CN111039888A - Compound for organic electroluminescent device and organic electroluminescent device thereof - Google Patents

Compound for organic electroluminescent device and organic electroluminescent device thereof Download PDF

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CN111039888A
CN111039888A CN201911337828.5A CN201911337828A CN111039888A CN 111039888 A CN111039888 A CN 111039888A CN 201911337828 A CN201911337828 A CN 201911337828A CN 111039888 A CN111039888 A CN 111039888A
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CN111039888B (en
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杜明珠
刘辉
赵倩
王英雪
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Changchun Hyperions Technology Co Ltd
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Changchun Haipurunsi Technology Co Ltd
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Abstract

The invention provides a compound for an organic electroluminescent device and the organic electroluminescent device thereof, relating to the technical field of organic photoelectric materials. The compound provided by the invention has high refractive index which can reach 2.00 by introducing two benzoxazole and/or benzothiazole groups into the structure, and can improve the transmittance of the semi-transmission electrode, adjust the light emitting direction and improve the light emitting efficiency when being used as a covering layer material. In addition, the compound provided by the invention optimizes the structure by introducing a specific substituent, improves the glass transition temperature, has excellent stability, and can effectively prolong the service life of a device when being used as a covering layer material of an organic electroluminescent device.

Description

Compound for organic electroluminescent device and organic electroluminescent device thereof
Technical Field
The invention relates to the technical field of organic photoelectric materials, in particular to a compound for an organic electroluminescent device and the organic electroluminescent device.
Background
An Organic Light-Emitting Diode (OLED) is an all-solid-state Light-Emitting device, and has the advantages of high brightness, high contrast, high definition, wide viewing angle, wide color gamut, ultra-thinness, ultra-Light, low power consumption, wide temperature, self-luminescence, high luminous efficiency, short reaction time, transparency, flexibility, and the like, is already commercially available in the fields of mobile phones, televisions, micro displays, and the like, is called as a "illusion display" by the industry, and will become a novel display technology with the greatest development potential in the future.
Since total reflection occurs at the interface of the ITO thin film of the organic light emitting diode and the glass substrate or the interface of the glass substrate and air, only 20% of the emitted light can be utilized, and the remaining 80% of the light is confined inside the device and converted into heat, which may adversely affect the device. In a top emission device, a high refractive index covering layer is usually disposed on the outer side of a semitransparent electrode to adjust the optical interference distance, reduce the total reflection effect of the device, and improve the light extraction efficiency. However, the types of the existing covering layer materials are single, so that the development of a novel covering layer material has important practical application value.
Disclosure of Invention
In view of the above problems in the prior art, the present invention provides a compound for an organic electroluminescent device and an organic electroluminescent device thereof.
The invention provides a compound for an organic electroluminescent device, which has a structure shown as the following formula (I):
Figure BDA0002331450170000011
l is selected from a single bond, and substituted or unsubstituted aryl of C6-C30;
x is O or S;
Ar1～Ar4independently selected from substituted or unsubstituted aryl of C6-C30, or substituted or unsubstituted heteroaryl of C3-C30, or Ar1、Ar2Bonded to the N atom to form a ring, said Ar3、Ar4Bonding with the N atom to form a ring;
m and n are independently selected from 0, 1,2 or 3;
R1、R2independently selected from H, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C30 aryl, or two adjacent R1The radicals being bonded to form a ring structure, or two adjacent R2The groups are bonded to form a ring structure;
when m is greater than 1, each R1Identical or different, when n is greater than 1, each R2The same or different
The invention also provides an organic electroluminescent device which comprises a covering layer, a cathode, an organic layer, an anode and a substrate, wherein the covering layer contains the compound for the organic electroluminescent device.
The invention has the beneficial effects that:
the invention firstly provides a compound for an organic electroluminescent device, which has high refractive index (the refractive index can reach 2.00) by introducing two benzoxazole and/or benzothiazole groups into the structure, and can improve the transmittance of a semi-transparent electrode, adjust the light emitting direction and improve the light emitting efficiency when being used as a covering layer material. In addition, the compound provided by the invention optimizes the structure by introducing a specific substituent, improves the glass transition temperature, has excellent stability, and can effectively prolong the service life of the device when being used as a covering layer material of an organic electroluminescent device.
The present invention also provides an organic electroluminescent device having high luminous efficiency and excellent life performance.
Drawings
FIG. 1 shows the compound prepared in example 1 of the present invention1H NMR chart.
FIG. 2 shows the compound prepared in example 2 of the present invention1H NMR chart.
FIG. 3 shows the compound prepared in example 4 of the present invention1H NMR chart.
FIG. 4 shows the compound prepared in example 6 of the present invention1H NMR chart.
FIG. 5 shows the compound prepared in example 7 of the present invention1H NMR chart.
FIG. 6 shows the compound prepared in example 9 of the present invention1H NMR chart.
FIG. 7 shows a compound prepared in example 11 of the present invention1H NMR chart.
Detailed Description
The following will clearly and completely describe the technical solutions of the specific embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of protection of the present invention.
The invention firstly provides a compound for an organic electroluminescent device, which has a structure shown as the following formula (I):
Figure BDA0002331450170000021
l is selected from a single bond, and substituted or unsubstituted aryl of C6-C30;
x is O or S;
Ar1～Ar4independently selected from substituted or unsubstituted aryl of C6-C30, or substituted or unsubstituted heteroaryl of C3-C30, or Ar1、Ar2Bonded to the N atom to form a ring, said Ar3、Ar4Bonding with the N atom to form a ring;
m and n are independently selected from 0, 1,2 or 3;
R1、R2independently selected from H, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C30 aryl, or two adjacent R1The radicals being bonded to form a ring structure, or two adjacent R2The groups are bonded to form a ring structure;
when m is greater than 1, each R1Identical or different, when n is greater than 1, each R2The same or different.
In the "substituted or unsubstituted" of the present invention, the substituents are independently selected from deuterium atom, cyano group, nitro group, halogen atom, alkyl group of C1 to C10, alkoxy group of C1 to C10, alkylthio group of C1 to C10, aryl group of C6 to C30, aryloxy group of C6 to C30, arylthio group of C6 to C30, heteroaryl group of C3 to C30, silyl group of C1 to C30, alkylamino group of C2 to C10, arylamine group of C6 to C30, or a combination of the above groups, for example: deuterium atom, cyano group, nitro group, halogen, methyl group, ethyl group, propyl group, isopropyl group, tert-butyl group, methoxy group, methylthio group, phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, phenanthryl group, benzophenanthryl group, perylenyl group, pyrenyl group, fluorenyl group, 9-dimethylfluorenyl group, benzyl group, phenoxy group, phenylthio group, dianilino group, dimethylamino group, carbazolyl group, 9-phenylcarbazolyl group, furyl group, thienyl group, triphenylsilyl group, trimethylsilyl group, trifluoromethyl group, phenothiazinyl group, phenoxazinyl group, acridinyl group, pyridyl group, pyrazinyl group, triazinyl group, pyrimidinyl group, etc., but not limited thereto, and the substituent may be a substituent other than those listed above as long as the technical effects of the present invention can be achieved. The substituent may be one or more, and when the substituent is plural, plural substituents may be the same or different.
The alkyl group in the present invention refers to a hydrocarbon group obtained by dropping one hydrogen atom from an alkane molecule, and it may be a straight-chain alkyl group, a branched-chain alkyl group or a cyclic alkyl group, and preferably has 1 to 15 carbon atoms, more preferably 1 to 10 carbon atoms, and particularly preferably 1 to 4 carbon atoms. Examples may include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, cyclopentyl, cyclohexyl, and the like, but are not limited thereto.
The alkoxy group in the present invention means a group in which an alkyl group is bonded to an oxygen atom, i.e., "alkyl-O-" group, wherein the alkyl group is as defined above. Examples may include methoxy, ethoxy, 2-propoxy, 2-cyclohexyloxy, and the like, but are not limited thereto.
Alkylthio in the context of the present invention refers to a group in which an alkyl group is attached to a sulfur atom, i.e., an "alkyl-S-" group, wherein alkyl is as defined above.
The aryl group in the present invention refers to a general term of monovalent group remaining after one hydrogen atom is removed from an aromatic nucleus carbon of an aromatic hydrocarbon molecule, and may be monocyclic aryl group, polycyclic aryl group or condensed ring aryl group, and preferably has 6 to 30 carbon atoms, more preferably 6 to 18 carbon atoms, and particularly preferably 6 to 14 carbon atoms. Examples may include phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, benzophenanthryl, perylenyl, pyrenyl, fluorenyl, benzofluorenyl, dibenzofluorenyl, spirobifluorenyl, and the like, but are not limited thereto.
The aryloxy group in the present invention means a group in which an aryl group is bonded to an oxygen atom, i.e., "aryl-O-" group, wherein the aryl group is as defined above.
Arylthio in the context of the present invention means a radical in which an aryl group is attached to a sulfur atom, i.e. "aryl-S-" groups, where aryl is as defined above.
The heteroaryl group in the present invention refers to a general term of a group in which one or more aromatic core carbons in an aryl group are replaced with a heteroatom including, but not limited to, oxygen, sulfur, nitrogen or silicon atom, preferably having 1 to 25 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 3 to 15 carbon atoms. The heteroaryl group may be a single ring, multiple rings or condensed rings, and examples may include furyl, thienyl, pyridyl, pyrazinyl, pyrimidinyl, phenothiazinyl, phenoxazinyl, benzopyrimidinyl, carbazolyl, triazinyl, benzothiazolyl, benzimidazolyl, dibenzothiophene, dibenzofuran, acridinyl, and the like, but are not limited thereto.
Examples of the silane group in the present invention include, but are not limited to, trimethylsilane, triethylsilane, triphenylsilane, trimethoxysilane, dimethoxyphenylsilane, diphenylmethylsilane, silane, diphenylenesilane, methylcyclobutylsilane, and dimethylfuransilane.
The alkylamino radical in the invention refers to amino-NH2Examples of the general name of the group in which the hydrogen atom is substituted with an alkyl group may include-N (CH)3)2、-N(CH2CH3)2And the like, but are not limited thereto.
The arylamino group in the invention refers to amino-NH2The hydrogen atom in (1) is a general term for a group obtained by substituting an aromatic group, which may be further substituted with the substituent described in the present invention. Examples may include, but are not limited to, the following structures:
Figure BDA0002331450170000041
the bonding to form a ring as described herein means that two groups are linked to each other by a chemical bond. As exemplified below:
Figure BDA0002331450170000042
in the present invention, the ring formed by bonding may be a five-membered ring or a six-membered ring or a fused ring, such as phenyl, naphthyl, cyclopentenyl, cyclopentylalkyl, cyclohexanophenyl, quinolyl, isoquinolyl, dibenzothienyl, phenanthryl or pyrenyl, but not limited thereto.
Preferably, the compound for organic electroluminescent devices represented by formula (I) is represented by any one of the following formulae (I-1) to (I-10):
Figure BDA0002331450170000043
Figure BDA0002331450170000051
in formula (I), L is preferably selected from any one of a single bond, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, and a substituted or unsubstituted naphthyl group.
More preferably, L is selected from a single bond or any of the following groups:
Figure BDA0002331450170000052
preferably, Ar is1～Ar4Independently selected from any one of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl and substituted or unsubstituted fluorenyl.
More preferably, Ar1～Ar4Independently selected from any one of the following groups:
Figure BDA0002331450170000061
preferably, Ar is1、Ar2Bonded to the N atom to form a ring, said Ar3、Ar4Bonded to the N atom to form a ring. Preferably, the compound for the organic electroluminescent device is selected from any one of the following compounds:
Figure BDA0002331450170000062
Figure BDA0002331450170000071
Figure BDA0002331450170000081
Figure BDA0002331450170000091
Figure BDA0002331450170000101
some specific structural forms of the compound for organic electroluminescent devices of the present invention are listed above, but the present invention is not limited to these listed chemical structures, and any substituent group as defined above should be included on the basis of the structure shown in formula (I).
The preparation method of the compound for the organic electroluminescent device can be prepared by a coupling reaction which is conventional in the field, and can be prepared by the following synthetic route, but the invention is not limited to the following steps:
when L is a single bond, the compound (a) and the compound (b) react through Suzuki to obtain an intermediate (A), and the intermediate (A) is reacted with a compound containing Ar1、Ar2、Ar3、Ar4The halide of the group is subjected to Buchwald reaction to obtain the target compound shown in the formula (I). Or, the compound (a) and the compound containing Ar1、Ar2Buchwald reaction of the halogenated compound of the group to obtain an intermediate (A1), reacting the compound (c) with Ar3、Ar4Performing Buchwald reaction on the halogenated compound of the group to obtain an intermediate (A2), performing boration reaction on the intermediate (A1) or the intermediate (A2), and performing Suzuki reaction on the intermediate (A2) or the intermediate (A1) to obtain the target compound shown in the formula (I).
Figure BDA0002331450170000111
When L is not a single bond, the diboride containing L group reacts with the compound (a) and the compound (c) through Suzuki reaction to obtain an intermediate (A3), and the intermediate (A3) is further reacted with the compound containing Ar1、Ar2、Ar3、Ar4The halide of the group is subjected to Buchwald reaction to obtain the target compound shown in the formula (I). Or a compound (a) with Ar1、Ar2Buchwald reaction of the halogenated compound of the group to obtain an intermediate (A1), reacting the compound (c) with Ar3、Ar4Buchwald reaction is carried out on the halogenated matters of the groups to obtain an intermediate (A2), and the intermediate (A1) and the intermediate (A2) are further reacted with diboride containing L groups through Suzuki reaction to obtain the target compound shown in the formula (I).
Figure BDA0002331450170000112
Wherein, the definition of each substituent is as described above, and the description is omitted.
The reaction conditions for the above reactions are not particularly limited in the present invention, and those well known to those skilled in the art may be used. The starting materials used in the above reactions are not particularly limited in the present invention, and may be commercially available products or prepared by methods known to those skilled in the art. The compound provided by the invention has the advantages of few synthesis steps, simple treatment and easiness in industrial production.
The invention also provides an organic electroluminescent device which comprises a covering layer, a cathode, an organic layer, an anode and a substrate, wherein the covering layer contains the compound for the organic electroluminescent device.
Regarding the organic electroluminescent device of the present invention, the organic layers may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, however, the structure of the organic electroluminescent device of the present invention is not limited by the above structure, and a plurality of organic layers may be omitted or provided at the same time, if necessary. For example, an electron blocking layer may be further provided between the hole transport layer and the light emitting layer, and a hole blocking layer may be further provided between the electron transport layer and the light emitting layer; organic layers having the same function may also be made into a stacked structure of 2 or more layers, for example, the hole transport layer may further include a first hole transport layer and a second hole transport layer, and the electron transport layer may further include a first electron transport layer and a second electron transport layer.
With regard to the organic electroluminescent device of the present invention, any material used for the layer as in the prior art can be used for the other layers except that the covering layer contains the compound for organic electroluminescent devices shown in (I).
As the anode of the organic electroluminescent device of the present invention, a material having a large work function can be used, and examples thereof include: metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides, e.g. zinc oxide, indium oxideIndium Tin Oxide (ITO) and Indium Zinc Oxide (IZO); combinations of metals with oxides, e.g. ZnO: Al or SnO2Sb; conductive polymers, e.g. poly (3-methyl compounds), poly [3,4- (ethylene-1, 2-dioxy) compounds](PEDOT), polypyrrole, polyaniline, and the like, but are not limited thereto.
As the cathode of the organic electroluminescent device of the present invention, a material having a small work function can be used, and examples thereof include: metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, or alloys thereof; materials of multilayer construction, e.g. LiF/Al or LiO2Al, etc., but are not limited thereto.
The hole transport layer of the organic electroluminescent device of the present invention is required to have a suitable ion potential and a high hole mobility, and an organic material based on arylamine, a conductive polymer, a block copolymer having both a conjugated portion and a non-conjugated portion, and the like can be used, but the present invention is not limited thereto. Examples thereof include: 4,4' -bis [ N- (1-naphthyl) -N-phenylamino ] biphenyl (NPB), 4,4, 4' -tris (N-carbazolyl) triphenylamine (TCTA), N ' -bis (3-methylphenyl) -N, N ' -diphenyl- [1, 1-biphenyl ] -4,4' -diamine (TPD), N ' -bis (naphthalen-1-yl) -N, N ' -diphenylbenzidine (a-NPD), and the like.
As for the light emitting layer of the organic electroluminescent device of the present invention, a red light emitting material, a green light emitting material, or a blue light emitting material can be used as the light emitting material, and two or more light emitting materials can be mixed if necessary. The light-emitting material may be a host material alone or a mixture of a host material and a dopant material, and the light-emitting layer is preferably formed using a mixture of a host material and a dopant material.
The electron transport layer of the organic electroluminescent device of the present invention is required to be a substance which has a high electron affinity, can efficiently transport electrons, and is less likely to generate impurities which become traps during production and use. The electron-transporting material used in the electron-transporting layer is not particularly limited, and (1) metal complexes such as aluminum complexes, beryllium complexes, and zinc complexes, (2) imidazole derivatives, benzimidazole derivatives, and phenanthroline derivatives can be usedAnd (3) a polymer compound, but not limited thereto. Examples thereof include: tris (8-hydroxyquinoline) aluminum (Alq)3) Phenanthroline derivatives such as 1,3, 5-tris (1-naphthyl-1H-benzimidazol-2-yl) benzene (TPBI) and 4, 7-diphenyl-1, 10-phenanthroline (BPhen).
The electron injection layer of the organic electroluminescent device of the present invention is mainly used for improving the efficiency of injecting electrons from the cathode into the electron transport layer and the light-emitting layer, and is required to have the ability to transport electrons, and an alkali metal salt such as lithium fluoride and cesium fluoride, an alkaline earth metal salt such as magnesium fluoride, a metal oxide such as aluminum oxide, or the like can be used.
Preferably, the capping layer includes a first capping layer containing the compound for organic electroluminescent device and a second capping layer containing a compound represented by the following formula (II):
Figure BDA0002331450170000121
wherein Ar is5-Ar8Each independently selected from any one of substituted or unsubstituted C6-C30 aryl.
Preferably, Ar is5-Ar8Each independently selected from any one of the following groups:
Figure BDA0002331450170000131
preferably, the compound represented by formula (II) is selected from any one of the following structures:
Figure BDA0002331450170000132
preferably, the organic layer includes a hole transport layer including a first hole transport layer containing a compound represented by the following formula (III) and a second hole transport layer containing a compound represented by the following formula (IV):
Figure BDA0002331450170000133
wherein Ar is9-Ar12Each independently selected from a substituted or unsubstituted C6-C30 aryl group or a substituted or unsubstituted C3-C30 heteroaryl group, and Ar9-Ar12At least one of which is a group of the formula (V), L4Selected from single bond or substituted or unsubstituted aryl of C6-C30, p is 1,2 or 3, q is 0, 1,2, 3 or 4, R3、R4Independently selected from H, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C30 aryl, or two adjacent R4The groups are bonded to form a ring structure, and when q is greater than 1, each R4The same or different;
Ar13-Ar15each independently selected from a substituted or unsubstituted C6-C30 aryl group or a substituted or unsubstituted C3-C30 heteroaryl group, and Ar13-Ar15At least one of which is a group of the formula (VI), L5Selected from single bond or substituted or unsubstituted aryl of C6-C30, R is 0, 1,2, 3 or 4, R5Selected from H, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C30 aryl, or two adjacent R5The groups are bonded to form a ring structure, and when R is greater than 1, each R5The same or different.
Preferably, the group of formula (V) is selected from any one of the following groups:
Figure BDA0002331450170000141
by way of example, the compound of formula (III) may be selected from any of the following structures:
Figure BDA0002331450170000142
Figure BDA0002331450170000151
preferably, the group of formula (VI) is selected from any one of the following groups:
Figure BDA0002331450170000152
by way of example, the compound of formula (IV) may be selected from any of the following structures:
Figure BDA0002331450170000153
Figure BDA0002331450170000161
the present invention is not particularly limited to the thickness of each organic layer of the organic electroluminescent device, and may be any thickness commonly used in the art.
The hole transport layer of the organic electroluminescent device adopts a double-layer structure and a specific structure, and generates a synergistic effect with the covering layer, so that the luminous efficiency of the device is effectively improved.
The organic electroluminescent device can be prepared by various methods such as solution coating such as spin coating and ink-jet printing or vacuum evaporation.
The raw materials used in the following examples are not particularly limited in their source, and may be commercially available products or prepared by methods known to those skilled in the art.
The mass spectrum used by the compound of the invention uses AXIMA-CFRplus matrix assisted laser desorption ionization flight mass spectrometer of Kratos Analytical company of Shimadzu corporation, and chloroform is used as a solvent;
elemental analysis using a Vario EL cube type organic element analyzer of Elementar corporation, Germany, the sample mass was 5 mg;
nuclear magnetic resonance (1HNMR) Using a Bruker-510 type nuclear magnetic resonance spectrometer (Bruker, Germany), 600MHz, CDCl3As solvent, TMS as internal standard.
Example 1: preparation of Compound 2
Figure BDA0002331450170000171
Under the protection of nitrogen, compound a-1(7.53g, 35.35mmol), compound b-1(6.23g, 35mmol), and K were added to a reaction flask2CO3(14.51g, 105mmol), 300mL of toluene solvent was stirred. Adding catalyst Pd (PPh)3)4(0.40g, 0.35mmol), 60mL of distilled water, the temperature was raised to reflux and the reaction was stirred for 10 h. After the reaction was completed, 80mL of distilled water was added to terminate the reaction. Filtration under reduced pressure gave a crude intermediate A-1, which was washed three times with distilled water and then recrystallized from toluene, ethanol (10: 1) to give 6.90g of the title compound A-1 in 74% yield.
Intermediate A-1(5.85g, 22mmol), 4-bromobiphenyl (20.72g, 88.90mmol) and sodium tert-butoxide (4.81g, 50mmol) were dissolved in 200ml of dehydrated toluene under nitrogen protection, and a toluene solution of palladium acetate (0.07g, 0.33mmol) and tri-tert-butylphosphine (0.24g, 1.32mmol) was added with stirring and the mixture was refluxed for 8 hours. After cooling, the mixture was filtered through a celite/silica gel funnel, the organic solvent was removed from the filtrate by distillation under reduced pressure, and the concentrated solution was recrystallized from toluene and ethanol (12: 1), followed by filtration to obtain (12.13g, 13.86mmol) of compound 2 in 63% yield.
Mass spectrum m/z: 874.42 (calculated value: 874.33). Theoretical element content (%) C62H42N4O2: c, 85.10; h, 4.84; n, 6.40; and O, 3.66. Measured elemental content (%): c, 85.17; h, 4.85; n, 6.42; and O, 3.68.1H NMR(600MHz, CDCl3): δ 7.85(s, 2H),7.75(d,2H),7.72-7.70(m,2H),7.59(dd,8H),7.54-7.51(m,4H), 7.50-7.48 (m,4H),7.44(t,8H),7.35-7.31(m,4H),7.30-7.26(m, 8H). FIG. 1 shows the compound obtained in example 1 of the present invention1H NMR chart. The above results confirmed that the obtained product was the objective product.
Example 2: preparation of Compound 4
Figure BDA0002331450170000172
Compound a-1(43.0g, 202mmol), iodobenzene (22.25ml, 200mmol), and sodium tert-butoxide (38.45g, 400mmol) were dissolved in 1800ml of dehydrated toluene under nitrogen, and a solution of palladium acetate (0.45g, 2mmol) and tri-tert-butylphosphine (1.6g, 8mmol) in toluene was added with stirring and the mixture was refluxed for 8 hours. After cooling, filtration through a celite/silica funnel, the organic solvent was removed from the filtrate by distillation under reduced pressure, the concentrate was recrystallized from toluene and ethanol (10: 1), and filtration gave (45.1g, 156mmol) of intermediate B-1 in 78% yield.
Intermediate B-1(40.5g, 140mmol), 1-iodonaphthalene (20.6ml, 141mmol) and sodium tert-butoxide (40.35g, 420mmol) were dissolved in 1500ml of dehydrated toluene under nitrogen protection, and a solution of palladium acetate (0.30g, 1.4mmol) and tri-tert-butylphosphine (1.15g, 5.6mmol) in toluene was added with stirring and the mixture was refluxed for 8 hours. After cooling, filtration through a celite/silica funnel, the organic solvent was removed from the filtrate by distillation under reduced pressure, the concentrate was recrystallized from toluene and ethanol (13: 1), and filtration gave (37.8g, 91mmol) of intermediate C-1 in 65% yield.
Intermediate C-1(20.75g, 50mmol) was dissolved in DMSO and diborane pinacol ester (14.5g, 55mmol), KOAc (14.7g, 150mmol), Pd (dppf) Cl was added2(0.55g, 0.75mmol), nitrogen substitution three times, at 80 degrees C under 6h reaction. After completion of the reaction, the reaction solution was extracted with toluene, dried over anhydrous sodium sulfate, and the crude product was passed through a silica gel column to obtain intermediate D-1(13.3g, 35mmol) in a yield of 70%.
Under the protection of nitrogen, intermediate C-1(12.58g, 30.30mmol), intermediate D-1(11.41g, 30mmol), and K were added to a reaction flask2CO3(13.82g, 100mmol), 300mL of toluene solvent was stirred. Adding catalyst Pd (PPh)3)4(0.35g, 0.30mmol), 70mL of distilled water, the temperature was raised to reflux and the reaction was stirred for 10 h. After the reaction was completed, 80mL of distilled water was added to terminate the reaction. Filtration under reduced pressure gave crude compound 4, which was washed three times with distilled water and then recrystallized from toluene, ethanol (10: 1) to give 14.29g of the title compound 4 in 71% yield.
Mass spectrum m/z: 670.36(Calculated values: 670.24). Theoretical element content (%) C46H30N4O2: c, 82.37; h, 4.51; n, 8.35; o, 4.77. Measured elemental content (%): c, 82.49; h, 4.52; n, 8.39; o, 4.79.1H NMR(600MHz, CDCl3): δ 8.39-8.35(m,1H),8.30(dd,1H),7.95-7.92(m,2H),7.78-7.75(m,2H),7.74-7.70(m, 2H),7.66(d,1H),7.65-7.60(m,3H),7.59-7.54(m,3H),7.52(dd,1H),7.45-7.43(m,2H), 7.28-7.20(m,6H),7.12-7.06(m,4H),7.01-6.99(m, 2H). FIG. 2 shows the compound prepared in example 2 of the present invention1H NMR chart. The above results confirmed that the obtained product was the objective product.
Example 3: preparation of Compound 18
Figure BDA0002331450170000181
Synthesis of intermediate B-1 and intermediate C-2 was carried out in the same manner as in example 2 except that 1-iodonaphthalene in example 2 was replaced with 4-iodobiphenyl.
Under nitrogen protection, intermediate C-2(26.74g, 60.60mmol), D-2(4.97g, 30mmol), K was added to the reaction flask2CO3(12.44g, 90mmol), 300mL of toluene solvent was stirred. Adding catalyst Pd (PPh)3)4(0.35g, 0.30mmol), 70mL of distilled water, the temperature was raised to reflux and the reaction was stirred for 10 h. After the reaction was completed, 80mL of distilled water was added to terminate the reaction. Filtration under reduced pressure gave crude compound 18, which was washed three times with distilled water and then recrystallized from toluene, ethanol (10: 1) to give 17.25g of the title compound 18 in 72% yield.
Mass spectrum m/z: 798.44 (calculated value: 798.30). Theoretical element content (%) C56H38N4O2: c, 84.19; h, 4.79; n, 7.01; and O, 4.01. Measured elemental content (%): c, 84.31; h, 4.80; n, 7.04; and O, 4.01. The above results confirmed that the obtained product was the objective product.
Example 4: preparation of Compound 37
Figure BDA0002331450170000191
Compound 37 can be obtained by replacing 1-iodonaphthalene with an equimolar amount of the group b-2 and carrying out the same procedures as in example 2. Mass spectrum m/z: 954.54 (calculated value: 954.39). Theoretical element content (%) C68H50N4O2: c, 85.51; h, 5.28; n, 5.87; and O, 3.35. Measured elemental content (%): c, 85.60; h, 5.29; n, 5.89; and O, 3.36.1H NMR(600MHz,CDCl3): δ 7.98(dd,2H),7.96(d,2H),7.84(dd,2H),7.84-7.80(m,4H),7.76-7.68(m,4H), 7.64-7.61(m,2H),7.55-7.53(m,4H),7.50(d,2H),7.47-7.42(m,2H),7.31-7.24(m,8H),7.11-7.07 (m,4H),7.00(d,2H),1.68(s, 12H). FIG. 3 shows the compound prepared in example 4 of the present invention1H NMR chart. The above results confirmed that the obtained product was the objective product.
Example 5: preparation of Compound 38
Compound 38 was obtained by substituting iodobenzene for equimolar 4-iodobiphenyl and 1-iodonaphthalene for equimolar 2-iodo-9, 9-dimethylfluorene, and the other steps were the same as in example 2. Mass spectrum m/z: 954.52 (calculated value: 954.39). Theoretical element content (%) C68H50N4O2: c, 85.51; h, 5.28; n, 5.87; and O, 3.35. Measured elemental content (%): c, 85.62; h, 5.26; n, 5.90; and O, 3.35. The above results confirmed that the obtained product was the objective product.
Example 6: preparation of Compound 40
Compound 40 was obtained by replacing 4-iodobiphenyl with an equimolar amount of 2-iodo-9, 9-dimethylfluorene and the same procedures as in example 3. Mass spectrum m/z: 878.49 (calculated value: 878.36). Theoretical element content (%) C62H46N4O2: c, 84.71; h, 5.27; n, 6.37; and O, 3.64. Measured elemental content (%): c, 84.79; h, 5.28; n, 6.40; and O, 3.65.1HNMR(600 MHz,CDCl3): δ 8.10(d,1H),7.91(s,4H),7.85-7.79(m,4H),7.79-7.74(m,2H),7.72(dd,2H), 7.70(d,1H),7.63-7.61(m,2H),7.53(dd,2H),7.44(dd,2H),7.33(d,2H),7.29(t,2H),7.25(t,2H), 7.16(dd,2H),7.11-7.07(m,4H),7.03-6.98(m,2H),1.71(s, 12H). FIG. 4 shows the compound prepared in example 6 of the present invention1H NMR chart. The above results confirmed that the obtained product was the objective product.
Example 7: preparation of Compound 55
Figure RE-GDA0002380990600000201
Compound 55 was obtained by replacing a-1 with an equimolar amount of a-2, 1-iodonaphthalene and an equimolar amount of 4-iodobiphenyl, and the other steps were carried out in the same manner as in example 2. Mass spectrum m/z: 754.31 (calculated value: 754.22). Theoretical element content (%) C50H34N4S2: c, 79.55; h, 4.54; n, 7.42; s, 8.49. Measured elemental content (%): c, 79.64; h, 4.56; n, 7.44; s, 8.53.1H NMR(600MHz,CDCl3): δ 8.27(t,2H),7.86(dd,2H),7.80-7.78(m,2H),7.59(dd,4H), 7.54-7.50(m,2H),7.49-7.41(m,6H),7.35-7.31(m,2H),7.31-7.26(m,6H),7.24(t,2H), 7.12-7.07 (m,4H),7.03-6.97(m, 2H). FIG. 5 shows the compound prepared in example 7 of the present invention1HNMR map. The above results confirmed that the obtained product was the objective product.
Example 8: preparation of Compound 63
Figure RE-GDA0002380990600000202
Compound a-2(13.75g, 60mmol), 4-iodobiphenyl (33.95g, 121.2mmol), and sodium tert-butoxide (11.53g, 120mmol) were dissolved in 400ml of dehydrated toluene under nitrogen protection, and a toluene solution of palladium acetate (0.14g, 0.6mmol) and tri-tert-butylphosphine (0.49g, 2.4mmol) was added with stirring, and the mixture was refluxed for 8 hours. After cooling, the mixture was filtered through a celite/silica funnel, the organic solvent was removed from the filtrate by distillation under reduced pressure, the concentrated solution was recrystallized from toluene and ethanol (10: 1), and the intermediate C-3 (24.00g, 45mmol) was obtained by filtration in 75% yield.
Under nitrogen protection, intermediate C-3(21.55g, 40.4mmol), D-2(3.32g, 20mmol), K were added to a reaction flask2CO3(8.29g, 60mmol), 300mL of toluene solvent was stirred. Adding catalyst Pd (PPh)3)4(023g, 0.20mmol), 80mL of distilled water, temperature was raised to reflux and the reaction stirred for 10 h. After the reaction was completed, 80mL of distilled water was added to terminate the reaction. Filtration under reduced pressure gave crude compound 63, which was washed three times with distilled water and then recrystallized from toluene, ethanol (12: 1) to give 13.18g of the aimed compound 63 in 67% yield.
Mass spectrum m/z: 982.46 (calculated value: 982.32). Theoretical element content (%) C68H46N4S2: c, 83.06; h, 4.72; n, 5.70; s, 6.52. Measured elemental content (%): c, 83.18; h, 4.73; n, 5.74; s, 6.51. The above results confirmed that the obtained product was the target product.
Example 9: preparation of Compound 71
Compound 71 was obtained by substituting 4-iodobiphenyl for an equimolar amount of iodobenzene and D-2 for an equimolar amount of 1, 4-naphthalenediboronic acid, and the other steps were the same as in example 8. Mass spectrum m/z: 728.35 (calculated value: 728.21). Theoretical element content (%) C48H32N4S2: c, 79.09; h, 4.43; n, 7.69; and S, 8.80. Measured elemental content (%): c, 79.18; h, 4.43; n, 7.71; and S, 8.83.1H NMR(600MHz,CDCl3): Δ 8.36(d,1H),8.25-8.18(m,4H),7.87(d,1H),7.81 (dd,1H),7.77(dd,1H),7.68(s,2H),7.48-7.41(m,2H),7.30-7.26(m,4H),7.24-7.20(m,4H), 7.11-7.07(m,8H),7.01-6.98(m, 4H). FIG. 6 shows the compound prepared in example 9 of the present invention1H NMR chart. The above results confirmed that the obtained product was the objective product.
Example 10: preparation of Compound 97
Figure RE-GDA0002380990600000211
Compound 97 can be obtained by replacing a-1 with an equimolar amount of a-3 and carrying out the same procedures as in example 1. Mass spectrum m/z: 906.42 (calculated value: 906.29). Theoretical element content (%) C62H42N4S2: c, 82.09; h, 4.67; n, 6.18; and S, 7.07. Measured elemental content (%): c, 82.18; h, 4.66; n, 6.20; and S, 7.08. The above results confirmed that the obtained product was the objective productAnd (5) preparing the product.
Example 11: preparation of Compound 100
Figure RE-GDA0002380990600000212
Compound 100 can be obtained by replacing a-2 with an equimolar amount of a-3, 4-iodobiphenyl with an equimolar amount of iodobenzene and performing the same procedures as in example 8. Mass spectrum m/z: 678.27 (calculated value: 678.19). Theoretical element content (%) C44H30N4S2: c, 77.85; h, 4.45; n, 8.25; and S, 9.45. Measured elemental content (%): c, 77.93; h, 4.44; n, 8.26; and S, 9.46.1H NMR(600MHz,CDCl3): δ 8.36(d,1H),8.25(d,1H),8.16(d,1H),7.94-7.88(m,4H), 7.85-7.79(m,2H),7.70(dd,1H),7.27(q,4H),7.23-7.20(m,4H),7.12-7.06(m,8H),7.01-6.98(m, 4H). FIG. 7 shows a compound prepared in example 11 of the present invention1H NMR chart. The above results confirmed that the obtained product was the objective product.
Example 12: preparation of Compound 103
Figure RE-GDA0002380990600000221
Compound 103 can be obtained by replacing a-1 with an equimolar amount of a-3 and carrying out the same procedures as in example 6. Mass spectrum m/z: 910.46 (calculated value: 910.32). Theoretical element content (%) C62H46N4S2: c, 81.73; h, 5.09; n, 6.15; and S, 7.04. Measured elemental content (%): c, 81.80; h, 5.10; n, 6.16; and S, 7.06. The above results confirmed that the obtained product was the objective product.
Example 13: measurement of refractive index
The measuring instrument is an M-2000 spectroscopic ellipsometer of J.A.Woollam, USA; the scanning range of the instrument is 245-1000 nm; the size of the glass substrate is 200 x 200mm, and the thickness of the material film is 60 nm. The results of measuring the refractive index at 620nm are shown in Table 1 below.
Refractive index (n) of the Compounds of Table 1
Compound (I) Refractive index (620nm)
Compound 2 1.97
Compound 4 1.95
Compound 18 1.98
Compound 37 1.92
Compound 38 1.95
Compound 40 1.97
Compound 55 1.95
Compound 63 2.00
Compound 71 1.92
Compound 97 1.96
Compound 100 1.99
Compound 103 1.98
Application examples 1 to 10: preparation of light emitting devices 1-10
Firstly, a cavity injection layer 2T-NATA/25nm, a cavity transport layer HT1/70nm and a cavity transport layer HT2/10nm are evaporated on an ITO (10nm)/Ag (100nm)/ITO (10nm) layer formed on an organic substrate layer by layer, and an emission layer is evaporated to be a main body BH: doping BD 7%/30 nm, evaporating an electron transport layer TPBI/40nm, evaporating an electron injection layer LiF/0.5nm, evaporating Mg/Ag with the thickness of 20nm to form a cathode, and finally evaporating the compound shown in the formula (I) of the invention with the thickness of 60nm in vacuum to form a covering layer.
Application examples 11 to 15: preparation of light emitting devices 11-15
Firstly, a cavity injection layer 2T-NATA/25nm, a cavity transport layer HT1/70nm and a cavity transport layer HT2/10nm are evaporated on an ITO (10nm)/Ag (100nm)/ITO (10nm) layer formed on an organic substrate layer by layer, and an emission layer is evaporated to be a main body BH: doping BD 7%/30 nm, evaporating an electron transport layer TPBI/40nm, evaporating an electron injection layer LiF/0.5nm, evaporating Mg/Ag with the thickness of 20nm to form a cathode, and finally evaporating the compound shown in the formula (I) of the invention with the thickness of 40nm in vacuum to form a first covering layer and evaporating the compound shown in the formula (II) with the thickness of 20nm in vacuum to form a second covering layer.
Comparative examples 16 to 17: preparation of light emitting devices 16-17
The difference from application examples 1-10 is that the coating layers are compounds CP-1, CP-2.
In the invention, the preparation of the device is completed by adopting a vacuum evaporation system and continuously evaporating under the vacuum uninterrupted condition. The materials are respectively arranged in different evaporation source quartz crucibles, and the temperatures of the evaporation sources can be independently controlled. The thermal evaporation rate of the organic material or the doped precursor organic material is generally set to 01nm/s, the evaporation rate of the doping material is adjusted according to the doping ratio; the evaporation rate of the electrode metal is 0.4-0.6 nm/s. Placing the processed glass substrate into an OLED vacuum coating machine, wherein the vacuum degree of the system should be maintained at 5 x 10 in the film manufacturing process-5And (3) evaporating an organic layer and a metal electrode respectively by replacing a mask plate under Pa, detecting the evaporation speed by using an inficon SQM160 quartz crystal film thickness detector, and detecting the thickness of the thin film by using a quartz crystal oscillator. A combined IVL test system is formed by test software, a computer, a K2400 digital source meter manufactured by Keithley of the United states and a PR788 spectral scanning luminance meter manufactured by Photo Research of the United states to test the driving voltage, the luminous efficiency and the CIE color coordinate of the organic electroluminescent device. The lifetime was measured using the M6000OLED lifetime test system from McScience. The environment of the test is atmospheric environment, and the temperature is room temperature.
The compounds involved in the application examples and comparative examples of the present invention are as follows:
Figure RE-GDA0002380990600000231
the luminous performance of the organic electroluminescent device prepared by the embodiment of the invention is shown in the following table 2:
table 2 test data of light emitting property of organic electroluminescent device
Figure RE-GDA0002380990600000241
The results show that the compound of the invention is used as a covering layer and applied to an organic electroluminescent device, can improve the luminous efficiency and the service life of the device, and is an organic luminescent material with excellent performance.
It is obvious that the above description of the embodiments is only intended to assist the understanding of the method of the invention and its core ideas. It should be noted that those skilled in the art can make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the protection scope of the present invention.

Claims (10)

1. A compound for an organic electroluminescent element, characterized by having a structure represented by the following formula (I):
Figure FDA0002331450160000011
l is selected from a single bond, and substituted or unsubstituted aryl of C6-C30;
x is O or S;
Ar1～Ar4independently selected from substituted or unsubstituted aryl of C6-C30, or substituted or unsubstituted heteroaryl of C3-C30, or Ar1、Ar2Bonded to the N atom to form a ring, said Ar3、Ar4Bonding with the N atom to form a ring;
m and n are independently selected from 0, 1,2 or 3;
R1、R2independently selected from H, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C30 aryl, or two adjacent R1The radicals being bonded to form a ring structure, or two adjacent R2The groups are bonded to form a ring structure;
when m is greater than 1, each R1Identical or different, when n is greater than 1, each R2The same or different.
2. The compound according to claim 1, wherein L is any one selected from a single bond, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, and a substituted or unsubstituted naphthyl group.
3. The compound for an organic electroluminescent element according to claim 1, wherein L is selected from a single bond and any one of the following groups:
Figure FDA0002331450160000012
4. the compound according to claim 1, wherein Ar is Ar1～Ar4Independently selected from any one of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl and substituted or unsubstituted fluorenyl, or Ar1、Ar2Bonded to the N atom to form a ring, said Ar3、Ar4Bonded to the N atom to form a ring.
5. The compound according to claim 1, wherein Ar is Ar1～Ar4Independently selected from any one of the following groups, or Ar1、Ar2Bonded to the N atom to form a ring, said Ar3、Ar4Bonding with the existing N atom to form a ring:
Figure FDA0002331450160000021
6. the compound according to claim 1, wherein the compound is selected from any one of the following compounds:
Figure FDA0002331450160000022
Figure FDA0002331450160000031
Figure FDA0002331450160000041
Figure FDA0002331450160000051
Figure FDA0002331450160000061
7. an organic electroluminescent element comprising a coating layer, a cathode, an organic layer, an anode and a substrate, wherein the coating layer contains the compound for organic electroluminescent element as claimed in any one of claims 1 to 6.
8. The organic electroluminescent device according to claim 7, wherein the capping layer comprises a first capping layer containing the compound for organic electroluminescent device according to any one of claims 1 to 6 and a second capping layer containing a compound represented by the following formula (II):
Figure FDA0002331450160000071
wherein Ar is5-Ar8Each independently selected from any one of substituted or unsubstituted C6-C30 aryl.
9. The organic electroluminescent device according to claim 8, wherein the compound of formula (II) is selected from any one of the following structures:
Figure FDA0002331450160000072
10. the organic electroluminescent device according to claim 7, wherein the organic layer comprises a hole transport layer comprising a first hole transport layer containing a compound represented by the following formula (III) and a second hole transport layer containing a compound represented by the following formula (IV):
Figure FDA0002331450160000073
Figure FDA0002331450160000081
wherein Ar is9-Ar12Each independently selected from a substituted or unsubstituted C6-C30 aryl group or a substituted or unsubstituted C3-C30 heteroaryl group, and Ar9-Ar12At least one of which is a group of the formula (V), L4Selected from single bond or substituted or unsubstituted aryl of C6-C30, p is 1,2 or 3, q is 0, 1,2, 3 or 4, R3、R4Independently selected from H, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C30 aryl, or two adjacent R4The groups are bonded to form a ring structure, and when q is greater than 1, each R4The same or different;
Ar13-Ar15each independently selected from a substituted or unsubstituted C6-C30 aryl group or a substituted or unsubstituted C3-C30 heteroaryl group, and Ar13-Ar15At least one of which is a group of the formula (VI), L5Selected from single bond or substituted or unsubstituted aryl of C6-C30, R is 0, 1,2, 3 or 4, R5Selected from H, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C30 aryl, or two adjacent R5The groups are bonded to form a ring structure, and when R is greater than 1, each R5The same or different.
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