CN110746412A - Diphenyl pyrimidine compound substituted by 9, 9-spirobifluorene and organic electroluminescent assembly thereof - Google Patents

Diphenyl pyrimidine compound substituted by 9, 9-spirobifluorene and organic electroluminescent assembly thereof Download PDF

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CN110746412A
CN110746412A CN201810816658.8A CN201810816658A CN110746412A CN 110746412 A CN110746412 A CN 110746412A CN 201810816658 A CN201810816658 A CN 201810816658A CN 110746412 A CN110746412 A CN 110746412A
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spirobifluorene
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黄贺隆
赵登志
徐伯伟
赖振昌
殷力嘉
张敏忠
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E Ray Optoelectronics Technology Co Ltd
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Abstract

The invention relates to a diphenyl pyrimidine compound substituted by 9, 9-spirobifluorene and an organic motor luminescent component using the same, wherein the compound is represented by the following formula (I), X1、A1And n is as defined in the specification;
Figure DDA0001740480660000011

Description

Diphenyl pyrimidine compound substituted by 9, 9-spirobifluorene and organic electroluminescent assembly thereof
Technical Field
The invention relates to a diphenyl pyrimidine compound substituted by 9, 9-spirobifluorene and an organic electroluminescent component using the same.
Background
Organic light emission is a method of converting electric energy into light energy using an organic material, and since an organic light emitting device has advantages of self-luminescence, long life, saturated color, wide color gamut, high efficiency, low driving voltage, low cost, etc. in the application of a display, it has attracted attention, and in order to apply the organic electroluminescent device to various fields and fields, various fields, in particular, development and research of novel organic materials are in progress.
The OLED assembly has at least one organic layer between an anode and a cathode. When a voltage is applied, holes and electrons are injected from the anode and cathode, respectively, into the one or more organic layers, and the injected holes and electrons migrate, respectively, to the oppositely charged electrode. When electrons and holes are confined to the same molecule, they recombine to form an "exciton" (exiton), which is a localized electron-hole pair in an excited state, and when returning from the excited state to the ground state, releases energy in the form of light or heat. In order to improve the charge transport capability and the light emitting efficiency of the device, besides using appropriate electron and hole transport/injection materials or improving the transport/injection materials, it is also possible to provide an improved structure of the organic electroluminescent device, such as an electron transport layer and/or a hole transport layer, or an electron blocking layer and/or a hole blocking layer laminated on the light emitting layer. In addition, by doping a guest material in the host material, the light emitting efficiency can be improved and the chromaticity can be adjusted. Several OLED materials and device configurations are described in U.S. patent nos. 4769292, 5844363, 5707745, 6596415, and 6465115, which are incorporated herein by reference in their entirety. Yi radium photoelectric technology has been applied in 2016 and proved in 2017 to be taiwan patent No. I582081, which shows certain novelty and effect of the electron transport material.
Since mobility (mobility) of holes and electrons in organic materials is different, OLED devices with multi-layer thin film structure have been developed to avoid quenching phenomenon in which recombination regions of holes and electrons are close to electrodes. As described above, since the mobility of electrons and holes is different in the organic material, if appropriate hole transport and electron transport layers are used, holes and electrons can be efficiently transported to the light emitting layer, the density of the electrons and holes in the light emitting layer is balanced, the recombination rate of the electrons and holes is increased, and the light emitting efficiency is further increased. In addition, the efficiency and lifetime of the device can be improved by appropriate combinations of the above organic layers. However, it has been difficult to find organic materials that meet the requirements of all practical display applications, especially for use in automotive displays or illumination sources, which have high temperature resistance and long lifetime characteristics.
Therefore, an organic material with significantly improved lifetime, light-emitting efficiency and heat resistance is needed to meet the requirement of diversified applications.
Disclosure of Invention
The invention aims to provide an organic material with long service life, good luminous efficiency and good heat resistance.
The invention provides a diphenyl pyrimidine compound substituted by 9, 9-spirobifluorene, which is represented by the following formula (I),
Figure BDA0001740480640000021
wherein, X1Represents a substituted or unsubstituted (C6-C30) aryl, a substituted or unsubstituted (5-to 30-membered) heteroaryl;
A1represents a substituted or unsubstituted (C6-C30) aryl, a substituted or unsubstituted (5-to 30-membered) heteroaryl;
X1and A1Are the same or(ii) is different and at least one is a substituted or unsubstituted (5-to 30-membered) heteroaryl;
n represents an integer of 1 or 2, and when n represents 2, A1Each of which may be the same or different.
In another aspect, the present invention provides an organic electroluminescent device, comprising:
a cathode;
an anode; and
organic layer: between the cathode and the anode, the diphenyl pyrimidine compound which is represented by the formula (I) and is substituted by 9, 9-spirobifluorene is contained.
The diphenyl pyrimidine compound which is represented by the formula (I) and is substituted by 9, 9-spirobifluorene can provide an organic material which has long service life, good luminous efficiency and good heat resistance, can meet the requirements of practical application of a display, and is particularly suitable to be used as a vehicle display or an OLED (organic light emitting diode) lighting source.
Drawings
FIG. 1 is a cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.
FIG. 2 is a cross-sectional view of another embodiment of an OLED device according to the present invention.
FIG. 3 is a cross-sectional view of another embodiment of an OLED device according to the present invention.
Detailed Description
The following description of the embodiments of the present invention is provided by way of specific examples, and the advantages and effects of the present invention will be readily apparent to those skilled in the art from the disclosure of the present specification. The invention is capable of other and different embodiments and its several details are capable of modification and various other changes in the details are capable of being made without departing from the spirit and scope of the present disclosure. Moreover, all ranges and values herein are inclusive and combinable. Any number or point within the ranges set forth herein, e.g., any integer, may be treated as the minimum or maximum value to derive a lower range, etc.
The diphenyl pyrimidine compound substituted by 9, 9-spirobifluorene is shown in the following formula (I),
Figure BDA0001740480640000031
wherein, X1Represents a substituted or unsubstituted (C6-C30) aryl, a substituted or unsubstituted (5-to 30-membered) heteroaryl;
A1represents a substituted or unsubstituted (C6-C30) aryl, a substituted or unsubstituted (5-to 30-membered) heteroaryl;
X1and A1Are the same or different and at least one is a substituted or unsubstituted (5-to 30-membered) heteroaryl;
n represents an integer of 1 or 2, and when n represents 2, A1Each of which may be the same or different.
In one embodiment, the 9, 9-spirobifluorene-substituted diphenylpyrimidine compound represented by the formula (I) is represented by the following formula (I-1), formula (I-2) or formula (I-3):
Figure BDA0001740480640000041
wherein, X1Represents a substituted or unsubstituted (C6-C30) aryl, a substituted or unsubstituted (5-to 30-membered) heteroaryl;
A1represents a substituted or unsubstituted (C6-C30) aryl, a substituted or unsubstituted (5-to 30-membered) heteroaryl;
X1and A1Are the same or different and at least one is a substituted or unsubstituted (5-to 30-membered) heteroaryl;
n represents an integer of 1 or 2, and when n represents 2, A1Each of which may be the same or different.
The invention relates to a of diphenyl pyrimidine compound which is represented by formula (I) and substituted by 9, 9-spirobifluorene1Substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (5-to 30-membered) heteroaryl, due to: the more planar structures are, the more beneficial the molecular stacking is, and the carrier transport effect is increased, butHowever, the number of carbons in the group should not be too large to avoid the formation of unnecessary crystals.
The invention relates to X of diphenyl pyrimidine compound which is represented by formula (I) and substituted by 9, 9-spirobifluorene1Is substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (5-to 30-membered) heteroaryl, and has the effect of inhibiting molecular crystallization. In one embodiment, X1Is pyridyl, quinolyl or naphthyl.
In another embodiment, X in the 9, 9-spirobifluorene-substituted diphenylpyrimidine compounds represented by the formula (I) of the present invention1One selected from the group consisting of:
Figure BDA0001740480640000042
wherein, Xr represents hydrogen, fluorine, cyano, C1-4 alkyl or unsubstituted C6-18 aryl.
In one embodiment, A in the 9, 9-spirobifluorene-substituted diphenylpyrimidine compounds represented by the formula (I) of the present invention1One selected from the group consisting of:
wherein L represents O or S;
Ar1to Ar6Each independently represents hydrogen, an unsubstituted C6-18 aryl group;
R1to R4Each independently represents hydrogen, a substituted or unsubstituted C6-12 aryl group, R1And R2Together with the carbon atom to which they are attached form a C6-18 fused aromatic ring system, or R3And R4Together with the carbon atoms to which they are attached form a C6-18 fused aromatic ring system; and
Y1and Y2One of which is a single bond and is attached to the compound of formula (I) and the other is hydrogen.
In one embodiment, when n is 1, the compound of formula (I) is represented by formula (I-2) or formula (I-3).
Figure BDA0001740480640000052
In one embodiment, when n is 2, the compound of formula (I) is represented by formula (I-6).
Figure BDA0001740480640000061
In another embodiment, when n is 2, the A1Are of different construction.
In the present specification, the term "substituted" in "substituted or unsubstituted" means that a hydrogen atom in a functional group is replaced with another atom or group (i.e., substituent). Each of the substituents is independently selected from at least one of the group consisting of: deuterium, halogen, C1-30 alkyl, C1-30 alkoxy, C6-30 aryl, C5-30 heteroaryl, C5-30 heteroaryl substituted with C6-30 aryl, benzimidazolyl, C3-30 cycloalkyl, C5-7 heterocycloalkyl, tri-C1-30 alkylsilyl, tri-C1-30 arylsilyl, di-C1-30 alkylC 6-30 arylsilyl, C1-30 alkyldi-C6-30 arylsilyl, C2-30 alkenyl, C2-30 alkynyl, cyano, di-C1-30 alkylamino, di-C6-30 arylboron, di-C1-30 alkylboron, C1-30 alkyl, C6-30 arylC 1-30 alkyl, C1-30 alkylC 6-30 aryl, carboxyl, nitro and hydroxyl.
In the present specification, "aryl" means an aryl group or an (arylene) group, and the aryl group means a monocyclic ring or a fused ring derived from an aromatic hydrocarbon, and for example, there may be mentioned: phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthryl, benzophenanthrenyl, anthryl, benzanthryl, indenyl, terphenyl, pyrenyl, fluorenyl,
Figure BDA0001740480640000062
Mesityl, tetracenyl, peryleneyl, Kuai-yl, naphthonaphthyl, acriluorenyl, propadienefluorenyl, benzoacriluorenyl and the like.
In the present specification, "heteroaryl" means heteroaryl or (arylene), and the heteroaryl may be a monocyclic ring, and for example, there may be mentioned: furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, piperidyl and the like, or a condensed ring condensed with at least one benzene ring, and examples thereof include: benzofuranyl, benzothienyl, isobenzofuranyl, dibenzofuranyl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzodioxolyl, benzpyrazolyl, or may be, for example, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazolyl, phenanthridinyl, dihydroacridinyl, imidazopyridinyl, naphthyridinyl, phthalidyl (phthalazinyl), acridinyl, phenanthrolinyl, indolyl, phenazinyl, and the like.
In specific embodiments, preferred embodiments of the 9, 9-spirobifluorene-substituted diphenylpyrimidine compound represented by the formula (I) of the present invention are shown in the following table 1, but not limited thereto.
[ Table 1]
Figure BDA0001740480640000091
Figure BDA0001740480640000101
Figure BDA0001740480640000111
Figure BDA0001740480640000121
The diphenyl pyrimidine compound represented by the formula (I) and substituted by 9, 9-spirobifluorene can bear long-term high temperature in an automobile due to the glass transition temperature of the diphenyl pyrimidine compound between 146 ℃ and 223 ℃, so that the diphenyl pyrimidine compound is particularly suitable for an organic electroluminescent component of a display for an automobile.
The present invention also provides an organic electroluminescent device, comprising:
a cathode;
an anode; and
organic layer: between the cathode and the anode, the diphenyl pyrimidine compound which is represented by the formula (I) and is substituted by 9, 9-spirobifluorene is contained.
The organic layer of the organic electroluminescent component of the present invention may be an electron transport layer, an electron injection layer, a light emitting layer, a hole blocking layer or an electron blocking layer, and in addition to the organic layer, the organic electroluminescent component may further comprise at least one layer selected from the group consisting of an electron transport layer, an electron injection layer, a light emitting layer, a hole blocking layer and an electron blocking layer, which is different from the organic layer, wherein the light emitting layer comprises a fluorescent or phosphorescent guest dopant and a host material corresponding to the fluorescent or phosphorescent guest dopant, respectively.
In one embodiment, the organic layer containing the 9, 9-spirobifluorene-substituted diphenylpyrimidine compound represented by the formula (I) of the present invention is preferably an electron transporting layer, and the thickness thereof is preferably 20 to 30 nm; the electron transport layer can use diphenyl pyrimidine compound substituted by 9, 9-spirobifluorene with the structure of formula (I) as single material, or combine diphenyl pyrimidine compound substituted by 9, 9-spirobifluorene with electric conduction dopant.
In another embodiment, the electron transport layer further comprises an N-type electrically conductive dopant, wherein the N-type electrically conductive dopant and the 9, 9-spirobifluorene-substituted diphenylpyrimidine compound having the structure of formula (I) according to the present invention generate chelation (chelation) to allow electrons to be more easily injected into the electron transport layer from the cathode, so that the problems of phase separation and quenching caused by poor compatibility of metal and electron transport material in the prior art can be solved, and the transport efficiency of the electron transport layer can be effectively improved.
The N-type electrically conductive dopant used in the electron transport layer may be an organic alkali/alkaline earth metal nitrate, carbonate, phosphate or quinolinate, and examples thereof include: lithium carbonate, lithium quinolate (Liq), lithium azide (lithium azide), rubidium carbonate, silver nitrate, barium nitrate, magnesium nitrate, zinc nitrate, cesium carbonate, cesium fluoride, cesium azide, and the like, wherein lithium quinolate is particularly preferred as the n-type electrically conductive dopant.
In one embodiment, the N-type electrically conductive dopant is present in an amount of 5 wt% to 50 wt% based on the weight of the electron transport layer.
The structure of the organic electroluminescent device of the present invention is described below with reference to the drawings.
FIG. 1 is a cross-sectional view of an embodiment of an OLED module according to the present invention. The organic electroluminescent device 100 includes a substrate 110, an anode 120, a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, an electron injection layer 170, and a cathode 180. The organic electroluminescent device 100 can be fabricated by sequentially depositing the above layers.
FIG. 2 is a cross-sectional view of another embodiment of the organic electroluminescent device of the present invention. The organic electroluminescent device 200 comprises a substrate 210, an anode 220, a hole injection layer 230, a hole transport layer 240, an exciton blocking layer 245, a light emitting layer 250, an electron transport layer 260, an electron injection layer 270 and a cathode 280, and the difference from FIG. 1 is that the exciton blocking layer 245 is disposed between the hole transport layer 240 and the light emitting layer 250.
FIG. 3 is a cross-sectional view of another embodiment of the organic electroluminescent device of the present invention. The organic electroluminescent device 300 comprises a substrate 310, an anode 320, a hole injection layer 330, a hole transport layer 340, a light emitting layer 350, an exciton blocking layer 355, an electron transport layer 360, an electron injection layer 370 and a cathode 380, and the difference from FIG. 1 is that the exciton blocking layer 355 is disposed between the light emitting layer 350 and the electron transport layer 360.
The organic electroluminescent device can be manufactured in a reverse structure of the device shown in fig. 1 to 3. In addition, one or more layers of the inverted structures can be added or subtracted according to the needs.
The materials of the hole injection layer, the hole transport layer, the exciton blocking layer, the electron blocking layer and the electron injection layer can be selected from common materials, for example, the electron transport material for forming the electron transport layer is different from the material of the light emitting layer, and has hole transport property, so that holes can be migrated in the electron transport layer, and the carrier accumulation caused by the dissociation energy difference of the light emitting layer and the electron transport layer can be prevented.
The 9, 9-spirobifluorene-substituted diphenylpyrimidine compound represented by the formula (I) has a triplet energy level higher than 2.2eV, a HOMO energy level deeper than 6.0eV, and good carrier mobility, and thus, when the compound is used in an electron transport layer, the compound can contribute to the promotion of relaxation of excitons in a light emitting layer to emit light.
Furthermore, examined U.S. Pat. No. 20170005275A1, which discloses a p-type doped hole transport layer doped with HT-D2 in HT3, and also discloses the use of Lithium quinolate (Liq) as an n-type dopant in an electron transport material (ET3), is incorporated herein by reference. Also, for example, U.S. patent nos. 5703436 and 5707745 disclose that the entire contents of the cathode, which is composed of, for example, magnesium/silver (Mg: Ag), and a transparent conductive Layer (ITO Layer) formed by sputter deposition, are incorporated into the present invention. In addition, the present invention incorporates the application and principles of each barrier layer disclosed in U.S. Pat. Nos. 6097147 and 20030230980, which are incorporated herein in their entirety. In addition, the present invention also refers to the related contents of the injection layer and the protection layer as exemplified in the U.S. Pat. No. 20040174116.
Other structures and materials may be used, such as organic electroluminescent devices containing polymer materials (PLEDs) as disclosed in U.S. Pat. No. 5247190. Furthermore, the present invention is also applicable to an organic electroluminescent device having only a single organic layer or a multi-layer organic electroluminescent device as disclosed in U.S. Pat. No. 5707745.
Any layers in the various embodiments may be formed using any suitable method, unless otherwise specified. For the organic layer, preferred formation methods include evaporation and inkjet printing as disclosed in U.S. Pat. Nos. 6013982 and 6087196, Organic Vapor Phase Deposition (OVPD) as disclosed in U.S. Pat. No. 6337102, and organic vapor inkjet deposition (OVJP) as disclosed in U.S. Pat. No. 10/233470, which are incorporated herein by reference. Other suitable methods include spin coating and solution-based processes. The solution-based process is preferably carried out in an environment that is not susceptible to oxidation, such as a nitrogen or inert gas environment. For other layers, evaporation is preferred. Preferred patterning methods include processes utilizing masks, as disclosed in U.S. patent nos. 6294398 and 6468819, and processes that integrate jet printing or organic vapor jet printing deposition and patterning, the disclosures of which are incorporated herein by reference. Of course, other methods may be used.
The diphenyl pyrimidine compound represented by formula (I) and substituted by 9, 9-spirobifluorene can be used for preparing amorphous films applied to organic electroluminescent components by vacuum deposition, wet coating methods (including spin coating and ink-jet methods) or printing methods.
The organic electroluminescent assembly of the invention can be applied to active or passive structures. Compared with the prior component, the organic electroluminescent component can obviously improve the luminous efficiency and prolong the service life. In addition, the organic electroluminescent component can emit white light by doping phosphorescent guest dopant, and can realize a full-color or colorful display panel by matching with the optical filter.
The following synthetic examples and examples illustrate the various properties and effects of the present invention. However, these synthesis examples and embodiments are only for illustrating and understanding the present invention, and the present invention is not limited to these examples.
Synthesis example 1: synthesis of Compounds 1-9
Figure BDA0001740480640000151
4-bromoacetophenone (10g, 50.23mmole) and 9,9' -spirodiclofen are mixed together]-2-Ylboronic acid (18.45g, 52.12mmole) was placed in the reaction vessel and 120ml of toluene was added. Will K2CO3(24.3g, 175.8mmole) was dissolved in 70ml of deionized water, and then added to a reaction vessel, followed by addition of Pd (PPh)3)4(1.74g, 1.507mmole) and EtOH 30ml were started with heating and stirring. The reaction was heated to 80 ℃ overnight. After the reaction, 300ml of deionized water was added, stirring was stopped after 30min, standing was carried out to allow for layering, after removal of the water layer, purification was carried out by silica gel chromatography, concentration was carried out to a thick, 300ml of hexane was added to precipitate, and the organic layers were combined and the solid was filtered to obtain a milky white solid A (about 15 g).
Figure BDA0001740480640000152
Compound A (10g, 23.01mmole) and 3-bromobenzaldehyde (5.11g, 27.6mmole) were placed in a reaction vessel, after sufficient water removal, Ethanol 150ml was added, stirring was turned on, and sodium hydroxide (0.276g, 6.9mmole) was added and stirred at room temperature for 16 hr. Thereafter, 3-pyridine amidoxime salt (3-amidopyradinium chloride) (3.97g, 25.2 mmol) and sodium hydroxide (1.3g, 34.4 mmol) were added thereto, 20ml of toluene was added thereto, and the heating apparatus was opened. The reaction was heated to 75 ℃ overnight. After completion of the reaction, the solid was filtered with 250ml of toluene, and the solid was filtered under heating and stirring to obtain a milky white solid B (about 6.4 g).
Figure BDA0001740480640000161
Compound B (10g, 14.23mmole) and naphthalen-1-ylboronic acid (2.93g, 17.07mmole) were placed in a reaction vessel, and 120ml of toluene was added. Will K2CO3(6.88g, 49.8mmole) was dissolved in 70ml of deionized water, and then added to a reaction vessel, followed by addition of Pd (PPh)3)4(0.65g, 0.56mmole) and EtOH 30ml were started with heating and stirring. The reaction was heated to 80 ℃ overnight. Adding 300mL deionized water after the reaction, stirring for 30min, standing for layering, extracting, adding silica gel for chromatographic purification, concentrating to thick, adding 300mL hexane for enhanced precipitation, mixing organic layers, and filteringAs a result, milk pale yellow solid compounds 1 to 9 (about 5.5g) were obtained.
The following shows1Measurement result of H NMR.
1H NMR(CDCl3,400MHz)δ9.86(s,1H),8.91-8.89(m,1H),8.73-8.70(m,1H),8.36-8.30(m,2H),8.26(d,2H),8.07(s,1H),7.97-7.85(m,6H),7.72-7.66(m,3H),7.54-7.52(m,3H),7.50-7.49(m,2H),7.48-7.36(m,6H),7.15(t,3H),7.03-7.02(m,1H),6.80(d,2H),6.74(d,1H).
Synthesis example 2: synthesis of Compounds 1-10
Compound B (10g, 14.23mmole) and dibenzo [ B, d ]]Furan-4-ylboronic acid (3.16g, 14.9mmole) was placed in a reaction vessel, and 120ml of toluene was added. Will K2CO3(6.88g, 49.8mmole) was dissolved in 70ml of deionized water, and then added to a reaction vessel, followed by addition of Pd (PPh)3)4(0.82g, 0.71mmole) and EtOH 30ml were started with heating and stirring. The reaction was heated to 80 ℃ overnight. After the reaction, 300ml of deionized water is added, the mixture is stirred for 30min, the mixture is kept stand to be layered and extracted, and the filtrate after the extraction is added with silica gel for chromatography purification. After concentration to a thick, 300ml of hexane was added to enhance precipitation, the organic layers were combined and the solid was filtered to give compounds 1-10 as milky white solids (about 6.1 g).
The following shows1Measurement result of H NMR.
1H NMR(CDCl3,400MHz)δ9.90(s,1H),8.93(d,1H),8.80(s,1H),8.74-8.73(m,1H),8.29-8.28(m,3H),8.11-8.10(m,2H),7.96-7.94(m,1H),7.88-7.87(m,1H),7.72-7.71(m,1H),7.71-7.70(m,3H),7.50-7.35(m,9H),7.14(t,7H),7.05(s,1H),6.74(d,2H),6.69(d,1H).
Synthesis example 3: synthesis of Compounds 1-11
Figure BDA0001740480640000171
Compound B (10g, 14.23mmole) and dibenzo [ B, d ]]Thien-4-ylboronic acid (3.4g, 14.9mmole) was placed inIn the reaction vessel, 120ml of toluene was added. Will K2CO3(6.88g, 49.8mmole) was dissolved in 70ml of deionized water, and then added to a reaction vessel, followed by addition of Pd (PPh)3)4(0.82g, 0.71mmole) and EtOH 30ml were started with heating and stirring. The reaction was heated to 80 ℃ overnight. Adding 300ml deionized water after the reaction, stirring for 30min, standing for layering, extracting, adding the filtrate after extraction into silica gel for chromatography, concentrating to thick, adding 300ml hexane for enhanced precipitation, organic layer laminating and filtering the solid to obtain milky white solid compound 1-11 (about 5 g).
The following shows1Measurement result of H NMR.
1H NMR(CDCl3,400MHz)δ9.88(s,1H),8.39(s,1H),8.73-8.72(m,1H),8.72(s,1H),8.35(d,1H),8.33-8.32(m,4H),8.22(s,1H),7.96-7.83(m,6H),7.74-7.71(m,2H),7.63-7.60(m,4H),7.50-7.34(m,6H),7.18(t,3H),7.04(s,1H),6.82(d,2H),6.73(s,1H).
Synthesis example 4: synthesis of Compounds 1-12
Figure BDA0001740480640000181
Compound B (10g, 14.23mmole) and (3- (pyridin-3-yl) phenyl) boronic acid (3.4g, 14.9mmole) were placed in a reaction vessel, and 120ml of toluene was added. Will K2CO3(6.88g, 49.8mmole) was dissolved in 70ml of deionized water, and then added to a reaction vessel, followed by addition of Pd (PPh)3)4(0.82g, 0.71mmole) and EtOH 30ml were started with heating and stirring. The reaction was heated to 80 ℃ overnight. Adding 300ml deionized water after the reaction, stirring for 30min, standing for layering, extracting, adding the filtrate after extraction into silica gel for chromatography, concentrating to thick, adding 300ml hexane for enhanced precipitation, organic layer laminating and filtering the solid to obtain milky white solid compound 1-12 (about 5.5 g).
The following shows1Measurement result of H NMR.
1H NMR(CDCl3,400MHz)δ9.87(s,1H),8.94-8.91(m,2H),8.87-8.74(m,1H),8.64-8.63(m,1H),8.49(s,1H),8.26(d,3H),8.07(s,1H),7.91(d,2H),7.89-7.88(m,4H),7.88(d,1H),7.82-7.67(m,7H),7.64-7.64(m,5H),7.17(t,3H),7.07-7.04(m,1H),6.83(d,2H),6.78(d,1H).
Synthesis example 5: synthesis of Compounds 1-13
Figure BDA0001740480640000182
Compound B (10g, 14.23mmole) and (10-phenylanthracen-9-yl) boronic acid (5.09g, 17.01mmole) were placed in a reaction vessel, and 120ml of toluene was added. Will K2CO3(6.88g, 49.8mmole) was dissolved in 70ml of deionized water, and then added to a reaction vessel, followed by addition of Pd (PPh)3)4(0.82g, 0.71mmole) and EtOH 30ml were started with heating and stirring. The reaction was heated to 80 ℃ overnight. Adding 300ml deionized water after reaction, stirring for 30min, standing for layering, extracting, adding the filtrate after extraction into silica gel for chromatography, concentrating to thick, adding 300ml hexane for enhanced precipitation, organic layer laminating, and filtering to obtain light yellow solid compound 1-13 (about 4.3 g).
The following shows1Measurement result of H NMR.
1H NMR(CDCl3,400MHz)δ9.85(s,1H),8.91-8.89(m,1H),8.73-8.78(m,1H),8.53-8.51(m,1H),8.34(t,1H),8.23-8.2(m,2H),8.07(s,1H),7.94(d,1H),7.89-7.81(m,4H),7.77-7.50(m,14H),7.42-7.34(m,8H),7.16-7.10(m,3H),7.01(d,1H),6.78(d,1H),6.75-6.72(m,1H).
Synthesis example 6: synthesis of Compounds 1-14
1- (4-bromophenyl) ethanone (1- (4-bromophenyl) ethanone) (19.9g, 100mmole), potassium hydroxide (1.68g, 30mmole) and 3-bromobenzaldehyde (18.5g, 100mmole) were placed in a 1000ml two-necked round-bottomed flask, respectively, and 300ml of ethanol was added thereto, followed by stirring at room temperature for 4 hours. After filtration, compound C (about 34.4g) was obtained as a cream solid.
(E) -3- (3-bromophenyl) -1- (4-bromophenyl) prop-2-en-1-one (9.15g, 25mmole), nicotinamidine hydrochloride (3.94g, 25mmole) and potassium hydroxide (1.68g, 30mmole) were placed in a 500ml two-necked round-bottomed flask, respectively, 150ml of ethanol was added, and heated to reflux. After 3 hours of reaction, the reaction mixture was allowed to stand to warm to room temperature, filtered, and the solid was washed with ethanol to obtain compound D (about 9.34 g) as a white solid.
Separately adding Pd (PPh)3)4(3.30g，2.9mmole)、K2CO3(20.1g, 145.6mmole), Compound D (17.0g, 36.4mmole) and 9,9' -spirodiclofen-2-yl-boronic acid (28.8g, 80.1mmole) were placed in a 1000ml two-necked round bottom flask, 160ml of toluene, 110ml of ethanol and 50ml of deionized water were added thereto, and the mixture was heated to reflux. After the reaction overnight, 100ml of ethyl acetate was added for extraction, the filtrate after extraction was purified by chromatography on packed silica gel, concentrated to a thick consistency, and 50ml of methanol was added to precipitate strongly, and the solid was combined with organic layers and filtered to give compounds 1 to 14 as milky white solids (about 20.5 g).
The following shows1Measurement result of H NMR.
1H NMR(CDCl3,400MHz),δ9.83(s,1H),8.82(t,1H),8.72(d,1H),8.30(s,1H),8.19(d,2H),8.08(d,1H),7.97-7.95(m,3H),7.89(t,4H),7.85(d,2H),7.73～7.70(m,2H),7.59(d,2H),7.54(d,1H),7.48-7.34(m,10H),7.15-7.10(m,5H),7.03(d,2H),6.80(d,3H),6.75(d,2H).
Synthesis example 7: synthesis of Compounds 1-15
1- (4-bromophenyl) ethanone (19.9g, 100mmole), potassium hydroxide (1.68g, 30mmole) and 4-bromobenzaldehyde (18.5g, 100mmole) were placed in a 1000ml two-necked round-bottomed flask, respectively, and 300ml of ethanol was added thereto, followed by stirring at room temperature for 4 hours. After filtration, compound E was obtained as a milky white solid (about 35.5 g).
Figure BDA0001740480640000211
Compound E (9.15g, 25mmole), nicotinamidine hydrochloride (3.94g, 25mmole) and potassium hydroxide (1.68g, 30mmole) were placed in a 500ml two-necked round-bottomed flask, 150ml ethanol was added, and the mixture was heated to reflux. After 3 hours of reaction, the reaction mixture was allowed to stand to warm to room temperature, filtered, and the solid was washed with ethanol to obtain compound F (about 8.45 g) as a white solid.
Figure BDA0001740480640000212
Separately adding Pd (PPh)3)4(1.65g，1.45mmole)、K2CO3(10.0g, 72.8mmole), Compound F (8.5g, 18.2mmole) and 9,9' -spirodiclofen-2-yl-boronic acid (14.4g, 40.1mmole) were placed in a 500ml two-necked round bottom flask, and 80ml of toluene, 55ml of ethanol and 25ml of deionized water were added thereto, followed by heating to reflux. After the reaction overnight, 50ml of ethyl acetate was added for extraction, the filtrate after extraction was purified by chromatography on packed silica gel, concentrated to a thick consistency, added with 30ml of methanol for enhanced precipitation, and the solid was combined with organic layers and filtered to give compound 1-15 as a cream solid (about 9.5 g).
The following shows1Measurement result of H NMR.
1H NMR(CDCl3,400MHz)δ9.84(s,1H),8.89(t,1H),8.71(d,1H),8.20(d,4H),7.95(d,3H),7.90-7.86(m,6H),7.70(d,2H),7.60(d,4H),7.43-7.37(m,7H),7.12(t,6H),7.03(s,2H),6.80(d,4H),6.74(d,2H).
Synthesis example 8: synthesis of Compounds 1-16
Figure BDA0001740480640000221
Compound B (10g, 14.23mmole) and pyrene-1-ylboronic acid (3.85g, 15.6mmole) were placed in a reaction vessel, and 120ml of toluene was added. Will K2CO3(6.88g, 49.8mmole) was dissolved in 70ml of deionized waterAdding water into the reaction tank, and adding Pd (PPh)3)4(0.82g, 0.71mmole) and EtOH 30ml were started with heating and stirring. The reaction was heated to 80 ℃ overnight. Adding 300ml deionized water after the reaction, stirring for 30min, standing for layering, extracting, adding the filtrate after extraction into silica gel for chromatography, concentrating to thick, adding 300ml hexane for enhanced precipitation, organic layer laminating and filtering the solid to obtain milky white solid compound 1-16 (about 5.1 g).
The following shows1Measurement result of H NMR.
1H NMR(CDCl3,400MHz)δ9.87(s,1H),8.62-8.91(m,1H),8.72-8.71(m,1H),8.49(s,1H),8.39(d,1H),8.28(d,1H),8.24-8.12(m,7H),8.09-8.02(m,4H),7.94(d,1H),7.90-7.68(m,6H),7.60(d,2H),7.42-7.35(m,4H),7.15-7.10(m,3H),7.01(d,1H),6.89(d,2H),6.84(d,1H).
Synthesis example 9: synthesis of Compounds 1-17
Figure BDA0001740480640000222
Compound B (10g, 14.23mmole) and terphenyl-2-ylboronic acid (4.06g, 14.9mmole) were put into a reaction vessel, and 120ml of toluene was added. Will K2CO3(6.88g, 49.8mmole) was dissolved in 70ml of deionized water, and then added to a reaction vessel, followed by addition of Pd (PPh)3)4(0.82g, 0.71mmole) and EtOH 30ml were started with heating and stirring. The reaction was heated to 80 ℃ overnight. Adding 300ml deionized water after the reaction, stirring for 30min, standing for layering, extracting, adding the filtrate after extraction into silica gel for chromatography, concentrating to thick, adding 300ml hexane for enhanced precipitation, organic layer laminating and filtering the solid to obtain milky white solid compounds 1-17 (about 5 g).
The following shows1Measurement result of H NMR.
1H NMR(CDCl3,400MHz)δ9.92(s,1H),8.96-8.95(m,2H),8.80-8.62(m,7H),8.31-8.27(m,3H),8.12(s,1H),8.02-7.89(m,5H),7.72-7.69(m,7H),7.65-7.63(m,2H),7.48-7.36(m,4H),7.15-7.12(m,3H),7.04(d,1H),6.81(d,2H),6.76(d,1H).
Synthesis example 10: synthesis of Compounds 1-37
Figure BDA0001740480640000231
Compound a (10g, 23.03mmole) and 3,5-dibromobenzaldehyde (3,5-dibromobenzaldehyde) (6.63g, 25.12mmole) were placed in a reaction vessel, 150ml of ethanol was added after sufficient water removal, stirring was turned on, and sodium methoxide (0.33g, 6.2mmole) was added and stirred at room temperature for 16 hours. Thereafter, 3-pyridine amidoxime salt (3-amidopyradinium chloride) (3.96g, 25.13mmole) and sodium hydroxide (1.6g, 40.3mmole) were added thereto, 30ml of toluene was added thereto, and the heating apparatus was opened, heated to 75 ℃ and reacted overnight. After the reaction was completed, the solid was collected by filtration, heated and stirred with 250ml of toluene and filtered to obtain compound G (about 4.7G) as a milky white solid.
Figure BDA0001740480640000232
Compound G (10G, 12.8mmole) and 1-naphthylboronic acid (1-naphthylboronic acid) (4.4G, 25.6mmole) were placed in a reaction vessel, and 120ml of toluene was added. Potassium carbonate (18.768g, 135.8mmole) was dissolved in 70ml of deionized water, and then added to the reaction tank, followed by tetrakis (triphenylphosphine) palladium (Pd (PPh)3)4) (2g, 1.73mmole) and 30ml of ethanol were heated with stirring until 80 ℃ and reacted overnight. After the reaction, 300ml of deionized water was added, stirring was stopped after 30 minutes to allow for layering, filtration was carried out to obtain a crude product, silica gel was added to the crude product using a soxhlet extractor to carry out chromatography purification, the crude product was concentrated to a thick state, 300ml of hexane was added to enhance precipitation, organic layers were laminated and the solid was filtered to obtain a cream solid compound 1-37 (about 6.29 g).
The following shows1Measurement result of H NMR.
1H NMR(CDCl3,400MHz),δ9.916(s,1H),8.96(d,1H),8.72(dd,1H),8.50(d,2H),8.32(d,2H),8.20-8.23(m,2H),8.11(d,2H),7.92(m,4H),7.84(m,4H),7.80(d,1H),7.61-7.67(m,4H),7.50-7.35(m,6H),7.14(t,7H),7.05(s,1H),6.74(d,2H),6.69(d,1H)
The physical property values of the above materials are shown in table 2. The measurement methods of the respective physical property values are as follows.
(1) Temperature of thermal cracking (T)d)
Thermal cracking properties of the resulting compound were measured using a thermogravimetric analyzer (Perkin Elmer, TGA8000) at a programmed temperature rate of 20 ℃/min under normal pressure in a nitrogen atmosphere, and the temperature at which the weight was reduced to 95% of the initial weight was the thermal cracking temperature (T; (thermal cracking temperature)d)。
(2) Glass transition temperature (T)g)
The prepared compound was measured using a differential scanning thermal analyzer (DSC; Perkin Elmer, DSC8000) at a temperature programmed rate of 20 deg.C/min.
(3) Energy level of Highest Occupied Molecular Orbital (HOMO)
In addition, the compound was made into a thin film, and the ionization potential value thereof was measured using a photoelectron spectrophotometer (Riken Keiki, Surface Analyzer) under the atmosphere, and the value was further converted to obtain the HOMO level value.
(4) Lowest Unoccupied Molecular Orbital (LUMO) energy level
The LUMO level is obtained by measuring the boundary value (onset) of the absorption wavelength of a thin film of the above compound with a UV/VIS spectrophotometer (Perkin Elmer, Lambda20), converting the value into a band gap value, and subtracting the band gap value from the HOMO level value.
(5) Triplet energy value (E)T)
The luminescence spectrum was measured at 77K using a fluorescence spectrometer (Perkin Elmer, LS55) and calculated to obtain ET。
[ Table 2]
Figure BDA0001740480640000241
Figure BDA0001740480640000251
Example 1: manufacture of organic electroluminescent assembly
Before loading the substrate on the evaporation system, the substrate is cleaned by a solvent and ultraviolet ozone for degreasing. The substrate is then transferred to a vacuum deposition chamber where all layers are deposited on top of the substrate. The following layers shown in fig. 2 were deposited sequentially using a heated evaporation boat (boat) under a vacuum of about 10 "6 torr:
a) anode: thickness of 135nm
b) Hole injection layer: 20 nm thick and comprises an HTM doped with 9% of a p-type electrically conductive dopant, wherein the p-type electrically conductive dopant is available from vash chemical inc, shanghai, and the HTM is available from Merck & co, inc;
c) hole transport layer: 170 nm in thickness, HTM;
d) exciton blocking layer: thickness 10 nm, HT (Yi radium photoelectric preparation);
e) light-emitting layer: a thickness of 25 nm, including EBH doped with 4% volume ratio BD, wherein BD and EBH are Yi radium photo-electric preparations;
f) electron transport layer: thickness 25 nm, compound 1-10 and doped lithium quinolinate (Liq, Yi radium photoelectric preparation), volume ratio 1: 1;
g) electron injection layer: 0.5 nm thick, lithium fluoride (LiF); and
h) a cathode, approximately 180 nanometers thick, comprising a 1.
The component structure can be represented as: ITO/HTM: p-type electrically conductive dopant (20 nm)/HTM (170 nm)/HT (10 nm)/EBH BD (25 nm)/Compound 1-2: liq (25 nm)/LiF (0.5 nm)/Al (180 nm).
Figure BDA0001740480640000261
After deposition to form the layers described above, the assembly is transferred from the deposition chamber to a dry box and then encapsulated with a UV curable epoxy resin and a glass cover plate containing a moisture absorber. The organic electroluminescent device has a light emitting region of 9 mm.
Examples 2 to 4: manufacture of organic electroluminescent assembly
An organic electroluminescent device was fabricated in the same manner as in example 1, except that the compounds 1 to 10 of the electron transport layer in example 1 were replaced with the compounds 1 to 12, 1 to 13 and 1 to 14, respectively. The layer structures of examples 2 to 4 were the same as those of example 1.
Comparative example 1: manufacture of organic electroluminescent assembly
The structure of the organic electroluminescent device was made similar to that of example 1, except that compound 1-2 of the electron transport layer in example 1 was replaced with compound EET09, and the structure of the organic electroluminescent device was represented as follows: ITO/HTM p-type electrically conductive dopant (20 nm)/HTM (170 nm)/HT (10 nm)/EBH BD (25 nm)/Compound EET 09: liq (25 nm)/LiF (0.5 nm)/Al (180 nm).
Wherein the compound EET09 is as described in japanese patent No. 2011003793 a. The electroluminescence properties of the organic electroluminescence devices thus produced were measured at room temperature using a constant current Source (KEITHLEY 2400Source meters, made by KEITHLEY instruments, inc., Cleveland, Ohio) and a luminance Meter (PHOTO RESEARCH spectrum PR 650, made by PHOTO RESEARCH, inc., Chatsworth, Calif.) and the driving voltage, the luminous efficiency and the value of LT95 were listed in table 3 based on the organic electroluminescence device of the comparative example (standard value is 1). The LT95 value is defined as the time taken for the luminance level to decrease to a level of 95% relative to the initial luminance, and is used as a measure for evaluating the lifetime or stability of the organic electroluminescent device.
[ Table 3]
As shown in Table 2, the 9, 9-spirobifluorene-substituted diphenylpyrimidine compound of the present invention represented by the formula (I) has a higher thermal decomposition temperature (T) than that of the comparative exampled) And glass transition temperature (T)g) And as shown in Table 3, the organic electroluminescent devices using the 9, 9-spirobifluorene-substituted diphenylpyrimidine compounds represented by the formula (I) of the present invention have a comparative effectGood luminous efficiency and lifetime.
Therefore, the diphenyl pyrimidine compound substituted by 9, 9-spirobifluorene represented by formula (I) of the present invention with good luminous efficiency and life can improve the problems of the prior art, has extremely high technical value, and the organic electroluminescent component made of the diphenyl pyrimidine compound substituted by 9, 9-spirobifluorene represented by formula (I) is particularly suitable for the display for vehicles or the OLED lighting source in the field without extremely high driving voltage.
The above-described embodiments are merely illustrative, and not restrictive, of the invention, which is defined by the scope of the appended claims. Furthermore, those skilled in the art should also make modifications, substitutions, omissions, and changes to the present invention without departing from the spirit and scope of the present invention.

Claims (15)

1. A9, 9-spirobifluorene-substituted diphenylpyrimidine compound represented by the following formula (I),
Figure FDA0001740480630000011
wherein, X1Represents a substituted or unsubstituted (C6-C30) aryl, a substituted or unsubstituted (5-to 30-membered) heteroaryl;
A1represents a substituted or unsubstituted (C6-C30) aryl, a substituted or unsubstituted (5-to 30-membered) heteroaryl;
X1and A1Are the same or different and at least one is a substituted or unsubstituted (5-to 30-membered) heteroaryl;
n represents an integer of 1 or 2, and when n represents 2, A1Each of which may be the same or different.
2. The 9, 9-spirobifluorene-substituted diphenylpyrimidine compound according to claim 1, which is represented by a structure of formula (I-1), formula (I-2) or formula (I-3):
Figure FDA0001740480630000012
wherein, X1Represents a substituted or unsubstituted (C6-C30) aryl, a substituted or unsubstituted (5-to 30-membered) heteroaryl;
A1represents a substituted or unsubstituted (C6-C30) aryl, a substituted or unsubstituted (5-to 30-membered) heteroaryl;
X1and A1Are the same or different and at least one is a substituted or unsubstituted (5-to 30-membered) heteroaryl;
n represents an integer of 1 or 2, and when n represents 2, A1Each of which may be the same or different.
3. The 9, 9-spirobifluorene-substituted diphenylpyrimidine compound according to claim 1, wherein X1Is pyridyl, quinolyl or naphthyl.
4. The 9, 9-spirobifluorene-substituted diphenylpyrimidine compound according to claim 1 or 2, wherein X1One selected from the group consisting of:
Figure FDA0001740480630000021
wherein, Xr represents hydrogen, fluorine, cyano, C1-4 alkyl or unsubstituted C6-18 aryl.
5. The 9, 9-spirobifluorene-substituted diphenylpyrimidine compound according to claim 1 or 2, wherein A is1One selected from the group consisting of:
Figure FDA0001740480630000022
wherein L represents O or S;
Ar1to Ar6Each independently represents hydrogen, an unsubstituted C6-18 aryl group;
R1to R4Each independently represents hydrogen, a substituted or unsubstituted C6-12 aryl group, R1And R2Together with the carbon atom to which they are attached form a C6-18 fused aromatic ring system or R3And R4Together with the carbon atoms to which they are attached form a C6-18 fused aromatic ring system; and
Y1and Y2One of which is a single bond and is attached to the compound of formula (I) and the other is hydrogen.
6. The 9, 9-spirobifluorene-substituted diphenylpyrimidine compound according to claim 5, wherein the unsubstituted C6-18 aryl group is a phenyl group, and the unsubstituted C6-12 aryl group is a phenyl group.
7. The 9, 9-spirobifluorene-substituted diphenylpyrimidine compound according to claim 1, wherein when n is 1, the compound of the formula (I) is represented by the formula (I-4) or the formula (I-5):
Figure FDA0001740480630000031
8. the 9, 9-spirobifluorene-substituted diphenylpyrimidine compound according to claim 1, wherein the compound of the formula (I) is represented by the formula (I-6) when n is 2,
Figure FDA0001740480630000032
9. the 9, 9-spirobifluorene-substituted diphenylpyrimidine compound according to claim 8, wherein A is1The structure is the same.
10. The 9, 9-spirobifluorene-substituted diphenylpyrimidine compound according to claim 1, 7 or 8, which is one of the following compound (1-1) to compound (1-38):
Figure FDA0001740480630000041
Figure FDA0001740480630000051
11. the 9, 9-spirobifluorene-substituted diphenylpyrimidine compound according to claim 1 or 2, wherein the heteroaryl group contains at least one heteroatom selected from the group consisting of N, O and S.
12. An organic electroluminescent device, comprising:
a cathode;
an anode; and
organic layer: between the cathode and anode, a 9, 9-spirobifluorene-substituted diphenylpyrimidine compound according to any one of claims 1 to 11 is contained.
13. The organic electroluminescent device according to claim 12, wherein the organic layer is at least one selected from an electron transport layer, an electron injection layer, a light emitting layer, a hole blocking layer, and an electron blocking layer.
14. The organic electroluminescent device according to claim 12 or 13, wherein the organic layer is an electron transport layer and has a thickness of 20 nm to 30 nm.
15. The organic electroluminescent device according to claim 13 or 14, wherein the electron transport layer contains N-type conductive dopants in an amount of 0 wt% to 50 wt%.
CN201810816658.8A 2018-07-24 2018-07-24 Diphenyl pyrimidine compound substituted by 9, 9-spirobifluorene and organic electroluminescent assembly thereof Pending CN110746412A (en)

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WO2017157983A1 (en) * 2016-03-17 2017-09-21 Merck Patent Gmbh Compounds with spirobifluorene-structures
TWI630260B (en) * 2017-12-21 2018-07-21 昱鐳光電科技股份有限公司 Quinoline-substituted diphenylpyrimidines compounds and organic electroluminescent devices using the same
CN110944988A (en) * 2017-07-20 2020-03-31 株式会社斗山 Organic light-emitting compound and organic electroluminescent element comprising same

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CN110944988A (en) * 2017-07-20 2020-03-31 株式会社斗山 Organic light-emitting compound and organic electroluminescent element comprising same
TWI630260B (en) * 2017-12-21 2018-07-21 昱鐳光電科技股份有限公司 Quinoline-substituted diphenylpyrimidines compounds and organic electroluminescent devices using the same

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