CN110835340A - Organic electroluminescent material and organic electroluminescent device - Google Patents
Organic electroluminescent material and organic electroluminescent device Download PDFInfo
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Abstract
The present invention provides a novel organic electroluminescent material and an organic electroluminescent device using the same. The organic electroluminescent material of the present invention is represented by the general formula (1) wherein L, L1、L2、R、R1～R4、X1～X4、Z1～Z6N, m, p, q and r have the meanings given in the description.
Description
Technical Field
The present invention relates to an organic compound which can be used as a light-emitting layer material of an organic electroluminescent device; the invention also relates to the application of the compound in an organic electroluminescent device.
Background
The research on organic electroluminescent materials and devices began in the 60's of the 20 th century. Organic electroluminescence can be classified into two major categories, electroluminescence and electrophosphorescence, according to the principle of luminescence. Triplet excitons of fluorescent materials undergo spin-forbidden effects and can only generate photons in a non-radiative form back to the ground state, resulting in the internal quantum efficiency of electroluminescence being limited to within 25%. The energy of singlet excitons and triplet excitons can be fully utilized by the electrophosphorescence, so that the internal quantum efficiency of the phosphorescent device can reach 100% in theory. In 1998, Ma et al, hong Kong university and Forrest et al, Princeton university, USA, respectively report electrophosphorescent materials and devices with a theoretical quantum efficiency of 100%. These important research works have greatly pushed the development of organic electroluminescent devices, making the research of organic electroluminescence an international hot spot.
Fluorescent OLED devices that can achieve a breakthrough of the 25% internal quantum efficiency limit mainly use the Thermally Activated Delayed Fluorescence (TADF) mechanism. The TADF mechanism utilizes a TAD having a small singlet-triplet energy level difference (Δ E)ST) The triplet excitons of the organic small molecule material can be converted into singlet excitons through a reverse system cross-over (RISC) process under the condition of absorbing environmental heat energy, and theoretically, the quantum efficiency in the device can reach 100 percent. However, the TADF materials reported at present have large roll-off efficiency at high brightness and short lifetime, which limits their application in full color display and white light illumination. Currently, a hypersensitive fluorescent system using TADF material as a host material to improve the exciton utilization rate is a focus of attention. In a thermal activation delayed fluorescence light-emitting system, a triplet state of a Thermal Activation Delayed Fluorescence (TADF) material serving as a host material returns to a singlet state through a reverse inter-system cross-over (RISC) process, and then energy is transferred to an object material to emit light, so that complete energy transfer can be realized at low concentration, concentration quenching can be reduced, and the cost of a device is reduced.
However, the current Thermal Activation Delayed Fluorescence (TADF) material has the situation that the hole transport capability and the electron transport capability are not matched, and the reverse system cross-over rate (k)RISC) Lower triplet-polaron annihilation (TPA) is more serious and the like.
KR1020130067177A discloses a general formula compound used as a phosphorescent host material to improve the luminous efficiency and lifetime of the device.
Patent EP3266772 discloses a class of organic electroluminescent compounds having a specific structural formula, and specifically discloses compounds having a plurality of carbazole structures.
However, the electron transport capability of such materials is still weak, and the charge recombination region cannot be widened, so that the device efficiency is low. Therefore, there is still room for improvement in the luminescence property of the conventional organic electroluminescent materials, and development of new organic electroluminescent materials is urgently needed in the art.
Documents of the prior art
Patent document
Patent document 1: KR1020130067177A
Patent document 2: EP3266772
Disclosure of Invention
As described above, in order to obtain high luminous efficiency and reduce the efficiency roll-off in the organic electroluminescent device, an organic electroluminescent material having more matched charge transport properties is required.
In view of the above, the main object of the present invention is to provide a thermally activated delayed fluorescence material with bipolar transmission capability; further, the organic electroluminescent material is applied to an organic electroluminescent device as a luminescent material or a host material.
That is, the present inventors have found that a compound having a terpolycarbazole structure (here, carbazole includes nitrogen-substituted carbazole) can achieve a good bipolar transport ability when incorporated as a light-emitting layer in an organic electroluminescent device.
Specifically, as one aspect of the present invention, there is provided an organic electroluminescent material comprising a compound represented by the following general formula (1),
in formula (1), L, L1、L2Are the same or different from each other and are each independently selected from the group consisting of a single bond, substituted or unsubstitutedC of (A)6～C30Arylene or substituted or unsubstituted C3～C30A heteroarylene group;
Z1～Z6independently of one another, from CR 'or an N atom, R' is a cyano group or an H atom, and Z1～Z61 or 2 are CR 'and R' is cyano;
the two A groups being identical or different, wherein X1～X4Independently of one another, selected from C atoms or N atoms, and X in the two A groups1～X4Is an N atom;
r represents substituted or unsubstituted C1～C12Alkyl, substituted or unsubstituted C6～C30Aryl or substituted or unsubstituted C3～C30A heteroaryl group, which is the same or different from each other when a plurality of R are present, and which may be condensed with an adjacent benzene ring or heterocycle;
R1represents substituted or unsubstituted C1～C12Alkyl, substituted or unsubstituted C6～C30Aryl or substituted or unsubstituted C3～C30A heteroaryl group; when there are more than one R1When a plurality of R1Identical or different from each other and may be fused with an adjacent benzene ring;
R2represents substituted or unsubstituted C1～C12Alkyl, substituted or unsubstituted C6～C30Aryl or substituted or unsubstituted C3～C30A heteroaryl group; when there are more than one R2When a plurality of R2Identical or different from each other and may be fused with an adjacent benzene ring;
R3represents substituted or unsubstituted C1～C12Alkyl, substituted or unsubstituted C6～C30Aryl or substituted or unsubstituted C3～C30A heteroaryl group; when there are more than one R3When a plurality of R3Identical or different from each other and may be fused with an adjacent benzene ring or heterocycle;
R4represents substituted or unsubstituted C1～C12Alkyl, substituted or unsubstituted C6～C30Aryl or substituted or unsubstituted C3～C30A heteroaryl group; when there are more than one R4When a plurality of R4Identical or different from each other and may be fused with an adjacent benzene ring;
m and n are integers of 0-3;
p, q and r are integers of 0-4;
substituted in "substituted or unsubstituted" by one or more substituents selected from C1～C12Alkyl of (C)1～C12Alkoxy group of (C)6～C12Aryl of (C)3～C12Substituted by a substituent in the heteroaryl, cyano or hydroxyl group.
As another aspect of the present invention, there is also provided a use of the organic electroluminescent material as described above in an organic electroluminescent device.
As still another aspect of the present invention, there is also provided an organic electroluminescent device comprising a first electrode, a second electrode and an organic layer interposed between the first electrode and the second electrode, characterized in that the organic layer contains therein an organic electroluminescent material as described above.
According to the invention, the compound containing the terpolycarbazole (or azacarbazole) group with the bipolar transmission structure can widen a charge recombination region, thereby reducing the efficiency roll-off of the device, and in addition, electron-withdrawing groups such as benzene cyano, pyridine cyano and the like are introduced into the compound, thereby being beneficial to the thermal activation of molecules to delay the fluorescence property, expanding a carrier recombination region, reducing the starting voltage and improving the efficiency.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below.
In the present specification, unless otherwise indicated, the following terms have the following meanings:
in the present invention, the expression of Ca to Cb means that the group has carbon atoms a to b, and the carbon atoms do not include the carbon atoms of the substituents unless otherwise specified. In the present invention, the expression of chemical elements includes the concept of chemically identical isotopes, such as the expression of "hydrogen", and also includes the concept of chemically identical "deuterium" and "tritium". In the present invention, "D" may be used to represent "deuterium".
In the present specification, the substitution in "substituted or unsubstituted" means being substituted by one or more selected from C1～C12Alkyl of (C)1～C12Alkoxy group of (C)6～C12Aryl of (C)3～C12The heteroaryl group, cyano group and hydroxyl group of (a) may be substituted with a substituent selected from halogen, cyano group, hydroxyl group, alkoxy group, alkyl group, aryl group and heteroaryl group, more specifically, with a substituent selected from fluorine, cyano group, methoxy group, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, phenyl group, biphenyl group, naphthyl group, phenanthryl group, fluorenyl group, dibenzofuranyl group, dibenzothienyl group, pyridyl group, quinolyl group, phenylpyridinyl group, pyridylphenyl group and the like being preferable.
In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 10. Specific examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, octyl, decyl, and the like.
In the present specification, the aryl group is not particularly limited, but preferably has 6 to 30 carbon atoms. Specific examples of aryl groups include phenyl, biphenyl, naphthyl, anthryl, phenanthryl, and the like.
In the present specification, the heteroaryl group is a heteroaryl group containing at least one of O, N, S, Si as a heteroatom, and the number of carbon atoms is preferably 3 to 30. Specific examples of heteroaryl groups include thienyl, furyl, pyrrolyl, imidazolyl, thiazolyl, oxazolyl, and the like.
In the present specification, the expression of the loop structure marked by "-" indicates that the linking site is located at any position on the loop structure where the linkage can be formed.
Hereinafter, a material for an organic electroluminescent device according to an aspect of the present invention will be described.
The material for an organic electroluminescent device of the present invention comprises a compound represented by the following general formula (1).
In the above general formula (1), the two A groups may be the same or different, wherein X1～X4Independently of one another, selected from C atoms or N atoms, and X in the two A groups1～X4Is an N atom. Preferably, X in each A group1～X4One of them is an N atom.
Specifically, the A group is selected from the following A1-A8 structures.
Wherein R represents substituted or unsubstituted C1～C12Alkyl, substituted or unsubstituted C6～C30Aryl or substituted or unsubstituted C3～C30And a heteroaryl group, which may be the same or different from each other when a plurality of R are present, and may be fused with an adjacent benzene ring or heterocycle. R4Represents substituted or unsubstituted C1～C12Alkyl, substituted or unsubstituted C6～C30Aryl or substituted or unsubstituted C3～C30A heteroaryl group; when there are more than one R4When a plurality of R4May be the same or different from each other, and may be fused with an adjacent benzene ring. In the above general formula (1), R1Represents substituted or unsubstituted C1～C12Alkyl, substituted or unsubstituted C6～C30Aryl or substituted or unsubstituted C3～C30A heteroaryl group; when there are more than one R1When a plurality ofR1May be the same or different from each other, and may be fused with an adjacent benzene ring. R2Represents substituted or unsubstituted C1～C12Alkyl, substituted or unsubstituted C6～C30Aryl or substituted or unsubstituted C3～C30A heteroaryl group; when there are more than one R2When a plurality of R2May be the same or different from each other, and may be fused with an adjacent benzene ring. Preferably, R, R as described above1、R2And R4Each independently selected from the group consisting of methyl, ethyl, isopropyl, tert-butyl, phenyl, naphthyl, anthracenyl, pyridyl, thienyl, thiazolyl, furyl and carbazolyl, each of which may have a substituent, and examples of the substituent are the same as those exemplified above for the substituent. In the general formula (1), m and n are integers of 0 to 3, preferably 0 to 2; p and q are integers of 0 to 4, preferably 0 to 2.
As C1～C12Examples of alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like, among which methyl, ethyl, n-propyl, isopropyl are preferred, and methyl is more preferred;
as C1～C12Alkoxy includes the above-mentioned C1～C12Examples of the alkyl group include groups bonded to-O-, such as methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy and the like, among which methoxy, ethoxy, propoxy and more preferably methoxy;
as C6～C30Examples of aryl groups include: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluorenyl, pyrenyl,
Fluoro, anthryl, benzo [ a ]]Anthracenyl, benzo [ c ]]Phenanthryl, triphenylene, benzo [ k ]]Fluoranthenyl, benzeneAnd [ g ]]Radical, benzo [ b]Triphenylene, picene, perylene, etc., of which phenyl and naphthyl are preferred, and phenyl is more preferred;
as C3～C30The heteroaryl group may be a nitrogen-containing heteroaryl group, an oxygen-containing heteroaryl group, a sulfur-containing heteroaryl group, and the like, and specific examples thereof include: pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolyl, isoquinolyl, naphthyridinyl, phthalazinyl, quinoxalinyl, quinazolinyl, phenanthridinyl, acridinyl, phenanthrolinyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl, indolyl, benzimidazolyl, indazolyl, imidazopyridinyl, benzotriazolyl, carbazolyl, furyl, thienyl, oxazolyl, thiazolyl, isoxazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, benzofuranyl, benzothienyl, benzoxazolyl, benzothiazolyl, benzisoxazolyl, benzisothiazolyl, benzoxadiazolyl, benzothiadiazolyl, dibenzofuranyl, dibenzothienyl, piperidyl, pyrrolidinyl, piperazinyl, morpholinyl, phenazinyl, phenothiazinyl, phenoxazinyl, and the like are preferred among them, pyridyl, quinolyl, pyrrolidinyl, piperazinyl, morpholinyl, phenazinyl, phenothiazinyl, and the like, Dibenzofuranyl and dibenzothienyl, and more preferably pyridyl.
In the present invention, the specific reason why the compound of the present invention has the mother nucleus of the terpolycarbazole (or azacarbazole) structure based on the combination of the above groups and the compound of the present invention has excellent performance as a material for a light-emitting layer is not clear, and it is presumed that the following reasons may be:
firstly, the electron donor is selected from a terpolycarbazole (or azacarbazole) group, and the electron donor group has better stability and is beneficial to the improvement of the performance of the organic electroluminescent device; compared with the traditional bi-carbazole group, the introduction of the azacarbazole such as the carboline molecule can obviously improve the electron mobility, the carbazole molecule has good hole transport capability, the molecule has excellent hole and electron transport performance simultaneously through the mutual matching combination of the carbazole and the azacarbazole, and the molecule has the excellent bipolar transport capability, so that the charge recombination region can be widened, and the efficiency roll-off of the device is reduced.
In addition, energy levels of the compound can be regulated and controlled by introducing different azacarbazole molecules and changing the structure and the substitution position of a matched receptor, so that materials with different energy levels are screened, and the materials of devices can be easily selected and matched.
In the above general formula (1), L, L1、L2Are the same or different from each other and are each independently selected from the group consisting of a single bond, substituted or unsubstituted C6～C30Arylene or substituted or unsubstituted C3～C30A heteroarylene group. Specifically, L, L is preferable1、L2Independently of one another, a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted phenanthrylene group or a substituted or unsubstituted pyridylene group.
In the above general formula (1), Z in the group B1～Z6Independently of one another, from a CR' or N atom; r' is a cyano group or a H atom, and Z1～Z61 or 2 of (a) is CR 'and R' is cyano.
Secondly, as the hole transmission capability of the organic electroluminescent molecules is often superior to the electron transmission capability of the organic electroluminescent molecules, the substituted groups have good electron transmission capability by introducing electron-withdrawing groups such as benzene cyano, pyridine cyano and the like into a molecular material system, and the electron-withdrawing groups contribute to the promotion of the electron transmission capability of the molecules; in addition, the group has strong electron-withdrawing ability, and effectively enhances the thermal activation delayed fluorescence ability of the molecule. That is, preferably, the B group is selected from the following B1-B8 structures.
Wherein R is3Represents substituted or unsubstituted C1～C12Alkyl, substituted or unsubstituted C6～C30Aryl or substituted or unsubstituted C3～C30A heteroaryl group;when there are more than one R3When a plurality of R3May be the same or different from each other, and may be fused with an adjacent benzene ring or heterocyclic ring.
r is an integer of 0 to 4, preferably 0 to 2.
More preferably, the group B is the structure of B1-B6, and when B is the group, the ambipolar transport ability of the compound is more balanced, and an organic electroluminescent device with better efficiency can be obtained. Particularly preferred are B3 and B4.
Further, preferable examples of the novel compounds of the general formula of the present invention include the following representative compounds P1 to P80:
in addition, the invention also provides the application of the compound containing the novel terpolycarbazole (or azacarbazole) structure in an organic electroluminescent device. The compound can be used as a guest material of a light-emitting layer and can also be used as a host material for sensitizing the guest material.
Specifically, an embodiment of the present invention provides an organic electroluminescent device comprising a first electrode, a second electrode, and one or more organic layers interposed between the first electrode and the second electrode, wherein the organic layers comprise the above-described terpolycarbazole (or azacarbazole) derivative.
Further, the organic layer between the first electrode and the second electrode at least includes a light-emitting layer, and usually further includes an organic layer such as an electron injection layer, an electron transport layer, a hole injection layer, a hole blocking layer, and the like, and among them, the organic layer containing the compound of the present invention can be used as, but not limited to, a light-emitting layer.
The compound of the present invention can be applied to organic electronic devices, for example, organic electroluminescent devices, lighting devices, organic thin-film transistors, organic field-effect transistors, organic thin-film solar cells, large-area sensors such as information labels, electronic artificial skin sheets and sheet-type scanners, electronic paper, organic EL panels, and the like.
Next, the organic electroluminescent device will be explained in detail.
The organic electroluminescent device includes first and second electrodes on a substrate, and an organic layer between the electrodes, which may be a multi-layered structure. For example, the organic layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.
As the substrate, a substrate used for a general organic light emitting display, for example: glass, polymer materials, glass with TFT components, polymer materials, and the like.
The anode material can be Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), and tin dioxide (SnO)2) Transparent conductive materials such as zinc oxide (ZnO), metal materials such as silver and its alloys, aluminum and its alloys, organic conductive materials such as PEDOT, and multilayer structures of these materials.
The cathode material can be selected from metals, metal mixtures and oxides such as magnesium silver mixture, LiF/Al, ITO and the like.
The hole transport layer may be, but is not limited to, a combination of one or more of the compounds listed below as HT1-HT 31.
A hole injection layer, including but not limited to a combination of one or more of the compounds listed below as HI-1-HI-3, may also be included in the organic electroluminescent device between the hole transport layer and the anode.
Device light emitting layer host materials include, but are not limited to, combinations of one or more of the compounds TDH1-TDH24 listed below.
The fluorescent doping material is selected from at least one of the following molecular structures:
the electron transport layer includes, but is not limited to, combinations of one or more of the compounds of ET1-ET57 listed below.
An electron injection layer may also be included in the organic electroluminescent device between the electron transport layer and the cathode, the electron injection layer material including, but not limited to, combinations of one or more of the following.
LiQ、LiF、NaCl、CsF、Li2O、Cs2CO3、BaO、Na、Li、Ca。
Examples
The present invention will be described in further detail below with reference to specific embodiments in order to make the present invention better understood by those skilled in the art.
Synthetic examples
The specific production method of the above-mentioned novel compound of the present invention will be described in detail below by taking a plurality of synthesis examples as examples, but the production method of the present invention is not limited to these synthesis examples.
Examples of chemicals used in the examples include xylene, ethyl acetate, N-dimethylformamide, toluene, methylene chloride, tetrahydrofuran, dioxane, 3, 6-dibromocarbazole, cuprous iodide, sodium carbonate, 4-bromoisophthalonitrile, cesium carbonate, potassium hydroxide, 4-toluenesulfonyl chloride, potassium phosphate, trans-1, 2-cyclohexanediamine, sodium hydride, ethylenediamine, tetrakis (triphenylphosphine) palladium, carbazole, α -carboline, 5H-pyrido [4, 3-b ] indole, 5-bromo-1, 3-benzenedinitrile, 1, 8-dibromo-3, 6-dimethyl-9H-carbazole, and the like.
The basic chemical materials are purchased from commercial chemical product suppliers, including but not limited to Shanghai Tankatake technology, Inc. and Xilongguo chemical, Inc.
Analytical testing of intermediates and compounds in the present invention used an ABCIEX mass spectrometer (4000QTRAP) and Brookfield nuclear magnetic resonance spectrometer (400M Hz).
The synthesis of the compounds of the present invention is briefly described below.
Synthesis example 1: synthesis of Compound P25
Preparation of intermediate M1
In a 1000mL single-neck flask equipped with magnetic stirring at room temperature, 3, 6-dibromocarbazole (50g, 153mmol) is dissolved in acetone (500mL), KOH (12.8g, 215mmol) is added, stirring is carried out at room temperature, 4-tosyl chloride (41.06g, 215mmol) is added, and the reflux reaction is carried out for 5h under the protection of nitrogen. TLC monitoring reaction PE: EA is 5: 1, raw material 3, 6-dibromo carbazole is 0.4, compound M1 is 0.6.
After the reaction is cooled to room temperature, the white solid is obtained by direct filtration, then the white solid is stirred and washed in water and then filtered, the obtained solid is stirred in ethyl acetate and then filtered, and the product 58g is obtained by drying.
Preparation of intermediate M2
In a 500mL single-neck flask equipped with magnetic stirring at room temperature, compound M1(5g, 10mmol) was dissolved in dioxane (50mL) and K was added3PO4(17g, 83mmol, 8eq) was stirred at room temperature, and α -carboline (4.6g, 26mmol), CuI (2.3g, 12mmol), trans 1, 2-cyclohexanediamine (1.43g, 12mmol) were added and reacted for 16h under nitrogen protection at 150 c.tlc monitoring the reaction PE: EA ═ 5: 1, compound M1 ═ 0.6, compound M2 ═ 0.3.
After the reaction is cooled to room temperature, dichloromethane is used for extraction, the organic phase is collected and dried by spinning, column chromatography is carried out by using a developing agent with PE: EA being 5: 1, and the product 5g is obtained by drying by spinning.
Preparation of intermediate M3
In a 100mL single-neck flask equipped with magnetic stirring at room temperature, compound M2(1g, 1.53mmol) was dissolved in tetrahydrofuran (50mL), sodium hydride (0.23g, 215mmol, 60% content) was added, and the mixture was stirred under heating and refluxed for 5h under nitrogen. The reaction was monitored by TLC for completion (PE: EA 2: 1, compound M2 0.7, compound M3 0.5, complete reaction)
After the reaction was cooled to room temperature, it was spin-dried to give a white solid, which was then stirred in water and filtered to give a solid which was stirred in ethyl acetate and then filtered, and dried to give about 0.6g of compound M3.
Preparation of Compound P25
400mL of xylene, compound M35 g (10mmol, 1eq), 2.25g (11mmol, 1.1eq) of 4-bromoisophthalonitrile, 3.57g (20mmol, 2eq) of cuprous iodide, 13g (40mmol, 4eq) of cesium carbonate, 1.16g (20mmol, 2eq) of ethylenediamine were placed in a 1000mL single-neck flask equipped with magnetic stirring at room temperature, stirred with nitrogen replaced 3 times, warmed to reflux, and reacted for 24 hours. The reaction mixture was cooled to room temperature, filtered, and the filtrate was spin-dried, silica gel column filtered with DCM to AE 1: 1 to give 4.5g of an off-white solid. The product was then washed with ethanol to remove impurities to give a crude product, which was then washed with toluene to give 3.7g of P25 as a white solid with 98.9% purity.
P25 Mass Spectrometry molecular weight theoretical value 625.2, and molecular weight detection value 625.5. Theoretical value of elemental analysis C, 80.62%; h, 3.71%; n, 15.67%, elemental analysis detection value C, 80.57%; h, 3.33%; n, 15.88 percent.
Synthesis example 2: synthesis of Compound P38
Preparation of intermediate M4
The preparation method and reaction equivalent are the same as those of an intermediate M2, α -carboline is replaced by 5H-pyrido [4, 3-b ] indole, and the TLC monitoring reaction is that PE: EA is 4: 1, a compound M1 is 0.6, and a compound M4 is 0.3.
After the reaction is cooled to room temperature, dichloromethane is used for extraction, an organic phase is collected and dried by spinning, column chromatography is carried out by using a developing agent with PE: EA being 4: 1, and 4.7g of a product is obtained by drying by spinning.
Preparation of intermediate M5
Preparation method and reaction equivalent are the same as that of intermediate M3, TLC monitors that the reaction is complete (PE: EA is 2: 1, compound M4 is 0.7, compound M5 is 0.5. the reaction is complete)
After the reaction was cooled to room temperature, it was spin-dried to give a white solid, which was then stirred in water and filtered to give a solid which was stirred in ethyl acetate and then filtered and dried to give about 0.57g of compound M5.
Preparation of Compound P38
400mL of xylene, compound M55 g (10mmol, 1eq), 2.25g (11mmol, 1.1eq) of 5-bromo-1, 3-benzenedinitrile, 3.57g (20mmol, 2eq) of cuprous iodide, 13g (40mmol, 4eq) of cesium carbonate, 1.16g (20mmol, 2eq) of ethylenediamine were placed in a 1000mL single-neck flask equipped with magnetic stirring at room temperature, the nitrogen was replaced 3 times, the temperature was raised to reflux, and the reaction was carried out for 24 hours. The reaction mixture was cooled to room temperature, filtered, and the filtrate was spin-dried, silica gel column filtered with DCM to AE 1: 1 to give 3.9g of an off-white solid. The product was then washed with ethanol to remove impurities to give a crude product, which was then washed with toluene to give 3.2g of P38 as a white solid with a purity of 99.1%.
P38 Mass Spectrometry molecular weight theoretical value 625.2, and molecular weight detection value 625.7. Theoretical value of elemental analysis C, 80.62%; h, 3.71%; n, 15.67%, elemental analysis detection value C, 80.33%; h, 3.53%; n, 15.91 percent.
Synthetic example 3: synthesis of Compound P55
Preparation of intermediate M6
In a 1000mL single-neck flask equipped with magnetic stirring at room temperature, 1, 8-dibromo-3, 6-dimethyl-9H-carbazole (54g, 153mmol) is dissolved in acetone (500mL), KOH (12.8g, 215mmol) is added and stirred at room temperature, 4-tosyl chloride (41.06g, 215mmol) is added, and the mixture is refluxed for 5 hours under the protection of nitrogen. TLC monitored the reaction PE: EA 5: 1, starting material 1, 8-dibromo-3, 6-dimethyl-9H-carbazole 0.4 and compound M1 0.7.
After the reaction is cooled to room temperature, the white solid is obtained by direct filtration, then the white solid is stirred and washed in water and then filtered, the obtained solid is stirred in ethyl acetate and then filtered, and the product of 62g is obtained by drying.
Preparation of intermediate M7
The preparation method and reaction equivalent are the same as those of an intermediate M2, α -carboline is replaced by 5H-pyrido [3, 2-b ] indole, and the TLC monitoring reaction is that PE: EA is 4: 1, a compound M7 is 0.6, and a compound M6 is 0.4.
After the reaction is cooled to room temperature, dichloromethane is used for extraction, an organic phase is collected and dried by spinning, column chromatography is carried out by using a developing agent with PE: EA being 4: 1, and 4.6g of a product is obtained by drying by spinning.
Preparation of intermediate M8
Preparation method and reaction equivalent as preparation of intermediate M3, TLC monitoring reaction completion (PE: EA 2: 1, compound M7 0.8, compound M8 0.5)
After the reaction was cooled to room temperature, it was spin-dried to give a white solid, which was then stirred in water and filtered to give a solid which was stirred in ethyl acetate and then filtered, and dried to give about 0.63g of compound M5.
Preparation of Compound P55
400mL of xylene, 85.2g (10mmol, 1eq) of the compound, 2.25g (11mmol, 1.1eq) of 5-bromo-1, 3-benzenedinitrile, 3.57g (20mmol, 2eq) of cuprous iodide, 13g (40mmol, 4eq) of cesium carbonate and 1.16g (20mmol, 2eq) of ethylenediamine were placed in a 1000mL single-neck flask equipped with magnetic stirring at room temperature, stirred, replaced with nitrogen 3 times, heated to reflux, and reacted for 24 hours. The reaction mixture was cooled to room temperature, filtered, and the filtrate was spin-dried, silica gel column filtered with DCM to AE 1: 1 to give 4g of an off-white solid. The product was then washed with ethanol to remove impurities to give a crude product, which was then washed with toluene to give 3.6g of P55 as a white solid with 98.7% purity.
P55 Mass Spectrometry molecular weight theoretical value 653.2, molecular weight detection value 653.7. Theoretical value of elemental analysis C, 80.84%; h, 4.16%; n, 15%, and an elemental analysis detection value C, 80.77%; h, 4.13%; and N, 15.13 percent.
The compound of the present invention can be obtained by the above-described synthesis method, but is not limited to these methods. Other methods such as Stille coupling, Grignard, Kumada-Tamao, and the like are also available to those skilled in the art, and any equivalent synthetic method may be selected as necessary as long as it can achieve the objective of producing the target compound.
Application examples
The technical effects and advantages of the present invention are demonstrated and verified by testing practical use performance by specifically applying the compound of the present invention to an organic electroluminescent device.
(A) Preparation of organic electroluminescent device (the Compound of the present invention as a dye Material)
The preparation process of the organic electroluminescent device is as follows:
the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;
placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3Pa, performing vacuum evaporation on the anode layer film to obtain HI-2 as a hole injection layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 10 nm;
evaporating HT-2 on the hole injection layer in vacuum to serve as a hole transport layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 80 nm;
the light-emitting layer of the device is vacuum evaporated on the hole transport layer, the light-emitting layer comprises a main material and a dye material, the evaporation rate of the main material TDH10 is adjusted to be 0.1nm/s by using a multi-source co-evaporation method, the dye evaporation rate in each example and each comparative example is set at a ratio of 30%, and the total evaporation film thickness is 30 nm;
vacuum evaporating an electron transport layer material ET-34 of the device on the light emitting layer, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 20 nm;
LiF with the thickness of 0.5nm is vacuum-evaporated on the Electron Transport Layer (ETL) to be used as an electron injection layer, and an Al layer with the thickness of 150nm is used as a cathode of the device.
(B) Method for testing organic electroluminescent device (the Compound of the present invention as a dye Material)
The driving voltage and current efficiency of the organic electroluminescent devices prepared in examples 1 to 8 and comparative example 1 were measured at the same luminance using a Photo-radiometer model ST-86LA model photoradiometer model PR 750 from Photo Research corporation (photoelectric instrument factory, university of beijing) and a Keithley4200 test system. Specifically, the voltage was raised at a rate of 0.1V per second, and it was determined that the luminance of the organic electroluminescent device reached 1000cd/m2The current density is measured at the same time as the driving voltage; the ratio of the luminance to the current density is the current efficiency.
Example 1
The following devices were prepared in the manner as described above using the compound P9 of the present invention as a dye material in the light-emitting layer, so as to have the following structures, and device performance tests were conducted in the manner as described above for the organic electroluminescent device test method.
ITO(150nm)/HI-2(10nm)/HT-2(40nm)/TDH10：30％P9(30nm)/ET34(20nm)/LiF(0.5nm)/Al(150nm)
Wherein 30% means that the weight ratio of P9 to TDH10 is 30%, which is also expressed in the following examples and comparative examples.
Example 2:
the following devices were prepared in the manner as described above using the compound P11 of the present invention as a dye material in the light-emitting layer, so as to have the following structures, and device performance tests were conducted in the manner as described above for the organic electroluminescent device test method.
ITO(150nm)/HI2(10nm)/HT2(40nm)/TDH10：30％P11(30nm)/ET34(20nm)/LiF(0.5nm)/Al(150nm)
Example 3:
the following devices were prepared in the manner as described above using the compound P12 of the present invention as a dye material in the light-emitting layer, so as to have the following structures, and device performance tests were conducted in the manner as described above for the organic electroluminescent device test method.
ITO(150nm)/HI2(10nm)/HT2(40nm)/TDH10：30％P12(30nm)/ET34(20nm)/LiF(0.5nm)/Al(150nm)
Example 4:
the following devices were prepared in the manner as described above using the compound P17 of the present invention as a dye material in the light-emitting layer, so as to have the following structures, and device performance tests were conducted in the manner as described above for the organic electroluminescent device test method.
ITO(150nm)/HI2(10nm)/HT2(40nm)/TDH10：30％P17(30nm)/ET34(20nm)/LiF(0.5nm)/Al(150nm)
Example 5:
the following devices were prepared in the manner as described above using the compound P20 of the present invention as a dye material in the light-emitting layer, so as to have the following structures, and device performance tests were conducted in the manner as described above for the organic electroluminescent device test method.
ITO(150nm)/HI2(10nm)/HT2(40nm)/TDH10：30％P20(30nm)/ET34(20nm)/LiF(0.5nm)/Al(150nm)
Example 6:
the following devices were prepared in the manner as described above using the compound P25 of the present invention as a dye material in the light-emitting layer, so as to have the following structures, and device performance tests were conducted in the manner as described above for the organic electroluminescent device test method.
ITO(150nm)/HI2(10nm)/HT2(40nm)/TDH10：30％P25(30nm)/ET34(20nm)/LiF(0.5nm)/Al(150nm)
Example 7:
the following devices were prepared in the manner as described above using the compound P38 of the present invention as a dye material in the light-emitting layer, so as to have the following structures, and device performance tests were conducted in the manner as described above for the organic electroluminescent device test method.
ITO(150nm)/HI2(10nm)/HT2(40nm)/TDH10：30％P38(30nm)/ET37(20nm)/LiF(0.5nm)/Al(150nm)
Example 8:
the following devices were prepared in the manner as described above using the compound P60 of the present invention as a dye material in the light-emitting layer, so as to have the following structures, and device performance tests were conducted in the manner as described above for the organic electroluminescent device test method.
ITO(150nm)/HI2(10nm)/HT2(40nm)/TDH10：30％P60(30nm)/ET34(20nm)/LiF(0.5nm)/Al(150nm)
Comparative example 1
The dye material selected for the organic electroluminescent device in comparative example 1 was R1, and compound R1 was obtained by the method exemplified in the above synthesis examples.
The following devices were prepared in accordance with the above-described method using the compound R1 as a dye material in the light-emitting layer to have the following structures, and device performance tests were conducted in accordance with the above-described organic electroluminescent device test method.
ITO(150nm)/HI2(10nm)/HT2(40nm)/TDH10：30％R1(30nm)/ET34(20nm)/LiF(0.5nm)/Al(150nm)
The organic electroluminescent device properties are given in the following table:
TABLE 1 organic electroluminescent device Properties
From the above table data it can be seen that:
example 4 electroluminescent device performance using the compound P17 of the present invention compared to the organic electroluminescent performance of the OLED using R1 dye in comparative example 1, P17 achieved higher current efficiency and lower driving voltage; this shows that the electron transport ability of the material can be obviously improved by introducing proper triazacyclonocarbazole into the dye. The organic electroluminescent device prepared by the method has the advantages of obviously reducing the driving voltage and improving the luminous efficiency.
Meanwhile, in the embodiment 5, compared with the OLED organic electroluminescent performance of the embodiment 4, which adopts the compound P20 of the invention as the dye, the OLED organic electroluminescent performance of the embodiment 4, which adopts the P17 as the dye, has the advantage that the P17 also obtains higher current efficiency and lower driving voltage; this shows that the introduction of a carboline group into a molecule can significantly reduce the driving voltage and improve the luminous efficiency compared to a carbazole group.
The results show that the novel organic material provided by the invention is used for an organic electroluminescent device, can effectively reduce the take-off and landing voltage and improve the current efficiency, has good stability and is a dye material with good performance.
As described above, the compound of the present invention can be used as a host material for a light-emitting layer to sensitize a guest fluorescent dye.
(C) Preparation of organic electroluminescent device (the Compound of the present invention as the host Material)
The preparation process of the organic electroluminescent device in the embodiment is as follows:
the glass plate coated with the ITO transparent conductive layer was sonicated in a commercial detergent, rinsed in deionized water, washed in acetone: ultrasonically removing oil in an ethanol mixed solvent, baking in a clean environment until the water is completely removed, cleaning by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;
placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3Pa, performing vacuum evaporation on the anode layer film to obtain HI-2 as a hole injection layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 10 nm;
evaporating HT-2 on the hole injection layer in vacuum to serve as a hole transport layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 80 nm;
the light-emitting layer of the device is vacuum evaporated on the hole transport layer, the light-emitting layer comprises a host material and a dye material, the evaporation rate of the host material in each of the examples and the comparative examples is adjusted to be 0.1nm/s by using a multi-source co-evaporation method, the evaporation rate of the dye F8 is set to be 30%, and the total evaporation film thickness is 30 nm;
vacuum evaporating an electron transport layer material ET-34 of the device on the light emitting layer, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 20 nm;
LiF with the thickness of 0.5nm is vacuum-evaporated on the Electron Transport Layer (ETL) to be used as an electron injection layer, and an Al layer with the thickness of 150nm is used as a cathode of the device.
(D) Method for testing organic electroluminescent device (Compound of the present invention as host Material)
The organic electroluminescent device prepared by the above process was subjected to the following performance measurement:
the driving voltage and current efficiency of the organic electroluminescent devices prepared in examples 9 to 16 and comparative example 2 were measured at the same luminance using a Photo-radiometer model ST-86LA model photoradiometer model PR 750 from Photo Research corporation (photoelectric instrument factory, university of beijing) and a Keithley4200 test system. Specifically, the voltage was raised at a rate of 0.1V per second, and it was determined that the luminance of the organic electroluminescent device reached 10000cd/m2The current density is measured at the same time as the driving voltage; the ratio of the luminance to the current density is the current efficiency.
Example 9
The following devices were prepared in the manner as described above using the compound P9 of the present invention as a host material in the light-emitting layer, and were subjected to device performance tests in accordance with the organic electroluminescent device test method described above.
ITO(150nm)/HI2(10nm)/HT2(40nm)/P9：30％F8(30nm)/ET34(20nm)/LiF(0.5nm)/Al(150nm)
Wherein 30% means that the weight ratio of the dye F8 to P9 is 30%, which is also expressed in the following examples and comparative examples.
Example 10
The following devices were prepared in the manner as described above using the compound P17 of the present invention as a host material in the light-emitting layer, and were subjected to device performance tests in accordance with the organic electroluminescent device test method described above.
ITO(150nm)/HI2(10nm)/HT2(40nm)/P17：30％F8(30nm)/ET34(20nm)/LiF(0.5nm)/Al(150nm)
Example 11
The following devices were prepared in the manner as described above using the compound P20 of the present invention as a host material in the light-emitting layer, and were subjected to device performance tests in accordance with the organic electroluminescent device test method described above.
ITO(150nm)/HI2(10nm)/HT2(40nm)/P20：30％F8(30nm)/ET34(20nm)/LiF(0.5nm)/Al(150nm)
Example 12
The following devices were prepared in the manner as described above using the compound P38 of the present invention as a host material in the light-emitting layer, and were subjected to device performance tests in accordance with the organic electroluminescent device test method described above.
ITO(150nm)/HI2(10nm)/HT2(40nm)/P38：30％F8(30nm)/ET34(20nm)/LiF(0.5nm)/Al(150nm)
Example 13
The following devices were prepared in the manner as described above using the compound P31 of the present invention as a host material in the light-emitting layer, and were subjected to device performance tests in accordance with the organic electroluminescent device test method described above.
ITO(150nm)/HI2(10nm)/HT2(40nm)/P31：30％F8(30nm)/ET34(20nm)/LiF(0.5nm)/Al(150nm)
Example 14
The following devices were prepared in the manner as described above using the compound P77 of the present invention as a host material in the light-emitting layer, and were subjected to device performance tests in accordance with the organic electroluminescent device test method described above.
ITO(150nm)/HI2(10nm)/HT2(40nm)/P77：30％F8(30nm)/ET34(20nm)/LiF(0.5nm)/Al(150nm)
Example 15
The following devices were prepared in the manner as described above using the compound P48 of the present invention as a host material in the light-emitting layer, and were subjected to device performance tests in accordance with the organic electroluminescent device test method described above.
ITO(150nm)/HI2(10nm)/HT2(40nm)/P48：30％F8(30nm)/ET34(20nm)/LiF(0.5nm)/Al(150nm)
Example 16
The following devices were prepared in the manner as described above using the compound P59 of the present invention as a host material in the light-emitting layer, and were subjected to device performance tests in accordance with the organic electroluminescent device test method described above.
ITO(150nm)/HI2(10nm)/HT2(40nm)/P59：30％F8(30nm)/ET34(20nm)/LiF(0.5nm)/Al(150nm)
Comparative example 2
The host material selected for the organic electroluminescent device in this comparative example was CBP
The following devices were prepared to have the following structures according to the above-described method using the compound CPB as a host material in the light-emitting layer, and device performance tests were performed according to the above-described organic electroluminescent device test method.
ITO(150nm)/HI2(10nm)/HT2(40nm)/CBP：30％F8(30nm)/ET34(20nm)/LiF(0.5nm)/Al(150nm)
The organic electroluminescent device properties are given in the following table:
TABLE 2 organic electroluminescent device Properties
From the above table data it can be seen that:
example 9 the organic electroluminescent property of the OLED using the compound P9 of the present invention as a host obtained higher current efficiency and lower driving voltage than the organic electroluminescent property of the OLED using CBP as a host in comparative example 2; the results show that the material based on the terpolycarbazole (or azacarbazole) has the advantages of obviously reducing the driving voltage and improving the luminous efficiency when being used as a main body to prepare the organic electroluminescent device.
Meanwhile, the organic electroluminescence performance of the OLED adopting the compound P17 of the invention as a dye in example 10 is higher in current efficiency and lower in driving voltage than that of the OLED adopting P20 as a main body in example 11 in P17; this shows that when the material is used as a main material, the carboline group is introduced into the receptor, which can obviously reduce the driving voltage and improve the luminous efficiency.
In addition, as can be seen from the comparison of examples 9 and 14 with examples 15 and 16, the organic electroluminescence property of the OLED using the compound P9 or P77 of the present invention as a host is superior to that of the OLED using the compound P48 or P59 of the present invention as a host, which is presumed to be mainly because: the compounds P9 and P77 are based on the B4 group and the B3 group as the B group, respectively, and the compounds P48 and P59 are based on the B7 group and the B8 group as the B group, respectively, as described above, when the B group is the B3 or B4 group, the bipolar transport ability of the compounds of the present invention is more balanced, enabling more efficient organic electroluminescent devices to be obtained.
The results show that when the novel organic material is used for the main body of the organic electroluminescent device, the novel organic material can effectively reduce the take-off and landing voltage, improve the current efficiency and have good stability.
Although the invention has been described in connection with the embodiments, the invention is not limited to the embodiments described above, and it should be understood that various modifications and improvements can be made by those skilled in the art within the spirit of the invention, and the scope of the invention is outlined by the appended claims.
Claims (11)
1. An organic electroluminescent material comprising a compound represented by the general formula (1),
wherein the content of the first and second substances,
L、L1、L2are the same or different from each other and are each independently selected from the group consisting of a single bond, substituted or unsubstituted C6～C30Arylene or substituted or unsubstituted C3～C30A heteroarylene group;
Z1～Z6independently of one another, from CR 'or an N atom, R' is a cyano group or an H atom, and Z1～Z61 or 2 are CR 'and R' is cyano;
the two A groups being identical or different, wherein X1～X4Independently of one another, selected from C atoms or N atoms, and X in the two A groups1～X4Is an N atom;
r represents substituted or unsubstituted C1～C12Alkyl, substituted or unsubstituted C6～C30Aryl or substituted or unsubstituted C3～C30A heteroaryl group, which is the same or different from each other when a plurality of R are present, and which may be condensed with an adjacent benzene ring or heterocycle;
R1represents substituted or unsubstituted C1～C12Alkyl, substituted or unsubstituted C6～C30Aryl or substituted or unsubstituted C3～C30A heteroaryl group; when there are more than one R1When a plurality of R1Identical or different from each other and may be fused with an adjacent benzene ring;
R2represents substituted or unsubstituted C1～C12Alkyl, substituted or unsubstituted C6～C30Aryl or substituted or unsubstituted C3～C30A heteroaryl group; when there are more than one R2When a plurality of R2Identical or different from each other and may be fused with an adjacent benzene ring;
R3represents substituted or unsubstituted C1～C12Alkyl, substituted or unsubstituted C6～C30Aryl or substituted or unsubstituted C3～C30A heteroaryl group; when there are more than one R3When a plurality of R3Identical or different from each other and may be fused with an adjacent benzene ring or heterocycle;
R4represents substituted or unsubstituted C1～C12Alkyl, substituted or unsubstituted C6～C30Aryl or substituted or unsubstituted C3～C30A heteroaryl group; when there are more than one R4When a plurality of R4Identical or different from each other and may be fused with an adjacent benzene ring;
m and n are integers of 0-3;
p, q, r are integers of 0 to 4,
in "substituted or unsubstitutedSubstituted by one or more substituents selected from C1～C12Alkyl of (C)1～C12Alkoxy group of (C)6～C12Aryl of (C)3～C12Substituted by a substituent in the heteroaryl, cyano or hydroxyl group.
2. The organic electroluminescent material as claimed in claim 1, wherein L, L is1、L2Independently of one another, a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted phenanthrylene group or a substituted or unsubstituted pyridylene group.
3. The organic electroluminescent material according to claim 1, wherein R is1、R2And R4Each independently selected from the group consisting of methyl, ethyl, isopropyl, tert-butyl, substituted or unsubstituted phenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted pyridyl, substituted or unsubstituted thienyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted furyl, substituted or unsubstituted carbazolyl,
substituted in "substituted or unsubstituted" by one or more substituents selected from C1～C12Alkyl of (C)1～C12Alkoxy group of (C)6～C12Aryl of (C)3～C12Substituted by a substituent in the heteroaryl, cyano or hydroxyl group.
4. The organic electroluminescent material of claim 1, wherein the group B is selected from the following structures B1-B8,
wherein R is3And r has the same meaning as in the general formula (1).
5. The organic electroluminescent material as claimed in claim 1, wherein X in each A group1～X4One of them is an N atom.
6. The organic electroluminescent material of claim 1, wherein the group A is selected from the structures A1-A8,
wherein, R, R4P and q have the same meanings as in the general formula (1).
7. The organic electroluminescent material according to claim 1, wherein the compound has a structure selected from the group consisting of P1 to P80.
8. Use of the organic electroluminescent material according to any one of claims 1 to 7 in an organic electroluminescent device.
9. Use according to claim 8, wherein the organic electroluminescent material is used as a guest material of the light-emitting layer or as a host material of the light-emitting layer.
10. An organic electroluminescent device comprising a first electrode, a second electrode and an organic layer comprising at least a light-emitting layer interposed between the first electrode and the second electrode, characterized in that the organic layer contains the organic electroluminescent material according to any one of claims 1 to 7.
11. The organic electroluminescent device according to claim 10, wherein the organic layer containing the organic electroluminescent material is a light-emitting layer.
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| Publication number | Priority date | Publication date | Assignee | Title |
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