0.7g, 2.5mmol), continues stirring 1 hour, warm naturally to room temperature, stir 3 hours, add
Enter aqueous ammonium chloride solution, extracted with methylene chloride liquid separation, merge organic phase and anhydrous magnesium sulfate drying is added, revolving is removed molten
Agent obtains intermediate (S-3).
Above-mentioned intermediate (S-3) is dissolved into 60mL acetic acid, potassium iodide (3.4g, 21mmol) and time phosphorus successively is being added
Sour sodium (3.6g, 34mmol), vacuumizes displacement oxygen, is vigorously stirred lower back flow reaction 3 hours, after being cooled to room temperature, filters
It to solid, is washed twice respectively with distilled water and methanol, drying obtains compound (S-4).Yield 57%.
Intermediate (S-4) and (S-5) equimolar ratio are mixed, the tetra-triphenylphosphine palladium of 0.05 equivalent, 2 equivalents are added
Sodium carbonate, toluene/ethanol/water=8/3/2 mixed solvent is cooled to room temperature, two back flow reaction 8 hours under nitrogen protection
Chloromethanes extraction, column chromatographed column, and obtained compound (A-1), comprehensive yield 29%.
Nuclear magnetic data: (DMSO-d6): 8.59 (s, 1H), 8.36 (d, 2H), 8.11-7.99 (m, 6H), 7.89 (d, 1H),
7.72-7.52 (m, 5H), 7.51-7.32 (m, 5H), 6.91 (m, 2H).
Mass spectral molecular ion peak: 498.
Embodiment 2: the synthesis of compound (A-7)
According to the similar synthetic method of embodiment 1, raw material 2- bromopyridine is substituted for 4- (2- pyridyl group)-bromobenzene, is obtained
Compound (A-7), comprehensive yield 27%.
Nuclear magnetic data (DMSO-d6): 8.78 (s, 1H), 8.70 (d, 4H), 8.38 (d, 2H), 8.21-8.01 (m, 6H),
7.92-7.58 (m, 8H), 7.51-7.31 (m, 7H), 6.91 (m, 2H).
Mass spectral molecular ion peak: 650.
Embodiment 3: the synthesis of compound (A-17)
According to the similar synthetic method of embodiment 1, raw material 2- bromopyridine is substituted for -4 bromopyridine of 2- phenyl, obtains chemical combination
Object (A-17).
Mass spectral molecular ion peak: 650.
Embodiment 4: the synthesis of compound (A-22)
2- bromopyridine (0.8g, 5.3mmol) is dissolved into anhydrous tetrahydro furan (10mL), displacement oxygen is vacuumized, in nitrogen
Compression ring cools to -78 DEG C under border, and tert-butyl lithium (4.7mL, 1.7M pentane solution) is slowly added dropwise, the temperature is kept to continue stirring 1
Hour, it is added compound (S-6) (0.9g, 2.5mmol), continues stirring 1 hour, warm naturally to room temperature, stir 3 hours, add
Enter aqueous ammonium chloride solution, extracted with methylene chloride liquid separation, merge organic phase and anhydrous magnesium sulfate drying is added, revolving is removed molten
Agent obtains intermediate (S-7).
Above-mentioned intermediate (S-7) is dissolved into 60mL acetic acid, potassium iodide (3.4g, 21mmol) and time phosphorus successively is being added
Sour sodium (3.6g, 34mmol), vacuumizes displacement oxygen, is vigorously stirred lower back flow reaction 3 hours, after being cooled to room temperature, filters
It to solid, is washed twice respectively with distilled water and methanol, drying obtains compound (S-8).Yield 48%.
Intermediate (S-8) and (S-9) are mixed with molar ratio 1:2.4, add the tetra-triphenylphosphine palladium of 0.1 equivalent, 4
The sodium carbonate of equivalent, toluene/ethanol/water=8/3/2 mixed solvent are cooled to room back flow reaction 10 hours under nitrogen protection
Temperature, methylene chloride extraction, column chromatographed column, and obtained compound (A-22), comprehensive yield 34%.
Mass ions peak: 664.
The synthesis of 5 compound of embodiment (A-25)
According to the similar synthetic method of embodiment 4, raw material 2- bromopyridine is substituted for 3- bromopyridine, while by raw material 2,6-
Dibromo-anthraquinone is substituted for 2,3- dibromo-anthraquinone, obtains compound (A-25), comprehensive yield 18%.
Mass spectral molecular ion peak: 664.
The synthesis of 6 compound of embodiment (A-33)
Compound (S-10) (1.2g, 5.3mmol) is dissolved into anhydrous tetrahydro furan (10mL), displacement oxygen is vacuumized
Gas cools to -78 DEG C in a nitrogen environment, and tert-butyl lithium (4.7mL, 1.7M pentane solution) is slowly added dropwise, keep the temperature after
Continuous stirring 1 hour, is added compound (S-11) (0.9g, 2.5mmol), continues stirring 1 hour, warms naturally to room temperature, stirring 3
Hour, aqueous ammonium chloride solution is added, is extracted with methylene chloride liquid separation, merges organic phase and anhydrous magnesium sulfate drying, revolving is added
Solvent is removed, intermediate (S-12) is obtained.
Above-mentioned intermediate (S-12) is dissolved into 60mL acetic acid, successively be added it is potassium iodide (3.4g, 21mmol) and secondary
Sodium phosphate (3.6g, 34mmol), vacuumizes displacement oxygen, is vigorously stirred lower back flow reaction 3 hours, after being cooled to room temperature, filtering
Solid is obtained, is washed twice respectively with distilled water and methanol, drying obtains compound (S-13).Yield 35%.
Intermediate (S-13) and phenyl boric acid are mixed with molar ratio 1:1.1, add four triphenylphosphines of 0.05 equivalent
Palladium, the sodium carbonate of 2 equivalents, toluene/ethanol/water=8/3/2 mixed solvent are cooling back flow reaction 10 hours under nitrogen protection
To room temperature, methylene chloride extraction, column chromatographed column, and obtained midbody compound (S-14).
Intermediate (S-14) and (S-15) are mixed with molar ratio 1:1.3, add four triphenylphosphines of 0.05 equivalent
Palladium, the sodium carbonate of 2 equivalents, toluene/ethanol/water=8/3/2 mixed solvent are cooling back flow reaction 10 hours under nitrogen protection
To room temperature, methylene chloride extraction, column chromatographed column, and obtained midbody compound (A-33), comprehensive yield 14%.
Embodiment 7: the synthesis of compound (A-29)
According to the similar synthetic method of embodiment 6, raw material compound (S-15) is replaced with into dibenzofurans -4- boric acid,
It is made compound (A-29), comprehensive yield 37%.
Mass spectral molecular ion peak: 726.
Luminescent properties
Using anthryl heterocyclic compound provided by the present invention as the electron transport layer materials of Organic Light Emitting Diode
In, the level structure of material, such as triplet energy level (T1) and singlet level (S1), it is highest occupied molecular orbital (HOMO), minimum
Unoccupied orbital (LUMO) plays a key role.For phosphorescent devices, triplet energy level be it is important, for fluorescent device,
Singlet level is important.
The HOMO and lumo energy of compound provided by the present invention can be measured by photoelectric effect, for example, by using
Conventional XPS (x-ray photoelectron spectroscopy), UPS (ultraviolet photoelectron spectroscopy), CV (cyclic voltammetry) or DPV in the art
The methods of (differential pulse voltammetry).It can also be calculated by quantum chemical methods, such as density functional theory, all be
The effective method for obtaining molecular orbital energy level.
Triplet energy level (the T of compound provided by the present invention1) can be measured by low temperature time resolved spectroscopy,
It can be obtained by quantum chemistry, such as density functional theory.The calculation method of quantum chemistry, can be by business software, such as
Gaussian software is calculated, and specific method can be found in WO2011141110.
Singlet level (the S of compound provided by the present invention1) can be measured by low temperature time resolved spectroscopy,
It can be measured, can also be obtained by quantum chemistry, such as density functional theory by room temperature stable state spectrum.Quantum chemistry
Calculation method can be calculated by business software, such as gaussian software, and method explanation can be found in US2013059924.
It should be noted that, HOMO, LUMO, T1And S1Absolute value depend on measurement method or calculation method used, even
For identical method, different processing steps, such as starting point and peak dot can provide different oxidations on cyclic voltammetry curve
Reduction potential, and then obtain different HOMO and LUMO values.Therefore, reasonable and significant comparison, it should with identical measurement
Method and identical processing step.In the description of the embodiment of the present invention, HOMO, LUMO and S1Value be based on density functional theory
It is calculated.Functional uses B3LYP, base group selection 6-31G*.Wherein HOMO and LUMO uses absolute value representation, unit of account
It is used uniformly electron-volt (eV).The following table 1 is HOMO, LUMO and S of part of compounds1Numerical tabular.
HOMO, LUMO and S of 1 compound of table1Numerical tabular
Organic light emitting diode device
A specific embodiment of the invention also provides a kind of organic light emitting diode device, the organic light emitting diode device
Include anthryl heterocyclic compound provided by embodiments of the present invention.
In some specific embodiments provided by the present invention, the electron transfer layer in above-mentioned Organic Light Emitting Diode includes
Above-mentioned anthryl heterocyclic compound.
In some specific embodiments provided by the present invention, the hole blocking layer in above-mentioned Organic Light Emitting Diode includes
Above-mentioned anthryl heterocyclic compound.
In some specific embodiments provided by the present invention, the luminescent layer in above-mentioned Organic Light Emitting Diode includes above-mentioned
Anthryl heterocyclic compound.
In some specific embodiments provided by the present invention, the anthryl heterocyclic compound is the organic light-emitting diodes
Fluorescent host material in the luminescent layer of pipe.
Organic light emitting diode device preparation example
The production of device involved in the present invention may be selected under type such as and carry out: first using the preparation method of industry routine
Suitable anode is selected, for introducing hole, anode surface can be deposited the work function that other materials changes anode, then be deposited
Organic layer then proceedes to evaporation cathode, plays the role of introducing electronics.
The organic layer can be one layer, be also possible to multilayer.Further, organic layer includes hole transmission layer, is shone
Layer and electron transfer layer.The hole transmission layer can also have the function of hole function of injecting, electronic blocking or exciton blocking function
Can, the electron transfer layer can also have the function of electronics injecting function, hole barrier or exciton blocking function, the luminescent layer
It can be doped structure.When the luminescent layer is doped structure, by the high referred to as material of main part of weight percent, by weight percent
It is known as guest materials than low.Material of main part can be only a kind of, or a variety of.When using doped structure, object material
The doping ratio of material is 0.1-49.9%, preferably 0.5-20%.
Electron transport layer materials can be used as using anthryl heterocyclic compound provided by the present invention, can also be used as hole
Barrier material can also be used as the fluorescent host material of luminescent layer.In the present embodiment, preferably as electron transport layer materials.
Device preparation step is as follows: cleaned ito glass substrate being placed in vacuum chamber, is evacuated to 10-5Pa, vapor deposition
Molybdenum trioxide (the MoO of one layer of 5nm3)；Continue be deposited one layer of 50nm N, N, N', N'- tetra- (2- naphthalene) biphenyl-4-1,1'-,
4'- diamines (TNB)；Continue the BD-1 and MADN of one layer of 20nm of total vapor deposition, doping concentration 3wt%；Continue that one layer of 40nm is deposited
Electron transport layer materials (anthryl heterocyclic compound provided by the present invention)；Continue the lithium fluoride that one layer of 1nm is deposited；Continue to steam
The aluminium electrode for plating one layer of 100nm obtains the device of the present invention of number 1-6.In addition, being electricity with compound ET-1 and compound ET-2
Son transmission layer material prepares comparative device C1 and C2 using method identical with device 1-6.
Measurement device 1-6 and the cut-in voltage of comparative device C1, C2, luminous efficiency and brightness decay are to initial value 95%
Time (T95) used, data see the table below 2:
2 device performance tables of data of table
| Device number | Electron transport material | Cut-in voltage (V) | Luminous efficiency (cd/A) | T95(h) |
| 1 | A-1 | 4.3 | 8.6 | 125 |
| 2 | A-7 | 4.4 | 8.7 | 146 |
| 3 | A-22 | 4.5 | 8.3 | 151 |
| 4 | A-25 | 4.5 | 8.4 | 153 |
| 5 | A-33 | 4.2 | 8.5 | 132 |
| 6 | A-29 | 4.5 | 8.2 | 162 |
| C1 | ET-1 | 5.1 | 8.1 | 115 |
| C2 | ET-2 | 4.4 | 8.3 | 78 |
In organic electroluminescence device, since the electrode stability of low work function is poor, the stabilization of high work function can only be used
Electrode, however in this way make electron injection performance decline, by be deposited one layer of lithium fluoride (LiF) electron injection can be improved,
It but still is inadequate.Dibenzofurans, dibenzothiophenes, azabenzofuran or azepine benzothiophene structure are a kind of
The group of good thermal stability, the present invention are introduced into molecular structure the carrier transport ability that molecule can be enhanced, so
And such molecule is still inadequate for the improvement of electron injection.The present invention further passes through to be introduced such as in the molecular structure
Py in logical formula (I)1And Py2The nitrogen-containing heterocycle group of expression, preferably mentions high molecular electronic transmission performance；On this basis with
When anthryl group connects, low molecular lumo energy can drop, so that the energy barrier between molecule and electrode further decreases, Jin Ergai
It has been apt to electron injection efficiency.In a specific embodiment of the invention, lead to Py in formula (I)1And Py2The nitrogen-containing heterocycle group of expression
Using pyridine groups, as schematical explanation.
As can be seen from Table 2, it is prepared using anthryl heterocyclic compound provided by the present invention as electron transport layer materials
The service life of Organic Light Emitting Diode is significantly better than comparative device C2, it may be said that the stability of bright the compounds of this invention is better than comparisonization
Close object ET-2；The Organic Light Emitting Diode that anthryl heterocyclic compound provided by the present invention is prepared as electron transport layer materials
Cut-in voltage is significantly better than comparative device C1, it may be said that bright the compounds of this invention is significant for the improvement of electron injection；This
Anthryl heterocyclic compound provided by inventing is excellent as the luminous efficiency of Organic Light Emitting Diode prepared by electron transport layer materials
In comparative device C1, it may be said that bright the compounds of this invention is very favorable for the improvement of electron-transport.
It will be understood by those skilled in the art that the respective embodiments described above are to realize specific embodiments of the present invention,
And in practical applications, can to it, various changes can be made in the form and details, without departing from the spirit and scope of the present invention.
Claims (10)
1. a kind of anthryl heterocyclic compound, with structure shown in formula (I):
Wherein,
L1、L2Each independently represent phenyl, naphthalene or anthryl；M, n each independently represents 0 or 1；
Py1、Py2It is each independently selected from such as one of flowering structure:
Ar1、Ar2Each independently represent C1-C12 alkyl, C6-C24 aryl or C3-C24 heteroaryl；P, q is each independently represented
0,1,2,3 or 4；
Ar3Structure shown in expression hydrogen, deuterium, fluorine, C6-C24 aryl or formula (Ia):
X indicates oxygen or sulphur,
X1-X8Nitrogen or CRa are each independently represented, the Ra indicates hydrogen, deuterium, fluorine, C1-C24 alkyl, C6-C36 aryl or C3-
C36 heteroaryl；
Ar4Structure shown in expression (Ib):
Y indicates oxygen atom or sulphur atom, Y1-Y8Each independently represent nitrogen-atoms or CRb, the Rb indicate hydrogen, deuterium, fluorine,
The heteroaryl of the alkyl of C1-C24, the aryl of C6-C36 or C3-C36；K indicates 1 or 2；
The anthryl of structure shown in G expression (Ic):
Work as L1、L2In the presence of, the L1、L29,10 of anthryl are connected to, L is worked as1、L2In the absence of, Py1、Py2Connect respectively
Meet 9,10 in anthryl；；Ar3It is connected to 6 or 7 of anthryl；Ar4It is connected to the two or three-digit of anthryl.
2. anthryl heterocyclic compound according to claim 1, which is characterized in that formula (Ia) or formula (Ib) are selected each independently
One of flowering structure freely:
Wherein,
R1、R2Each independently represent hydrogen, deuterium, C1-C24 alkyl, C6-C36 aryl or C3-C36 heteroaryl.
3. anthryl heterocyclic compound according to claim 1, which is characterized in that Py1、Py2It is pyridyl group.
4. anthryl heterocyclic compound according to claim 1, which is characterized in that L1With L2For identical group；Ar1With Ar2For
Identical group；And m is equal with n, p is equal with q.
5. anthryl heterocyclic compound according to claim 1, which is characterized in that the anthryl heterocyclic compound by carbon, hydrogen,
Four kinds of nitrogen, oxygen element compositions.
6. anthryl heterocyclic compound according to claim 1, which is characterized in that Ar3Indicate phenyl, tolyl, ethylbenzene,
Propyl phenyl, butylbenzene base, naphthalene, xenyl, triphenylene or 9- phenyl anthryl.
7. anthryl heterocyclic compound according to claim 1, which is characterized in that Ar3With Ar4For identical group, k 1.
8. anthryl heterocyclic compound according to claim 1, which is characterized in that Ar3For hydrogen.
9. anthryl heterocyclic compound according to claim 1, which is characterized in that have selected from one of following structure:
10. application of the anthryl heterocyclic compound of any of claims 1-9 in organic electroluminescence device.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811650626.1A CN109705108A (en) | 2018-12-31 | 2018-12-31 | A kind of anthryl heterocyclic compound and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811650626.1A CN109705108A (en) | 2018-12-31 | 2018-12-31 | A kind of anthryl heterocyclic compound and its application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109705108A true CN109705108A (en) | 2019-05-03 |
Family
ID=66260628
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811650626.1A Withdrawn CN109705108A (en) | 2018-12-31 | 2018-12-31 | A kind of anthryl heterocyclic compound and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109705108A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283178A (en) * | 2019-07-15 | 2019-09-27 | 陕西莱特光电材料股份有限公司 | A kind of heterocyclic compound and its synthetic method and the organic electroluminescent device comprising the compound |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120097932A1 (en) * | 2010-10-25 | 2012-04-26 | Samsung Mobile Display Co., Ltd. | Condensed-cyclic compound, organic light-emitting diode comprising the same and flat panel display device comprising the organic light-emitting diode |
| KR20130075982A (en) * | 2011-12-28 | 2013-07-08 | 주식회사 두산 | Anthracene-based compound and organic electroluminescence device using the same |
| KR20150130650A (en) * | 2014-05-13 | 2015-11-24 | 삼성디스플레이 주식회사 | Organic light-emitting devices |
| CN107235899A (en) * | 2017-07-13 | 2017-10-10 | 长春海谱润斯科技有限公司 | A kind of new acridine compound and its organic luminescent device |
| CN107602467A (en) * | 2017-09-18 | 2018-01-19 | 长春海谱润斯科技有限公司 | One kind contains anthracene compound and its synthetic method and organic electroluminescence device |
| CN108475736A (en) * | 2015-11-17 | 2018-08-31 | 保土谷化学工业株式会社 | Organic electroluminescent device |
-
2018
- 2018-12-31 CN CN201811650626.1A patent/CN109705108A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120097932A1 (en) * | 2010-10-25 | 2012-04-26 | Samsung Mobile Display Co., Ltd. | Condensed-cyclic compound, organic light-emitting diode comprising the same and flat panel display device comprising the organic light-emitting diode |
| KR20130075982A (en) * | 2011-12-28 | 2013-07-08 | 주식회사 두산 | Anthracene-based compound and organic electroluminescence device using the same |
| KR20150130650A (en) * | 2014-05-13 | 2015-11-24 | 삼성디스플레이 주식회사 | Organic light-emitting devices |
| CN108475736A (en) * | 2015-11-17 | 2018-08-31 | 保土谷化学工业株式会社 | Organic electroluminescent device |
| CN107235899A (en) * | 2017-07-13 | 2017-10-10 | 长春海谱润斯科技有限公司 | A kind of new acridine compound and its organic luminescent device |
| CN107602467A (en) * | 2017-09-18 | 2018-01-19 | 长春海谱润斯科技有限公司 | One kind contains anthracene compound and its synthetic method and organic electroluminescence device |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110283178A (en) * | 2019-07-15 | 2019-09-27 | 陕西莱特光电材料股份有限公司 | A kind of heterocyclic compound and its synthetic method and the organic electroluminescent device comprising the compound |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105399696B (en) | Organic electroluminescent compounds and organic photoelectric devices using the same | |
| CN102212066B (en) | Condensed-cyclic compound and the organic light-emitting device comprising this condensed-cyclic compound | |
| TWI642678B (en) | Semiconducting material comprising a phosphepine matrix compound | |
| CN108864068A (en) | A kind of compound and organic light-emitting display device | |
| Liu et al. | Novel bipolar host materials based on 1, 3, 5-triazine derivatives for highly efficient phosphorescent OLEDs with extremely low efficiency roll-off | |
| CN107573326A (en) | New benzotriazole derivatives and the organic electroluminescence device using the derivative | |
| CN102227485A (en) | Novel compound for organic photoelectric device and organic photoelectric device including same | |
| CN108586441A (en) | A kind of compound, a kind of organic light-emitting display device | |
| CN103958486A (en) | Spirobifluorene compounds for light emitting devices | |
| WO2018173598A1 (en) | Organic electroluminescent element | |
| CN106232591A (en) | Electron transport material and the Organnic electroluminescent device comprising it | |
| KR20200096158A (en) | Multicyclic compound and organic light emitting device comprising same | |
| CN109134446A (en) | A kind of hot activation delayed fluorescence material and the organic light-emitting display device comprising it | |
| JP2018512726A (en) | Semiconductor materials and naphthofuran matrix compounds for semiconductor materials | |
| CN108727405A (en) | A kind of heteroaromatic compounds and organic light-emitting display device | |
| WO2019208991A1 (en) | Novel heterocyclic compound and organic light emitting device using same | |
| CN110964062A (en) | Iridium complex and organic electroluminescent device using the same | |
| CN110483576A (en) | One kind fused heterocyclic compound containing phosphine and its preparation method and application | |
| CN113004295B (en) | Triazine electron transport material, preparation method and application thereof | |
| CN108912105A (en) | A kind of double carbazole compounds symmetrically replaced and its application | |
| CN113039183B (en) | Novel compound and organic light emitting device comprising the same | |
| CN109280064A (en) | Organo-metallic compound and organic luminescent device including it | |
| CN108299282A (en) | A kind of aromatic amine compound symmetrically replaced and the application in OLED device | |
| CN112334472B (en) | Novel compound and organic light emitting device comprising the same | |
| CN109705108A (en) | A kind of anthryl heterocyclic compound and its application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20190503 |
|
| WW01 | Invention patent application withdrawn after publication |