CN111153919A - Luminescent material, application thereof and organic electroluminescent device comprising luminescent material - Google Patents

Luminescent material, application thereof and organic electroluminescent device comprising luminescent material Download PDF

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CN111153919A
CN111153919A CN202010017691.1A CN202010017691A CN111153919A CN 111153919 A CN111153919 A CN 111153919A CN 202010017691 A CN202010017691 A CN 202010017691A CN 111153919 A CN111153919 A CN 111153919A
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CN111153919B (en
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段炼
张跃威
张东东
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Tsinghua University
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Abstract

The invention relates to a novel compound, application thereof and an organic electroluminescent device containing the compound, wherein the compound has a structure shown in the following formula:
Figure DDA0002359517000000011
wherein, Y1And Y2Are independently N or B, X1、X2、X3And X4Are each independently of the other NR1Or BR2，Ra、Rb、RcAnd RdEach independently represents a single substituent up to the maximum permissible substituents, and each is independently selected from hydrogen, deuterium, or one of the following substituted or unsubstituted groups: one of C1-C36 chain alkyl, C3-C36 cycloalkyl, C1-C10 alkoxy, halogen, cyano, nitro, hydroxyl, silyl, amino, substituted or unsubstituted C6-C30 arylamino, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl. The compound of the present invention shows excellent device performance and stability when used as a light emitting material in an OLED device. The invention also protects the organic electroluminescent device adopting the compound with the general formula.

Description

Luminescent material, application thereof and organic electroluminescent device comprising luminescent material
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to a novel organic compound, application thereof and an organic electroluminescent device containing the compound.
Background
Organic Light Emission Diodes (OLED) are a kind of devices with sandwich-like structure, which includes positive and negative electrode films and Organic functional material layers sandwiched between the electrode films. Because the OLED device has the advantages of high brightness, fast response, wide viewing angle, simple process, flexibility and the like, the OLED device is concerned in the field of novel display technology and novel illumination technology. At present, the technology is widely applied to display panels of products such as novel lighting lamps, smart phones and tablet computers, and further expands the application field of large-size display products such as televisions, and is a novel display technology with fast development and high technical requirements.
As OLEDs continue to advance in both lighting and display areas, much attention has been paid to research into their core materials, since an efficient, long-lived OLED device is generally the result of an optimized arrangement of device structures and various organic materials. In order to prepare an OLED light-emitting device with lower driving voltage, better light-emitting efficiency and longer service life, the performance of the OLED device is continuously improved, the structure and the manufacturing process of the OLED device need to be innovated, and photoelectric functional materials in the OLED device need to be continuously researched and innovated, so that functional materials with higher performance can be prepared. Based on this, the OLED material industry has been working on developing new organic electroluminescent materials to achieve low starting voltage, high luminous efficiency and better lifetime of the device.
In the aspect of selection of OLED materials, the fluorescent material with singlet state luminescence has the advantages of long service life, low price and low efficiency; triplet-emitting phosphorescent materials are efficient, but expensive, and blue-emitting materialsThe problem of lifetime of (a) has not been solved. Adachi at kyushu university of japan proposes a new class of organic light emitting materials, i.e., Thermally Activated Delayed Fluorescence (TADF) materials. Singlet-triplet energy gap (Delta E) of the materialST) Very small (<0.3eV), triplet excitons may be converted into singlet excitons by reverse intersystem crossing (RISC) to emit light, and thus the internal quantum efficiency of the device may reach 100%.
The MR-TADF material has the advantages of high color purity and high luminous efficiency, and has attracted extensive attention in the scientific research and industrial fields. However, due to the pair of peripheral substituents S1The energy level influence is small, namely the luminous color of the material is difficult to regulate and control, the light color of the material is always limited in a blue-deep blue region, and the further application of the MR-TADF material in the fields of high-resolution display, full-color display, white light illumination and the like is greatly limited.
Disclosure of Invention
In order to solve the above technical problems, the present invention provides a novel organic compound, wherein the specific general formula of the compound of the present invention is shown as the following formula (1):
Figure BDA0002359516980000021
in the formula (I), ring A, ring B, ring C and ring D each independently represent an aromatic ring or a heteroaromatic ring;
said Y is1And Y2Each is independently N or B; said X1、X2、X3And X4Are each independently NR1Or BR2；
The R is1Rings A and/or R which are each independently optionally adjacent theretoaRing B and/or RbRing C and/or RcOr ring D and/or RdLinked to form a ring or not linked to form a ring, wherein the linkage to form a ring may be through-O-, -S-, -CR3R4-or a single bond;
the R is2Rings A and/or R which are each independently optionally adjacent theretoaRing B and/or RbRing C and/or RcOr ring D and/or RdConnected or not connected to form a ringWhen they are linked to form a ring, they may be linked to form a ring via-O-, -S-, -CR3R4-or a single bond;
the R is1、R2、R3And R4Each independently selected from one of the following substituted or unsubstituted groups: C1-C36 chain alkyl, C3-C36 cycloalkyl, C6-C30 arylamine, C3-C30 heteroarylamino, C6-C60 monocyclic aryl, C6-C60 fused ring aryl, C6-C60 aryloxy, C5-C60 monocyclic heteroaryl or C5-C60 fused ring heteroaryl;
the R isa、Rb、RcAnd RdEach independently represents a single substituent up to the maximum permissible substituents, and each is independently selected from hydrogen, deuterium, or one of the following substituted or unsubstituted groups: one of halogen, chain alkyl of C1-C36, cycloalkyl of C3-C36, alkoxy of C1-C10, thioalkoxy of C1-C10, carbonyl, carboxyl, nitro, cyano, amino, arylamino of C6-C30, heteroarylamino of C3-C30, monocyclic aryl of C6-C60, condensed ring aryl of C6-C60, aryloxy of C6-C60, monocyclic heteroaryl of C5-C60 and condensed ring heteroaryl of C5-C60;
the R isa、Rb、RcAnd RdMay be bonded to each other and may correspondingly form, together with ring A, ring B, ring C or ring D, a substituted or unsubstituted C6-C30 aryl group or a substituted or unsubstituted C3-C30 heteroaryl group;
when the above groups have substituents, the substituents are respectively and independently selected from any one of deuterium, halogen, chain alkyl of C1-C30, cycloalkyl of C3-C30, alkoxy of C1-C10, thioalkoxy of C1-C10, carbonyl, carboxyl, nitro, cyano, amino, arylamino of C6-C30, heteroarylamino of C3-C30, monocyclic aryl of C6-C60, condensed ring aryl of C6-C60, aryloxy of C6-C60, monocyclic heteroaryl of C5-C60 and condensed ring heteroaryl of C5-C60.
Preferably, at least one hydrogen in the structural formula of the compound represented by the formula (I) is substituted.
Preferably, ring A, ring B, ring C and ring D in formula (I) each independently represent any one of monocyclic aromatic ring or fused aromatic ring of C5-C20, monocyclic heterocyclic ring or fused heterocyclic ring of C4-C20; still preferably, the a, ring B, ring C and ring D each independently represent any one of a monocyclic aromatic ring or a fused aromatic ring of C5 to C10, a monocyclic heterocyclic ring or a fused heterocyclic ring of C4 to C10; most preferably, the a, ring B, ring C and ring D are each independently selected from any one of a benzene ring, a naphthalene ring or a fluorene ring.
Preferably, the specific general formula of the compound of the present invention is shown in the following formula (1):
Figure BDA0002359516980000031
said Y is1And Y2Each is independently N or B; said X1、X2、X3And X4Are each independently NR1Or BR2；
The R is1Ring a and/or R independently and adjacently adjacent to each otheraRing b and/or RbRing c and/or RcOr ring d and/or RdLinked to form a ring or not linked to form a ring, wherein the linkage to form a ring may be through-O-, -S-, -CR3R4-or a single bond;
the R is2Ring a and/or R independently and adjacently adjacent to each otheraRing b and/or RbRing c and/or RcOr ring d and/or RdLinked to form a ring or not linked to form a ring, wherein the linkage to form a ring may be through-O-, -S-, -CR3R4-or a single bond;
the R isa、Rb、Rc、Rd、R3And R4Are as defined in formula (I).
Still preferably, the specific general formula of the compound of the present invention is represented by any one of the following formulas (2) to (4):
Figure BDA0002359516980000032
in formulae (2) to (4), X1、X2、X3、X4、Ra、Rb、RcAnd RdAre as defined in formula (I).
More preferably, the specific general formula of the compound of the present invention is represented by formula (2), wherein in formula (2), X is1、X2、X3And X4Are each independently NR1，Ra、Rb、RcAnd RdAre as defined in formula (I).
More preferably, the specific general formula of the compound of the present invention is represented by formula (3), wherein in formula (3), X is1、X2Are each independently NR1，X3、X4Are respectively independent and are respectively BR2，Ra、Rb、RcAnd RdAre as defined in formula (I).
More preferably, the specific general formula of the compound of the present invention is represented by formula (4), wherein in formula (4), X1、X2、X3And X4Are respectively independent and are respectively BR2，Ra、Rb、RcAnd RdAre as defined in formula (I).
Still more preferably, in the above general formulae (1) to (4) of the present invention, R is1Rings a and/or R independently adjacent theretoaRing b and/or RbRing c and/or RcOr ring d and/or RdWhen the connection is performed to form a ring, the connection is performed through a single bond; the R is2Rings a and/or R independently adjacent theretoaRing b and/or RbRing c and/or RcOr ring d and/or RdWhen they are linked to form a ring, they are linked by a single bond.
More preferably, in the above general formulae (1) to (4) of the present invention, R isa、Rb、RcAnd RdEach independently selected from hydrogen, deuterium, or one of the following substituted or unsubstituted groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-butylPentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2, 2-trifluoroethyl, phenyl, naphthyl, anthracenyl, benzanthryl, phenanthryl, benzophenanthryl, pyrenyl, perylenyl, fluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, couplet phenyl, terphenyl, quaterphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis-or trans-indenofluorenyl, trimeric indenyl, isotridecyl, spirotrimeric indenyl, spiroisotridecyl, furanyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, 2-trifluoromethyl, pentacenyl, terphenyl, biphenyl, terphenyl, quat, Isoindolyl, carbazolyl, indenocarbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5, 6-quinolyl, benzo-6, 7-quinolyl, benzo-7, 8-quinolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthroimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalimidazolyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthroizolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazahrenyl, 2, 7-diazapyryl, 2, 3-diazapyryl, 1, 6-diazapyryl, 1, 8-diazenyl, 4,5,9, 10-tetraazaperyl, pyrazinyl, phenazinyl, phenothiazinyl, naphthyridinyl, azacarbazolyl, benzocarbazinyl, phenanthrolinyl, 1,2, 3-triazolyl, 1,2, 4-triazolyl, benzotriazolyl, 1,2, 3-oxadiazolyl, 1,2, 4-oxadiazolyl, 1,2, 5-oxadiazolyl, 1,2, 3-thiadiazolyl, 1,2, 4-thiadiazolyl, 1,2, 5-thiadiazolyl, 1,3, 4-thiadiazolyl, 1,3, 5-triazinyl, 1,2, 4-triazinyl, 1,2, 3-triazinyl, tetrazolyl, 1,2,4, 5-tetrazinyl, 1,2,3, 4-tetrazinyl, 1,2,3, 5-tetrazinyl, purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, 9-dimethylazinyl, triarylamino, adamantane, fluorophenyl, methylphenyl, trimethylphenyl, cyanophenylTetrahydropyrrole, piperidine, methoxyl, silicon base, or combination of two substituent groups;
when the above groups have substituents, the substituents are respectively and independently selected from any one of halogen, chain alkyl of C1-C12, cycloalkyl of C3-C12, alkoxy or thioalkoxy of C1-C6, arylamino of C6-C30, heteroaryl of C3-C30, monocyclic aromatic hydrocarbon or fused ring aromatic hydrocarbon group of C6-C30, monocyclic heteroaromatic hydrocarbon or fused ring heteroaromatic hydrocarbon group of C3-C30.
Still further preferably, the specific general formula of the compound of the present invention is represented by any one of the formulae (5) to (7):
Figure BDA0002359516980000041
in formulae (5) to (7), the R1～R24Each independently selected from hydrogen, deuterium, or one of the following substituted or unsubstituted groups: halogen, chain alkyl of C1-C36, cycloalkyl of C3-C36, alkoxy of C1-C10, thioalkoxy of C1-C10, carbonyl, carboxyl, nitro, cyano, amino, arylamino of C6-C30, heteroarylamino of C3-C30, monocyclic aryl of C6-C60, condensed ring aryl of C6-C60, aryloxy of C6-C60, monocyclic heteroaryl of C5-C60, condensed ring heteroaryl of C5-C60, and R is one of R6-C36, cycloalkyl of C3-C36, alkoxy of C1-C10, aryl of C3, aryl of C5-C539, aryl of C5-C601～R24Wherein adjacent two groups may be bonded to each other to form a single bond, or may be bonded to form, together with an adjacent benzene ring, one of a substituted or unsubstituted C5-C30 five-or six-membered aryl ring, a substituted or unsubstituted C5-C30 five-or six-membered heteroaryl ring;
z is1And Z2Each independently selected from hydrogen or a single bond. Preferably, Z1Is a single bond, Z2Is hydrogen; or preferably, Z2Is a single bond, Z1Is hydrogen; or preferably, Z1And Z2Are all hydrogen; or preferably, Z1And Z2Are all single bonds.
Further, the compound represented by the general formula (1) of the present invention may preferably be a compound having the following specific structure: p-1 to P-544, these compounds being representative only:
Figure BDA0002359516980000051
Figure BDA0002359516980000061
Figure BDA0002359516980000071
Figure BDA0002359516980000081
Figure BDA0002359516980000091
Figure BDA0002359516980000101
Figure BDA0002359516980000111
Figure BDA0002359516980000121
Figure BDA0002359516980000131
Figure BDA0002359516980000141
Figure BDA0002359516980000151
Figure BDA0002359516980000161
Figure BDA0002359516980000171
Figure BDA0002359516980000181
Figure BDA0002359516980000191
Figure BDA0002359516980000201
Figure BDA0002359516980000211
Figure BDA0002359516980000221
Figure BDA0002359516980000231
Figure BDA0002359516980000241
Figure BDA0002359516980000251
Figure BDA0002359516980000261
Figure BDA0002359516980000271
Figure BDA0002359516980000281
Figure BDA0002359516980000291
Figure BDA0002359516980000301
Figure BDA0002359516980000311
Figure BDA0002359516980000321
Figure BDA0002359516980000331
Figure BDA0002359516980000341
Figure BDA0002359516980000351
Figure BDA0002359516980000361
Figure BDA0002359516980000371
Figure BDA0002359516980000381
Figure BDA0002359516980000391
Figure BDA0002359516980000401
Figure BDA0002359516980000411
Figure BDA0002359516980000421
Figure BDA0002359516980000431
Figure BDA0002359516980000441
Figure BDA0002359516980000451
Figure BDA0002359516980000461
Figure BDA0002359516980000471
Figure BDA0002359516980000481
Figure BDA0002359516980000491
Figure BDA0002359516980000501
Figure BDA0002359516980000511
the present invention also provides an organic electroluminescent device comprising a substrate 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 layer comprises a compound represented by any one of the above general formula (i), general formula (1) to formula (7).
Specifically, embodiments of the present invention provide an organic electroluminescent device including a substrate, and an anode layer, a plurality of light emitting functional layers, and a cathode layer sequentially formed on the substrate; the light-emitting functional layer comprises a hole injection layer, a hole transport layer, a light-emitting layer and an electron transport layer, wherein the hole injection layer is formed on the anode layer, the hole transport layer is formed on the hole injection layer, the cathode layer is formed on the electron transport layer, and the light-emitting layer is arranged between the hole transport layer and the electron transport layer; among them, the light-emitting layer preferably contains the compound of the general formula of the present invention represented by any one of the general formula (i) and the general formulae (1) to (7).
The specific reason why the above-mentioned compound of the present invention is excellent as an electron transport layer material in an organic electroluminescent device is not clear, and the following reason is presumed:
the general formula compound (shown in the following formula) of the invention is used for amplifying a conjugated framework of a classical MR-TADF material, introducing more nitrogen atoms or boron atoms, realizing the obvious red shift behavior of a target MR-TADF material while keeping the large HOMO and LUMO orbits of a BN rigid framework overlapped, and obtaining the emission of green light, yellow light and even red light.
Figure BDA0002359516980000521
The OLED device prepared by the compound has narrow half-peak width and shows obvious multiple resonance effect, thereby greatly enriching the material system of multiple resonance-thermal activation delayed fluorescence and the range of luminescent color; the high-performance light-emitting diode has low starting voltage, high light-emitting efficiency and better service life, can meet the requirements of current panel manufacturing enterprises on high-performance materials, and shows good application prospects.
Drawings
FIG. 1: the structure of the organic electroluminescent device prepared by the invention is shown in the figure, wherein 1 is a substrate, 2 is an anode, 3 is a hole transport layer, 4 is an organic luminescent layer, 5 is an electron transport layer, and 6 is a cathode.
Detailed Description
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.
Basic chemical raw materials of various chemicals used in the present invention, such as petroleum ether, tert-butylbenzene, ethyl acetate, sodium sulfate, toluene, dichloromethane, potassium carbonate, boron tribromide, N-diisopropylethylamine, reaction intermediate, and the like, are commercially available from shanghai tatarian technologies ltd and silong chemical ltd. The mass spectrometer used for determining the following compounds was a ZAB-HS type mass spectrometer measurement (manufactured by Micromass, UK).
In the following, briefly describing the method for synthesizing the compound of the present invention, X is first synthesized using n-butyllithium, t-butyllithium or the like1、X2、X3And X4The hydrogen and Cl atoms between/on the surface are subjected to ortho-metallation. Subsequently, boron tribromide is added to perform lithium-boron metal exchange, and then Bronsted base (e.g., N-diisopropylethylamine) is added to perform Tandem boron hybrid-krafts Reaction (Tandem Bora-Friedel-Crafts Reaction), thereby obtaining the target product.
Figure BDA0002359516980000531
More specifically, the following gives a synthetic method of a representative specific compound of the present invention.
Synthetic examples
Synthesis example 1:
Figure BDA0002359516980000541
synthesis of Compound P-4-1
Figure BDA0002359516980000542
To a 100 ml two-necked flask, amine (3.00g, 11.52mmol), 1, 3-dibromo-2-chlorobenzene (3.12g, 11.52mmol), sodium tert-butoxide (2.77g, 28.81mmol), tri-tert-butylphosphine (70mg, 0.35mmol), palladium acetate (100mg, 0.46mmol), and 40 ml of toluene were added in this order under a nitrogen atmosphere, and the reaction was stopped after 12 hours at 90 ℃. Cooled to room temperature, 50 ml of ethanol are added, and the mixture is filtered with suction. The filter cake was washed successively with water and ethanol to give white powder P-4-1(3.4 g).
Synthesis of Compound P-4
Figure BDA0002359516980000543
A solution of tert-butyllithium in pentane (11.18mL, 1.60M, 17.89mmol) was slowly added to a 0 ℃ solution of P-4-1(3.00g, 4.07mmol) in tert-butylbenzene (60mL), and the reaction was then allowed to warm to 60 ℃ for 3 hours each. After the reaction was complete, the temperature was reduced to-30 ℃ and boron tribromide (4.48g, 17.89mmol) was slowly added and stirring continued at room temperature for 0.5 h. N, N-diisopropylethylamine (3.15g, 24.40mmol) was added at room temperature and the reaction was continued at 145 ℃ for 5 hours and stopped. The solvent was spun dry in vacuo and passed through a silica gel column (developing solvent: ethyl acetate: petroleum ether: 50:1) to give the title compound P-4(0.28g, 10% yield, 99.46% analytical purity by HPLC) as a yellow solid. MALDI-TOF-MS results: molecular ion peaks: 680.36 elemental analysis results: theoretical value: c, 84.74; h, 3.85; b, 3.18; n,8.23 (%); experimental values: c, 84.64; h, 3.85; b, 3.28; n,8.23 (%).
Synthesis example 2:
Figure BDA0002359516980000551
synthesis of Compound P-19-1
Figure BDA0002359516980000552
This example is essentially the same as the synthesis of compound P-4-1, except that: in this case, an amine replacing the desired substance. The objective compound P-19-1(3.6g) was a white solid.
Synthesis of Compound P-19
Figure BDA0002359516980000553
This example is essentially the same as the synthesis of compound P-4, except that: in this case, P-4-1 is replaced by P-19-1 in an equal amount. The title compound P-19(0.18g, 6% yield, 99.75% purity by HPLC) was a yellow solid. MALDI-TOF-MS results: molecular ion peaks: 736.46 elemental analysis results: theoretical value: c, 84.80; h, 4.65; b, 2.94; n,7.61 (%); experimental values: c, 84.90; h, 4.55; b, 2.84; n,7.71 (%).
Synthetic example 3:
Figure BDA0002359516980000561
synthesis of Compound P-9-1
Figure BDA0002359516980000562
This example is essentially the same as the synthesis of compound P-4-1, except that: in this case, amines and halides are substituted for the desired substances. The objective compound P-9-1(3.2g) was a white solid.
Synthesis of Compound P-9
Figure BDA0002359516980000563
This example is essentially the same as the synthesis of compound P-4, except that: in this case, P-4-1 is replaced by P-9-1 in an equal amount. The title compound, P-9(0.22g, 8% yield, 99.66% purity by HPLC) was a yellow solid. MALDI-TOF-MS results: molecular ion peaks: 676.38 elemental analysis results: theoretical value: c, 85.24; h, 3.28; b, 3.20; n,8.28 (%); experimental values: c, 85.14; h, 3.38; b, 3.30; n,8.18 (%).
Synthetic example 4:
Figure BDA0002359516980000571
synthesis of Compound P-62-1
Figure BDA0002359516980000572
This example is essentially the same as the synthesis of compound P-4-1, except that: in this case, amines and halides are substituted for the desired substances. The objective compound P-62-1(4.8g) was a white solid.
Synthesis of Compound P-62
Figure BDA0002359516980000573
This example is essentially the same as the synthesis of compound P-4, except that: in this case, P-4-1 is replaced by P-62-1 in an equal amount. The title compound, P-9(0.48g, 12% yield, 99.36% purity by HPLC), was an orange-red solid. MALDI-TOF-MS results: molecular ion peaks: 980.75 elemental analysis results: theoretical value: c, 88.18; h, 3.91; b, 2.20; n,5.71 (%); experimental values: c, 88.28; h, 3.91; b, 2.30; n,5.51 (%).
Synthesis example 5:
Figure BDA0002359516980000581
synthesis of Compound P-155-1
Figure BDA0002359516980000582
This example is essentially the same as the synthesis of compound P-4-1, except that: in this case, amines and halides are substituted for the desired substances. The objective compound P-155-1(3.9g) was a white solid.
Synthesis of Compound P-62
Figure BDA0002359516980000583
This example is essentially the same as the synthesis of compound P-4, except that: in this case, P-4-1 is replaced by P-62-1 in an equal amount. The title compound, P-9(0.23g, 8% yield, 99.85% purity by HPLC) was an orange-red solid. MALDI-TOF-MS results: molecular ion peaks: 712.52 elemental analysis results: theoretical value: c, 80.94; h, 2.83; b, 3.04; f, 5.33; n,7.87 (%); experimental values: c, 80.92; h, 2.82; b, 3.04; f, 5.34; n,7.87 (%).
Synthetic example 6:
Figure BDA0002359516980000591
synthesis of Compound P-5-1
Figure BDA0002359516980000592
This example is essentially the same as the synthesis of compound P-4-1, except that: in this case, amines and halides are substituted for the desired substances. The objective compound P-5-1(4.2g) was a white solid.
Synthesis of Compound P-62
Figure BDA0002359516980000593
This example is essentially the same as the synthesis of compound P-4, except that: in this case, P-4-1 is replaced by P-5-1 in an equivalent amount. The title compound, P-9(0.23g, 8% yield, 99.85% purity by HPLC) was an orange-red solid. MALDI-TOF-MS results: molecular ion peaks: 676.02 elemental analysis results: theoretical value: c, 85.24; h, 3.28; b, 3.20; n,8.28 (%); experimental values: c, 85.14; h, 3.28; b, 3.30; n,8.28 (%).
Synthetic example 7:
Figure BDA0002359516980000601
synthesis of Compound P-62-1
Figure BDA0002359516980000602
This example is essentially the same as the synthesis of compound P-4-1, except that: in this case, amines and halides are substituted for the desired substances. The objective compound P-62-1(4.6g) was a white solid.
Synthesis of Compound P-62
Figure BDA0002359516980000603
This example is essentially the same as the synthesis of compound P-4, except that: in this case, P-4-1 is replaced by P-62-1 in an equal amount. The title compound, P-9(0.36g, 9% yield, 99.55% purity by HPLC), was an orange-red solid. MALDI-TOF-MS results: molecular ion peaks: 980.65 elemental analysis results: theoretical value: c, 88.18; h, 3.91; b, 2.20; n,5.71 (%); experimental values: c, 88.18; h, 3.91; b, 2.20; n,5.71 (%).
Synthesis example 8:
Figure BDA0002359516980000611
synthesis of Compound P-154-1
Figure BDA0002359516980000612
This example is essentially the same as the synthesis of compound P-4-1, except that: in this case, amines and halides are substituted for the desired substances. The objective compound P-154-1(3.6g) was a white solid.
Synthesis of Compound P-154
Figure BDA0002359516980000613
This example is essentially the same as the synthesis of compound P-4, except that: in this case, P-4-1 is replaced by P-154-1 in an equal amount. The title compound, P-9(0.20g, 7% yield, 99.38% purity by HPLC), was an orange-red solid. MALDI-TOF-MS results: molecular ion peaks: 1002.02 elemental analysis results: theoretical value: c, 80.94; h, 2.83; b, 3.04; f, 5.33; n,7.87 (%); experimental values: c, 80.94; h, 2.85; b, 3.04; f, 5.31; n,7.86 (%).
Synthetic example 9:
Figure BDA0002359516980000621
synthesis of Compound P-177-1
Figure BDA0002359516980000622
This example is essentially the same as the synthesis of compound P-4-1, except that: in this case, amines and halides are substituted for the desired substances. The objective compound P-177-1(3.6g) was a white solid.
Synthesis of Compound P-177
Figure BDA0002359516980000623
A solution of tert-butyllithium in pentane (18.59mL, 1.60M, 29.75mmol) was slowly added to a 0 deg.C solution of P-177-1(3.00g, 4.96mmol) in tert-butylbenzene (60mL), and the reaction was then allowed to warm to 60 deg.C in sequence for 3 hours each. After the reaction was complete, the temperature was reduced to-30 ℃ and boron tribromide (3.73g, 14.88mmol) was slowly added and stirring was continued at room temperature for 0.5 hour. N, N-diisopropylethylamine (1.92g, 14.88mmol) was added at room temperature and the reaction was continued at 145 ℃ for 12 hours and then cooled to room temperature, whereupon phenylmagnesium bromide (2.70g, 14.88mmol) was added and the reaction was stopped after 2 hours. The solvent was spun off in vacuo and passed through a silica gel column (developing solvent: ethyl acetate: petroleum ether: 50:1) to give the title compound P-177(0.17g, 5% yield, HPLC assay purity 99.32%) as a yellow solid. MALDI-TOF-MS results: molecular ion peaks: 681.35 elemental analysis results: theoretical value: c, 84.63; h, 4.44; b, 4.76; n,6.17 (%); experimental values: c, 84.64; h, 4.43; b, 4.66; n,6.27 (%).
Synthetic example 10:
Figure BDA0002359516980000631
synthesis of Compound P-237-1
Figure BDA0002359516980000632
This example is essentially the same as the synthesis of compound P-4-1, except that: in this case, amines and halides are substituted for the desired substances. The objective compound, P-237-1(5.6g), was a white solid.
Synthesis of Compound P-237
Figure BDA0002359516980000633
This example is essentially the same as the synthesis of compound P-177, except that: in this case, P-177-1 is replaced by P-237-1 in an equal amount. The title compound, P-237(0.18g, 4.5% yield, 99.28% purity by HPLC) was a yellow solid. MALDI-TOF-MS results: molecular ion peaks: 833.02 elemental analysis results: theoretical value: c, 86.47; h, 4.60; b, 3.89; n,5.04 (%); experimental values: c, 86.47; h, 4.50; b, 3.89; n,5.14 (%).
Synthetic example 11:
Figure BDA0002359516980000641
synthesis of Compound P-179-1
Figure BDA0002359516980000642
This example is essentially the same as the synthesis of compound P-4-1, except that: in this case, amines and halides are substituted for the desired substances. The title compound, P-179-1(3.6g), was a white solid.
Synthesis of Compound P-179
Figure BDA0002359516980000643
This example is essentially the same as the synthesis of compound P-4, except that: in this case, P-4-1 is replaced by P-179-1 in an amount equivalent to that of the substance. The title compound P-179(0.16g, 6% yield, 99.63% purity by HPLC) was an orange yellow solid. MALDI-TOF-MS results: molecular ion peaks: 677.02 elemental analysis results: theoretical value: c, 85.14; h, 3.87; b, 4.79; n,6.21 (%); experimental values: c, 85.24; h, 3.77; b, 4.78; n,6.21 (%).
Synthetic example 12:
Figure BDA0002359516980000651
synthesis of Compound P-185-1
Figure BDA0002359516980000652
This example is essentially the same as the synthesis of compound P-4-1, except that: in this case, amines and halides are substituted for the desired substances. The objective compound P-185-1(4.6g) was a white solid.
Synthesis of Compound P-185
Figure BDA0002359516980000653
This example is essentially the same as the synthesis of compound P-177, except that: in this case, P-177-1 is replaced by P-185-1 in equal amount. The title compound P-185(0.22g, 6.6% yield, 99.52% purity by HPLC) was an orange yellow solid. MALDI-TOF-MS results: molecular ion peaks: 673.02 elemental analysis results: theoretical value: c, 85.65; h, 3.29; b, 4.82; n,6.24 (%); experimental values: c, 85.66; h, 3.19; b, 4.81; n,6.34 (%).
Synthetic example 13:
Figure BDA0002359516980000661
synthesis of Compound P-187-1
Figure BDA0002359516980000662
This example is essentially the same as the synthesis of compound P-4-1, except that: in this case, amines and halides are substituted for the desired substances. The objective compound, P-187-1(4.6g), was a white solid.
Synthesis of Compound P-187
Figure BDA0002359516980000663
This example is essentially the same as the synthesis of compound P-4, except that: in this example, P-4-1 is replaced by P-187-1 in an amount equivalent to the amount of the substance. The title compound, P-187(0.22g, 8% yield, 99.48% purity by HPLC), was an orange-red solid. MALDI-TOF-MS results: molecular ion peaks: 673.02 elemental analysis results: theoretical value: c, 85.65; h, 3.29; b, 4.82; n,6.24 (%); experimental values: c, 85.55; h, 3.19; b, 4.92; n,6.34 (%).
Synthesis example 14:
Figure BDA0002359516980000671
synthesis of Compound P-347-1
Figure BDA0002359516980000672
This example is essentially the same as the synthesis of compound P-4-1, except that: in this case, amines and halides are substituted for the desired substances. The objective compound P-347-1(3.1g) was a white solid.
Synthesis of Compound P-347
Figure BDA0002359516980000673
A solution of tert-butyllithium in pentane (18.59mL, 1.60M, 29.75mmol) was slowly added to a 0 ℃ solution of P-347-1(2.34g, 4.96mmol) in tert-butylbenzene (60mL), and the reaction was then allowed to warm to 60 ℃ for 3 hours each. After the reaction was complete, the temperature was reduced to-30 ℃ and boron tribromide (4.97g, 19.82mmol) was slowly added and stirring continued at room temperature for 0.5 h. N, N-diisopropylethylamine (2.56g, 19.82mmol) was added at room temperature and the reaction was continued at 145 ℃ for 12 hours and then cooled to room temperature, whereupon phenylmagnesium bromide (3.59g, 19.82mmol) was added and the reaction was stopped after 2 hours. The solvent was dried by evaporation in vacuo and passed through a silica gel column (developing solvent: ethyl acetate: petroleum ether: 50:1) to give the title compound P-347(0.30g, 9% yield, 99.62% analytical purity by HPLC) as a yellow solid. MALDI-TOF-MS results: molecular ion peaks: 678.42 elemental analysis results: theoretical value: c, 85.03; h, 4.46; b, 6.38; n,4.13 (%); experimental values: c, 85.13; h, 4.46; b, 6.28; n,4.13 (%).
Synthetic example 15:
Figure BDA0002359516980000681
synthesis of Compound P-368
Figure BDA0002359516980000682
This example is essentially the same as the synthesis of compound P-347, except that: in this case, the phenylmagnesium bromide was replaced by an equivalent amount of tolylmagnesium bromide. The title compound, P-9(0.29g, 8% yield, 99.28% purity by HPLC) was a green solid. MALDI-TOF-MS results: molecular ion peaks: 734.25 elemental analysis results: theoretical value: c, 85.08; h, 5.22; b, 5.89; n,3.82 (%); experimental values: c, 85.18; h, 5.22; b, 5.79; n,3.82 (%).
Synthetic example 16:
Figure BDA0002359516980000683
synthesis of Compound P-408
Figure BDA0002359516980000691
This example is essentially the same as the synthesis of compound P-347, except that: in this case, the phenylmagnesium bromide is replaced by the same amount of tert-butylbenzylmagnesium bromide. The title compound P-408(0.40g, 9% yield, 99.44% purity by HPLC) was a yellow solid. MALDI-TOF-MS results: molecular ion peaks: 902.02 elemental analysis results: theoretical value: c, 85.18; h, 6.93; b, 4.79; n,3.10 (%); experimental values: c, 85.08; h, 6.93; b, 4.79; n,3.20 (%).
Synthetic example 17:
Figure BDA0002359516980000692
synthesis of Compound P-359-1
Figure BDA0002359516980000693
This example is essentially the same as the synthesis of compound P-4-1, except that: in this case, amines and halides are substituted for the desired substances. The objective compound P-359-1(3.5g) was a white solid.
Synthesis of Compound P-62
Figure BDA0002359516980000701
This example is essentially the same as the synthesis of compound P-347, except that: in this case, P-347-1 is replaced by P-359-1 in an equal amount. The title compound P-359(0.22g, 6.6% yield, 99.34% purity by HPLC) as a yellow solid. MALDI-TOF-MS results: molecular ion peaks: 674.02 elemental analysis results: theoretical value: c, 85.54; h, 3.89; b, 6.42; n,4.16 (%); experimental values: c, 85.64; h, 3.89; b, 6.32; n,4.16 (%).
Synthetic example 18:
Figure BDA0002359516980000702
synthesis of Compound P-363-1
Figure BDA0002359516980000703
This example is essentially the same as the synthesis of compound P-4-1, except that: in this case, amines and halides are substituted for the desired substances. The objective compound P-363-1(3.6g) was a white solid.
Synthesis of Compound P-363
Figure BDA0002359516980000711
This example is essentially the same as the synthesis of compound P-347, except that: in this case, P-347-1 is replaced by an equivalent amount of P-363-1. The title compound P-363(0.26g, 8% yield, 99.74% purity by HPLC) was an orange yellow solid. MALDI-TOF-MS results: molecular ion peaks: 670.02 elemental analysis results: theoretical value: c, 86.05; h, 3.31; b, 6.45; n,4.18 (%); experimental values: c, 86.15; h, 3.21; b, 6.46; n,4.17 (%).
The technical effects and advantages of the invention are shown and verified by testing practical use performance by specifically applying the compound of the invention to an organic electroluminescent device.
The organic electroluminescent device includes a first electrode, a second electrode, and an organic material layer between the two electrodes. The organic material may be divided into a plurality of regions, for example, the organic material layer may include a hole transport region, a light emitting layer, and an electron transport region.
As a material of the anode, an oxide transparent conductive material such as Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), tin dioxide (SnO2), or zinc oxide (ZnO), or any combination thereof can be used. The cathode may be made of magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag), or any combination thereof.
The hole transport region is located between the anode and the light emitting layer. The hole transport region may be a Hole Transport Layer (HTL) of a single layer structure including a single layer containing only one compound and a single layer containing a plurality of compounds. The hole transport region may also be a multilayer structure including at least one of a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), and an Electron Blocking Layer (EBL).
The material of the hole transport region may be selected from, but is not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylenevinylene, polyaniline/dodecylbenzenesulfonic acid (Pani/DBSA), poly (3, 4-ethylenedioxythiophene)/poly (4-styrenesulfonate) (PEDOT/PSS), polyaniline/camphorsulfonic acid (Pani/CSA), polyaniline/poly (4-styrenesulfonate) (Pani/PSS), aromatic amine derivatives, and the like.
The light-emitting layer includes a light-emitting dye (i.e., dopant) that can emit different wavelength spectra, and may also include a Host material (Host). The light emitting layer may be a single color light emitting layer emitting a single color of red, green, blue, or the like. The single color light emitting layers of a plurality of different colors may be arranged in a planar manner in accordance with a pixel pattern, or may be stacked to form a color light emitting layer. When the light emitting layers of different colors are stacked together, they may be spaced apart from each other or may be connected to each other. The light-emitting layer may be a single color light-emitting layer capable of emitting red, green, blue, or the like at the same time.
The electron transport region may be an Electron Transport Layer (ETL) of a single-layer structure including a single-layer electron transport layer containing only one compound and a single-layer electron transport layer containing a plurality of compounds. The electron transport region may also be a multilayer structure including at least one of an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), and a Hole Blocking Layer (HBL).
The preparation process of the organic electroluminescent device is described as follows with reference to the attached figure 1: an anode 2, a hole transport layer 3, an organic light emitting layer 4, an electron transport layer 5, and a cathode 6 are sequentially deposited on a substrate 1, and then encapsulated. In the preparation of the organic light-emitting layer 4, the organic light-emitting layer 4 is formed by a co-deposition method using a wide band gap material source, an electron donor material source, an electron acceptor material source, and a resonance TADF material source.
Specifically, the preparation method of the organic electroluminescent device comprises the following steps:
1. the anode material coated glass plate 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;
2. placing the glass plate with the anode in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3Pa, forming a hole injection layer by vacuum evaporation of a hole injection material on the anode layer film, wherein the evaporation rate is 0.1-0.5 nm/s;
3. vacuum evaporating hole transport material on the hole injection layer to form a hole transport layer with an evaporation rate of 0.1-0.5nm/s,
4. vacuum evaporating an electron blocking layer on the hole transport layer, wherein the evaporation rate is 0.1-0.5 nm/s;
5. the organic light-emitting layer of the device is vacuum evaporated on the electron barrier layer, the organic light-emitting layer material comprises a main material and TADF dye, and the evaporation rate of the main material, the evaporation rate of the sensitizer material and the evaporation rate of the dye are adjusted by a multi-source co-evaporation method to enable the dye to reach a preset doping proportion;
6. vacuum evaporating a hole blocking layer on the organic light-emitting layer, wherein the evaporation rate is 0.1-0.5 nm/s;
7. forming an electron transport layer on the hole blocking layer by vacuum evaporation of an electron transport material of the device, wherein the evaporation rate is 0.1-0.5 nm/s;
8. LiF is evaporated on the electron transport layer in vacuum at a speed of 0.1-0.5nm/s to serve as an electron injection layer, and an Al layer is evaporated on the electron transport layer in vacuum at a speed of 0.5-1nm/s to serve as a cathode of the device.
The embodiment of the invention also provides a display device which comprises the organic electroluminescent device provided as above. The display device can be specifically a display device such as an OLED display, and any product or component with a display function including the display device, such as a television, a digital camera, a mobile phone, a tablet computer, and the like. The display device has the same advantages as the organic electroluminescent device compared with the prior art, and the description is omitted here.
The organic electroluminescent device according to the invention is further illustrated by the following specific examples.
Device example 1
The structure of the organic electroluminescent device prepared in this example is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:3wt％P-4(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
wherein the anode material is ITO; the hole injection layer is made of HI, the total thickness is generally 5-30nm, and the thickness is 10nm in the embodiment; the hole transport layer is made of HT, and the total thickness is generally 5-500nm, 40nm in this embodiment; host is a main body material with wide band gap of an organic light-emitting layer, the compound P-4 of the invention is dye and the doping concentration is 3 wt%, the thickness of the organic light-emitting layer is generally 1-200nm, in this embodiment 30 nm; the material of the electron transport layer is ET, the thickness is generally 5-300nm, in this embodiment 30 nm; the electron injection layer and the cathode material are selected from LiF (0.5nm) and metallic aluminum (150 nm).
A DC voltage was applied to the organic electroluminescent element D1 prepared in this example, and 10cd/m was measured2The characteristics in light emission were such that yellow light emission (driving voltage of 2.6V) having a wavelength of 545nm, a half-peak width of 38nm, CIE color coordinates (x, y) (0.36,0.62), and an external quantum efficiency EQE of 28.8% was obtained.
Device example 2
The same preparation method as that of the device example 1 except that the wide band gap type Host material used in the light emitting layer was replaced with the TADF type Host TD, the specific device structure was as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD:3wt％P-4(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance measurement results of the organic electroluminescent device D2 prepared in this example are as follows: applying a DC voltage, and measuring 10cd/m2The characteristics in light emission were such that yellow light emission (driving voltage of 2.4V) having a wavelength of 548nm, a half-peak width of 41nm, CIE color coordinates (x, y) ═ 0.37,0.63, and an external quantum efficiency EQE of 31.4% was obtained.
Device example 3
The same procedure as in device example 1 was followed except that the dye used in the light-emitting layer was replaced with P-19 from P-4. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:3wt％P-19(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D3 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m2The characteristics in light emission were such that yellow light emission (drive voltage of 2.6V) having a wavelength of 548nm, a half-peak width of 40nm, CIE color coordinates (x, y) (0.37,0.64), and an external quantum efficiency EQE of 28.3% was obtained.
Device example 4
The same preparation method as that of device example 1 was used except that the wide band gap type Host material Host in the light-emitting layer was replaced with TADF type Host TD and the dye was replaced with P-4 to P-19. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD:3wt％P-19(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D4 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m2The characteristics in light emission were such that yellow light emission (drive voltage of 2.6V) having a wavelength of 550nm, a half-width of 42nm, CIE color coordinates (x, y) (0.38,0.64), and an external quantum efficiency EQE of 30.4% was obtained.
Device example 5
The same procedure as in device example 1 was followed except that the dye in the light-emitting layer was replaced with P-9 from P-4. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:3wt％P-9(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
the organic electroluminescence prepared in this exampleDevice D5 device performance results were determined as follows: applying a DC voltage, and measuring 10cd/m2The characteristics in light emission were such that yellow light emission (driving voltage of 2.6V) having a wavelength of 555nm, a half-peak width of 35nm, CIE color coordinates (x, y) (0.37,0.63), and external quantum efficiency EQE of 29.3% was obtained.
Device example 6
The same preparation method as that of device example 1 was used except that the wide band gap type Host material Host in the light-emitting layer was replaced with TADF type Host TD and the dye was replaced with P-4 to P-9. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD:3wt％P-9(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D6 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m2The characteristics in light emission were such that yellow light emission (driving voltage of 2.6V) with a wavelength of 557nm, a peak width at half maximum of 37nm, CIE color coordinates (x, y) (0.37,0.62), and an external quantum efficiency EQE of 33.6% was obtained.
Device example 7
The same procedure as in device example 1 was followed except that the dye in the light-emitting layer was replaced with P-5 from P-4. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:3wt％P-5(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D7 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m2The characteristics in light emission were that orange-yellow light emission (driving voltage of 2.8V) having a wavelength of 575nm, a half-width of 42nm, CIE color coordinates (x, y) (0.41,0.61), and external quantum efficiency EQE of 23.3% was obtained.
Device example 8
The same preparation method as that of device example 1 was used except that the wide band gap type Host material Host in the light-emitting layer was replaced with TADF type Host TD and the dye was replaced with P-4 to P-5. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD:3wt％P-5(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D8 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m2The characteristics in light emission were such that orange emission (driving voltage of 2.4V) with a wavelength of 577nm, a half-peak width of 44nm, CIE color coordinates (x, y) ═ 0.41,0.60, and an external quantum efficiency EQE of 27.4% was obtained.
Device example 9
The same procedure as in device example 1 was followed except that the dye in the light-emitting layer was replaced with P-177 from P-4. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:3wt％P-177(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D9 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m2The green emission (driving voltage of 2.8V) having a wavelength of 526nm, a half-peak width of 41nm, CIE color coordinates (x, y) (0.32,0.61), and an external quantum efficiency EQE of 28.3% was obtained as characteristics in the emission.
Device example 10
The same preparation method as that of device example 1 was used except that the wide band gap type Host material Host in the light-emitting layer was replaced with TADF type Host TD and the dye was replaced with P-177 from P-4. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD:3wt％P-177(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D10 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m2The green emission (driving voltage of 2.4V) having a wavelength of 528nm, a half-width of 45nm, CIE color coordinates (x, y) ═ 0.32,0.60, and an external quantum efficiency EQE of 31.4% was obtained as characteristics in the emission.
Device example 11
The same procedure as in device example 1 was conducted except that the dye in the light-emitting layer was replaced with P-347 from P-4. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:3wt％P-347(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D11 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m2The characteristics in light emission were such that yellow light emission (driving voltage of 2.8V) having a wavelength of 560nm, a half-peak width of 39nm, CIE color coordinates (x, y) (0.34,0.60), and an external quantum efficiency EQE of 28.3% was obtained.
Device example 12
The same preparation method as that of device example 1 was used except that the wide band gap type Host material Host in the light-emitting layer was replaced with TADF type Host TD and the dye was replaced with P-4 to P-347. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD:3wt％P-347(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D12 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m2The characteristics in light emission were such that yellow light emission (drive voltage of 2.4V) having a wavelength of 561nm, a half-peak width of 42nm, CIE color coordinates (x, y) (0.32,0.59), and an external quantum efficiency EQE of 30.4% was obtained.
Device example 13
The same procedure as in device example 1 was followed except that the dye in the light-emitting layer was replaced with P-408 from P-4. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:3wt％P-408(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D13 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m2The characteristics in light emission were such that yellow light emission (driving voltage of 2.8V) with a wavelength of 565nm, a half-peak width of 45nm, CIE color coordinates (x, y) ═ 0.39,0.58, and an external quantum efficiency EQE of 29.6% was obtained.
Device example 14
The same preparation method as that of device example 1 was used except that the wide band gap type Host material Host in the light-emitting layer was replaced with TADF type Host TD and the dye was replaced with P-408 from P-4. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD:3wt％P-408(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D14 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m2The characteristics in light emission were such that yellow light emission (driving voltage of 2.6V) having a wavelength of 566nm, a half-width of 46nm, CIE color coordinates (x, y) ═ 0.39,0.56, and an external quantum efficiency EQE of 31.4% was obtained.
Device example 15
The same procedure as in device example 1 was followed except that the dye in the light-emitting layer was replaced with P-363 from P-4. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/Host:3wt％P-363(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D15 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m2The characteristics in light emission were such that orange-red light emission (driving voltage of 2.8V) with a wavelength of 585nm, a half-peak width of 46nm, CIE color coordinates (x, y) ═ 0.55,0.42, and an external quantum efficiency EQE of 29.6% was obtained.
Device example 16
The same preparation method as that of device example 1 was used except that the wide band gap type Host material Host in the light-emitting layer was replaced with TADF type Host TD and the dye was replaced with P-4 to P-363. The device structure is as follows:
ITO/HI(10nm)/HT(30nm)/EBL(10nm)/TD:3wt％P-363(30nm)/HBL(10nm)ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device D16 prepared in this example were as follows: applying a DC voltage, and measuring 10cd/m2The characteristics in light emission were such that orange-red light emission (driving voltage of 2.4V) with a wavelength of 586nm, a peak width at half maximum of 47nm, CIE color coordinates (x, y) ═ 0.55,0.40, and external quantum efficiency EQE of 31.3% was obtained.
Comparative device example 1
The same preparation method as that of device example 1 was used except that the compound P-4 of the present invention used in the light-emitting layer was replaced with the compound P1 of the prior art, and the specific device structure was as follows:
ITO/HI(10nm)/HT(40nm)/Host:3wt％P1(30nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device DD1 prepared in this example are as follows: when a dc voltage was applied and the characteristics at 10cd/m2 light emission were measured, blue light emission (driving voltage of 3.6V) with a wavelength of 459nm, a full width at half maximum of 28nm, CIE color coordinates (x, y) ((0.13, 0.09)) and an external quantum efficiency EQE of 13.5% was obtained.
Comparative device example 2
The same preparation method as that of device example 2 except that the compound P-4 of the present invention used in the light-emitting layer was replaced with the compound P1 in the prior art, and a specific device structure was as follows:
ITO/HI(10nm)/HT(40nm)/TD:3wt％P1(30nm)/ET(30nm)/LiF(0.5nm)/Al(150nm)
the device performance results of the organic electroluminescent device DD2 prepared in this example are as follows: applying a DC voltage, and measuring 10cd/m2The characteristics in light emission were such that blue light emission (drive voltage of 3.3V) having a wavelength of 460nm, a peak width at half maximum of 28nm, CIE color coordinates (x, y) (0.13,0.09), and external quantum efficiency EQE of 18.4% was obtained.
The structural formulas of the various organic materials used in the above examples are as follows:
Figure BDA0002359516980000761
Figure BDA0002359516980000771
Figure BDA0002359516980000781
specific performance data of the organic electroluminescent devices D1 to D16 and the devices DD1 and DD2 prepared in the above respective device examples are detailed in table 1 below.
Table 1:
Figure BDA0002359516980000782
Figure BDA0002359516980000791
the experimental data show that the compound provided by the invention can realize the obvious red shift behavior of the target MR-TADF material while maintaining the large HOMO and LUMO orbital overlap of BN rigid framework by amplifying the conjugated framework of the classical MR-TADF material and introducing more nitrogen atoms or boron atoms. As can be seen from the half-peak width of the electroluminescence spectrum, the embodiment confirms that the material has effective multiple resonance effect, thereby greatly enriching the material system of multiple resonance-thermal activation delayed fluorescence and the range of luminescent color, and having good application prospect.
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.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (15)

1. A compound of the general formula (I):
Figure FDA0002359516970000011
in the formula (I), ring A, ring B, ring C and ring D each independently represent an aromatic ring or a heteroaromatic ring;
said Y is1And Y2Each is independently N or B; said X1、X2、X3And X4Are each independently NR1Or BR2；
The R is1Rings A and/or R which are each independently optionally adjacent theretoaRing B and/or RbRing C and/or RcOr ring D and/or RdLinked to form a ring or not linked to form a ring, wherein the linkage to form a ring may be through-O-, -S-, -CR3R4-or a single bond;
the R is2Rings A and/or R which are each independently optionally adjacent theretoaRing B and/or RbRing C and/or RcOr ring D and/or RdLinked to form a ring or not linked to form a ring, wherein the linkage to form a ring may be through-O-, -S-, -CR3R4-or a single bond;
the R is1、R2、R3And R4Each independently selected from one of the following substituted or unsubstituted groups: C1-C36 chain alkyl, C3-C36 cycloalkyl, C6-C30 arylamine, C3-C30 heteroarylamino, C6-C60 monocyclic aryl, C6-C60 fused ring aryl, C6-C60 aryloxy, C5-C60 monocyclic heteroaryl or C5-C60 fused ring heteroaryl;
the R isa、Rb、RcAnd RdEach independently represents a single substituent up to the maximum permissible substituents, and each is independently selected from hydrogen, deuterium, or one of the following substituted or unsubstituted groups: one of halogen, chain alkyl of C1-C36, cycloalkyl of C3-C36, alkoxy of C1-C10, thioalkoxy of C1-C10, carbonyl, carboxyl, nitro, cyano, amino, arylamino of C6-C30, heteroarylamino of C3-C30, monocyclic aryl of C6-C60, condensed ring aryl of C6-C60, aryloxy of C6-C60, monocyclic heteroaryl of C5-C60 and condensed ring heteroaryl of C5-C60;
the R isa、Rb、RcAnd RdCan be bonded to each other and together with ring A, ring B, ring C or ring D, to form, correspondingly, a substituted or unsubstituted C6 ℃; EA C30 aryl or substituted or unsubstituted C3-C30 heteroaryl;
when the above groups have substituents, the substituents are respectively and independently selected from any one of deuterium, halogen, chain alkyl of C1-C30, cycloalkyl of C3-C30, alkoxy of C1-C10, thioalkoxy of C1-C10, carbonyl, carboxyl, nitro, cyano, amino, arylamino of C6-C30, heteroarylamino of C3-C30, monocyclic aryl of C6-C60, condensed ring aryl of C6-C60, aryloxy of C6-C60, monocyclic heteroaryl of C5-C60 and condensed ring heteroaryl of C5-C60.
2. The compound of general formula (I) as claimed in claim 1, wherein ring A, ring B, ring C and ring D each independently represent any one of monocyclic aromatic ring or fused aromatic ring of C5-C20, monocyclic heterocyclic ring or fused heterocyclic ring of C4-C20;
preferably, the a, ring B, ring C and ring D each independently represent any one of a monocyclic aromatic ring or a fused aromatic ring of C5 to C10, a monocyclic heterocyclic ring or a fused heterocyclic ring of C4 to C10;
more preferably, the a, ring B, ring C and ring D are each independently selected from any one of a benzene ring, a naphthalene ring or a fluorene ring.
3. A compound of general formula (la) according to claim 1 or 2, represented by the following formula (1):
Figure FDA0002359516970000021
in formula (1):
said Y is1And Y2Each is independently N or B; said X1、X2、X3And X4Are each independently NR1Or BR2；
The R is1Ring a and/or R independently and adjacently adjacent to each otheraRing b and/or RbRing c and/or RcOr ring d and/or RdLinked to form a ring or not linked to form a ring, wherein the linkage to form a ring may be through-O-, -S-, -CR3R4-or a single bond;
the R is2Ring a and/or R independently and adjacently adjacent to each otheraRing b and/or RbRing c and/or RcOr ring d and/or RdLinked to form a ring or not linked to form a ring, wherein the linkage to form a ring may be through-O-, -S-, -CR3R4-or a single bond;
the R isa、Rb、Rc、Rd、R3And R4Are as defined in formula (I).
4. A compound of general formula (la) according to claim 1 or 3, represented by any one of the following formulae (2) to (4):
Figure FDA0002359516970000022
in formulae (2) to (4), X1、X2、X3、X4、Ra、Rb、RcAnd RdAre as defined in formula (I).
5. A compound of general formula (la) according to claim 1 or 3, represented by the following formula (2):
Figure FDA0002359516970000031
in the formula (2), X1、X2、X3And X4Are each independently NR1，Ra、Rb、RcAnd RdAre as defined in formula (I).
6. A compound of general formula (la) according to claim 1 or 3, represented by the following formula (3):
Figure FDA0002359516970000032
in the formula (3), X1、X2Are each independently NR1，X3、X4Are respectively independent and are respectively BR2，Ra、Rb、RcAnd RdAre as defined in formula (I).
7. A compound of general formula (la) according to claim 1 or 3, represented by the following formula (4):
Figure FDA0002359516970000033
in the formula (4), X1、X2、X3And X4Are respectively independent and are respectively BR2，Ra、Rb、RcAnd RdAre as defined in formula (I).
8. A compound of formula (la) according to any one of claims 3 to 7, wherein in formulae (1) to (4):
the R is1Rings a and/or R independently adjacent theretoaRing b and/or RbRing c and/or RcOr ring d and/or RdWhen the connection is performed to form a ring, the connection is performed through a single bond;
or, said R2Rings a and/or R independently adjacent theretoaRing b and/or RbRing c and/or RcOr ring d and/or RdWhen they are linked to form a ring, they are linked by a single bond.
9. The compound of formula (I), formula (1) to formula (4) as claimed in any one of claims 1 to 8,
the R isa、Rb、RcAnd RdEach independently selected from hydrogen, deuterium, or one of the following substituted or unsubstituted groups: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cycloPentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, trifluoromethyl, pentafluoroethyl, 2,2, 2-trifluoroethyl, phenyl, naphthyl, anthryl, benzanthryl, phenanthryl, benzophenanthryl, pyrenyl, anthryl, perylenyl, fluoranthenyl, tetracenyl, pentacenyl, benzopyrenyl, biphenyl, idophenyl, terphenyl, quaterphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis-or trans-indenofluorenyl, triindenyl, isotridendenyl, spirotrimeric indenyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thienyl, benzothienyl, isobenzothienyl, dibenzothienyl, pyrrolyl, isoindolyl, carbazolyl, 2-ethylhexyl, trifluoromethyl, 2, 2-trifluoroethyl, pentacenyl, benzopyrenyl, biphenyl, terphenyl, terphenylyl, terphenylenyl, terphenylindenyl, terp, Indenocarbazolyl, pyridyl, quinolyl, isoquinolyl, acridinyl, phenanthridinyl, benzo-5, 6-quinolyl, benzo-6, 7-quinolyl, benzo-7, 8-quinolyl, pyrazolyl, indazolyl, imidazolyl, benzimidazolyl, naphthoimidazolyl, phenanthrimidazolyl, pyridoimidazolyl, pyrazinoimidazolyl, quinoxalimidazolyl, oxazolyl, benzoxazolyl, naphthooxazolyl, anthraoxazolyl, phenanthroxazolyl, 1, 2-thiazolyl, 1, 3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyrazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1, 5-diazoanthrenyl, 2, 7-diazepanyl, 2, 3-diazapyl, 1, 6-diazapyl, 1, 8-diazapyl, 4, 5-diazenylene group, 4,5,9, 10-tetraazaperylene group, pyrazinyl group, phenazinyl group, phenothiazinyl group, naphthyridinyl group, azacarbazolyl group, benzocarbazinyl group, phenanthrolinyl group, 1,2, 3-triazolyl group, 1,2, 4-triazolyl group, benzotriazolyl group, 1,2, 3-oxadiazolyl group, 1,2, 4-oxadiazolyl group, 1,2, 5-oxadiazolyl group, 1,2, 3-thiadiazolyl group, 1,2, 4-thiadiazolyl group, 1,2, 5-thiadiazolyl group, 1,3, 4-thiadiazolyl group, 1,3, 5-triazinyl group, 1,2, 4-triazinyl group, 1,2, 3-triazinyl group, tetrazolyl group, 1,2,4, 5-tetrazinyl group, 1,2,3, 4-tetrazinyl group, 1,2,3, 5-tetrazinyl group, Purinyl, pteridinyl, indolizinyl, benzothiadiazolyl, 9-dimethylazinyl, triarylamino, adamantane, fluorophenyl, methylphenyl, trimethylphenyl, cyanophenyl, tetrahydropyrrole, piperidineMethoxy, silyl, or a combination of two substituent groups selected from the above;
when the above groups have substituents, the substituents are respectively and independently selected from any one of halogen, chain alkyl of C1-C12, cycloalkyl of C3-C12, alkoxy or thioalkoxy of C1-C6, arylamino of C6-C30, heteroaryl of C3-C30, monocyclic aromatic hydrocarbon or fused ring aromatic hydrocarbon group of C6-C30, monocyclic heteroaromatic hydrocarbon or fused ring heteroaromatic hydrocarbon group of C3-C30.
10. The compound of general formula (la) according to claim 1 or 5, represented by the following formula (5):
Figure FDA0002359516970000051
in the formula (5), R is1～R24Each independently selected from hydrogen, deuterium, or one of the following substituted or unsubstituted groups: halogen, chain alkyl of C1-C36, cycloalkyl of C3-C36, alkoxy of C1-C10, thioalkoxy of C1-C10, carbonyl, carboxyl, nitro, cyano, amino, arylamino of C6-C30, heteroarylamino of C3-C30, monocyclic aryl of C6-C60, condensed ring aryl of C6-C60, aryloxy of C6-C60, monocyclic heteroaryl of C5-C60, condensed ring heteroaryl of C5-C60, and R is one of R6-C36, cycloalkyl of C3-C36, alkoxy of C1-C10, aryl of C3, aryl of C5-C539, aryl of C5-C601～R24Wherein adjacent two groups may be bonded to each other to form a single bond, or may be bonded to form, together with an adjacent benzene ring, one of a substituted or unsubstituted C5-C30 five-or six-membered aryl ring, a substituted or unsubstituted C5-C30 five-or six-membered heteroaryl ring;
z is1And Z2Each independently selected from hydrogen or a single bond;
preferably, Z1Is a single bond, Z2Is hydrogen;
preferably, Z2Is a single bond, Z1Is hydrogen;
preferably, Z1And Z2Are all hydrogen;
preferably, Z1And Z2Are all single bonds.
11. The compound of general formula (la) according to claim 1 or 6, represented by the following formula (6):
Figure FDA0002359516970000052
in the formula (6), R is1～R24Each independently selected from hydrogen, deuterium, or one of the following substituted or unsubstituted groups: halogen, chain alkyl of C1-C36, cycloalkyl of C3-C36, alkoxy of C1-C10, thioalkoxy of C1-C10, carbonyl, carboxyl, nitro, cyano, amino, arylamino of C6-C30, heteroarylamino of C3-C30, monocyclic aryl of C6-C60, condensed ring aryl of C6-C60, aryloxy of C6-C60, monocyclic heteroaryl of C5-C60, condensed ring heteroaryl of C5-C60, and R is one of R6-C36, cycloalkyl of C3-C36, alkoxy of C1-C10, aryl of C3, aryl of C5-C539, aryl of C5-C601～R24Wherein adjacent two groups may be bonded to each other to form a single bond, or may be bonded to form, together with an adjacent benzene ring, one of a substituted or unsubstituted C5-C30 five-or six-membered aryl ring, a substituted or unsubstituted C5-C30 five-or six-membered heteroaryl ring;
z is1And Z2Each independently selected from hydrogen or a single bond;
preferably, Z1Is a single bond, Z2Is hydrogen;
preferably, Z2Is a single bond, Z1Is hydrogen;
preferably, Z1And Z2Are all hydrogen;
preferably, Z1And Z2Are all single bonds.
12. A compound of formula (la) according to claim 1 or 7, represented by the following formula (7):
Figure FDA0002359516970000061
in the formula (7), R is1～R24Each independently selected from hydrogen, deuterium or substitutedUnsubstituted one of the following groups: halogen, chain alkyl of C1-C36, cycloalkyl of C3-C36, alkoxy of C1-C10, thioalkoxy of C1-C10, carbonyl, carboxyl, nitro, cyano, amino, arylamino of C6-C30, heteroarylamino of C3-C30, monocyclic aryl of C6-C60, condensed ring aryl of C6-C60, aryloxy of C6-C60, monocyclic heteroaryl of C5-C60, condensed ring heteroaryl of C5-C60, and R is one of R6-C36, cycloalkyl of C3-C36, alkoxy of C1-C10, aryl of C3, aryl of C5-C539, aryl of C5-C601～R24Wherein adjacent two groups may be bonded to each other to form a single bond, or may be bonded to form, together with an adjacent benzene ring, one of a substituted or unsubstituted C5-C30 five-or six-membered aryl ring, a substituted or unsubstituted C5-C30 five-or six-membered heteroaryl ring;
z is1And Z2Each independently selected from hydrogen or a single bond;
preferably, Z1Is a single bond, Z2Is hydrogen;
preferably, Z2Is a single bond, Z1Is hydrogen;
preferably, Z1And Z2Are all hydrogen;
preferably, Z1And Z2Are all single bonds.
13. A compound of formula (la) according to claim 1, selected from the compounds of the following specific structures:
Figure FDA0002359516970000071
Figure FDA0002359516970000081
Figure FDA0002359516970000091
Figure FDA0002359516970000101
Figure FDA0002359516970000111
Figure FDA0002359516970000121
Figure FDA0002359516970000131
Figure FDA0002359516970000141
Figure FDA0002359516970000151
Figure FDA0002359516970000161
Figure FDA0002359516970000171
Figure FDA0002359516970000181
Figure FDA0002359516970000191
Figure FDA0002359516970000201
Figure FDA0002359516970000211
Figure FDA0002359516970000221
Figure FDA0002359516970000231
Figure FDA0002359516970000241
Figure FDA0002359516970000251
Figure FDA0002359516970000261
Figure FDA0002359516970000271
Figure FDA0002359516970000281
Figure FDA0002359516970000291
Figure FDA0002359516970000301
Figure FDA0002359516970000311
Figure FDA0002359516970000321
Figure FDA0002359516970000331
Figure FDA0002359516970000341
Figure FDA0002359516970000351
Figure FDA0002359516970000361
Figure FDA0002359516970000371
Figure FDA0002359516970000381
Figure FDA0002359516970000391
Figure FDA0002359516970000401
Figure FDA0002359516970000411
Figure FDA0002359516970000421
Figure FDA0002359516970000431
Figure FDA0002359516970000441
Figure FDA0002359516970000451
Figure FDA0002359516970000461
Figure FDA0002359516970000471
Figure FDA0002359516970000481
Figure FDA0002359516970000491
Figure FDA0002359516970000501
Figure FDA0002359516970000511
Figure FDA0002359516970000521
Figure FDA0002359516970000531
14. use of a compound as claimed in any one of claims 1 to 13 as a light-emitting layer material in an organic electroluminescent device.
15. An organic electroluminescent device comprising a first electrode, a second electrode and one or more organic layers interposed between said first and second electrodes, characterized in that said organic layers comprise at least one compound according to any one of claims 1 to 13.
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