CN111205293A - Heterocyclic compound, display panel and display device - Google Patents

Heterocyclic compound, display panel and display device Download PDF

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CN111205293A
CN111205293A CN202010088268.0A CN202010088268A CN111205293A CN 111205293 A CN111205293 A CN 111205293A CN 202010088268 A CN202010088268 A CN 202010088268A CN 111205293 A CN111205293 A CN 111205293A
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CN111205293B (en
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高威
张磊
代文朋
牛晶华
黄高军
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Xiamen Tianma Microelectronics Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
    • C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
    • C07D493/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
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    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D491/00—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00
    • C07D491/02—Heterocyclic compounds containing in the condensed ring system both one or more rings having oxygen atoms as the only ring hetero atoms and one or more rings having nitrogen atoms as the only ring hetero atoms, not provided for by groups C07D451/00 - C07D459/00, C07D463/00, C07D477/00 or C07D489/00 in which the condensed system contains two hetero rings
    • C07D491/04—Ortho-condensed systems
    • C07D491/044—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring
    • C07D491/048—Ortho-condensed systems with only one oxygen atom as ring hetero atom in the oxygen-containing ring the oxygen-containing ring being five-membered
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
    • H10K50/858—Arrangements for extracting light from the devices comprising refractive means, e.g. lenses
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
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    • H10K85/649—Aromatic compounds comprising a hetero atom
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene

Abstract

The invention discloses a heterocyclic compound, which has the chemical formula 1]The general structure of the compound is shown in the specification,
Figure DDA0002382812210000011
the two-five membered heterocyclic mother nucleus in the compound has a large rigid plane conjugated structure, can promote the interaction among molecules, is favorable for forming the close packing among the molecules, can effectively improve the refractive index of the compound, and simultaneouslyThe compound has a low absorption coefficient in a visible light region, and is suitable for being used as a capping layer material of an OLED top-emitting device. When the compound is used as a capping layer material of an OLED top-emitting device, the luminous efficiency of the device can be effectively improved, and the long-time working stability of the device is improved. The compound can also be used as an electron transport material or an electron injection material to improve the light emitting performance of the device.

Description

Heterocyclic compound, display panel and display device
Technical Field
The application relates to the technical field of organic electroluminescent materials, in particular to a heterocyclic compound, a display panel and a display device.
Background
The organic electroluminescent device structure mainly comprises electrodes, a hole transport layer, a luminescent layer, an electron transport layer and the like, and although the luminous efficiency of the organic electroluminescent device structure is much higher than that of other light-emitting devices (such as an LED, a TFT and the like), the internal quantum efficiency of the organic electroluminescent device structure is close to 100%, but the external quantum efficiency of the organic electroluminescent device structure is only about 20%. Researches show that the surface refractive index of a 0LED device can be changed by introducing a light extraction layer into the structure of a traditional device, and the limitation of factors such as substrate mode loss, surface plasma loss, waveguide effect and the like on light is eliminated, so that the light loss is reduced, the light extraction efficiency of the device is improved, and the light emitting efficiency of an OLED is improved to a certain extent. In order to improve the light extraction efficiency of the device, it is currently effective to use a light extraction Layer (CPL). The light extraction layer can reduce the surface plasma effect of the metal electrode, and the light extraction direction and the light extraction efficiency can be adjusted. In addition, the light extraction layer also needs to have minimum absorption in visible light and more proper refractive index, and has very similar properties for three colors of red, green and blue, but the types of materials which can be used as the light extraction layer are limited, and the development of more types of light extraction materials by OLED workers is urgently needed.
Disclosure of Invention
In view of the above, an object of the present invention is to provide a heterocyclic compound having a general structure shown in [ chemical formula 1 ]:
Figure BDA0002382812190000021
wherein, X1-X5Each independently selected from a carbon atom or a nitrogen atom; when X1, X2, X3, X4, X5 are selected from nitrogen atoms, Ar1, Ar2, Ar3, Ar4, Ar5 attached to the nitrogen atoms are absent;
Y1and Y2Each independently selected from a sulfur atom, an oxygen atom or-NR3，R3Selected from hydrogen, phenyl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C20 heteroaryl;
R1and R2Each independently selected from hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C20 heteroaryl;
Ar1-Ar5each independently selected from the group consisting of absent, hydrogen, biphenyl, naphthyl, phenanthryl, anthracenyl, pyrenyl, triphenylenyl;
Ar6selected from hydrogen atom, phenyl, pyridyl, biphenyl, naphthyl, phenanthryl, anthryl, pyrenyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C20 heteroaryl;
Ar1-Ar5wherein up to three substituents are simultaneously hydrogen atoms.
The compound provided by the invention is used as a cap layer material, so that the efficiency of the device can be obviously improved, and the service life of the device can be prolonged.
The compound has stable structure and excellent film forming performance, can be used as a light extraction material on an OLED device, can improve the transmittance of a semi-transmission electrode, reduce the surface plasma effect of a metal electrode, simultaneously can adjust the light emitting direction and the light emitting efficiency, and improve the external quantum efficiency of the OLED device, thereby effectively improving the light emitting efficiency of the device and enabling the transmittance in a visible light range to reach more than 80%.
The compound for a cap layer of the present invention is excellent in molecular arrangement and can form a stable thin film with increasing bulk density. Further, the high Tg and Td suppresses recrystallization, and thus, the organic light emitting device is not affected by heat generated when the organic light emitting device is driven, and the organic light emitting device can be improved in lifetime by reducing contamination inside the organic light emitting device due to external air and moisture.
Drawings
Fig. 1 is a schematic structural diagram of an organic light emitting display panel according to an embodiment of the present invention.
FIG. 2 is a general structural formula of the compound of the present invention.
Fig. 3 is a schematic structural diagram of a display device according to an embodiment of the present invention.
Detailed Description
In order to better understand the technical solution of the present application, the following detailed description is made on the embodiments of the present application.
It should be understood that the embodiments described are only a few embodiments of the present application, 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 protection scope of the present application.
The terminology used in the embodiments of the present application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used in the examples of this application and the appended claims, the singular forms "a", "an", and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise.
It should be understood that the term "and/or" as used herein is merely one type of association that describes an associated object, meaning that three relationships may exist, e.g., a and/or B may mean: a exists alone, A and B exist simultaneously, and B exists alone. In addition, the character "/" herein generally indicates that the former and latter related objects are in an "or" relationship.
In the description herein, it is to be understood that the terms "substantially", "approximately", "about", "approximately", "substantially", and the like in the claims and the examples herein are intended to be generally accepted as not being an exact value within a reasonable process operating range or tolerance.
One aspect of the present invention provides a heterocyclic compound having a general structure as shown in [ chemical formula 1 ]:
Figure BDA0002382812190000041
wherein, X1-X5Each independently selected from a carbon atom or a nitrogen atom; when X1, X2, X3, X4, X5 are selected from nitrogen atoms, Ar1, Ar2, Ar3, Ar4, Ar5 attached to the nitrogen atoms are absent;
Y1and Y2Each independently selected from a sulfur atom, an oxygen atom or-NR3，R3Selected from hydrogen, phenyl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C20 heteroaryl;
R1and R2Each independently selected from hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C20 heteroaryl;
Ar1-Ar5each independently selected from the group consisting of absent, hydrogen, biphenyl, naphthyl, phenanthryl, anthracenyl, pyrenyl, triphenylenyl;
Ar6selected from hydrogen atom, phenyl, pyridyl, biphenyl, naphthyl, phenanthryl, anthryl, pyrenyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C20 heteroaryl;
Ar1-Ar5wherein up to three substituents are simultaneously hydrogen atoms.
The five-membered heterocyclic unit in the heterocyclic compound has a large rigid plane conjugated structure, improves the delocalization capability of pi electrons and pi-pi interaction among molecules, improves the self-assembly performance of the molecules, is favorable for close packing among the molecules, can realize more ordered molecular arrangement, and improves the refractive index of the molecules. Meanwhile, the heterocyclic compound contains sulfur or oxygen, has high electron-rich property and high polarizability, and is favorable for obtaining a material with high refractive index. Therefore, the compound is suitable to be used as a cap layer material with high refractive index to be applied to an organic electroluminescent device, so that the light extraction efficiency is improved, and the luminous efficiency of the device is improved. The heterocyclic compound is connected with a five-membered heterocyclic ring and at least two Ar groups on a main body structure, the whole molecular structure presents a dendritic structure, the planarity of molecules is properly broken, the molecular configuration can effectively slow down the molecular crystallization trend, the molecules can more easily form an amorphous film, and the film forming stability of the film is improved; the tendency of the stability of the thin film deterioration caused by the heat generated by the long-time operation of the device is effectively inhibited.
The heterocyclic compound of the invention can introduce different types of substituent groups to modify the five-membered heterocyclic unit by a chemical synthesis method, and adjust the solubility, the thermal stability and the optical performance of the whole molecule.
According to one embodiment of the compounds of the present invention, wherein X is1-X5Each independently selected from carbon atom or nitrogen atom, and X1-X5At least one nitrogen atom. In the compound, a carbon atom and a nitrogen atom on a pyridine ring are overlapped with each other by an sp2 hybridized orbital to form a sigma bond, so that a plane six-membered ring is formed. Each atom has a p orbital perpendicular to the plane of the ring, each p orbital has an electron, the p orbitals overlap laterally to form a closed large pi bond, the number of pi electrons is 6, and the rule of 4n +2 is met. Thus, pyridine has a certain aromaticity. The nitrogen atom also has an sp2 hybridized orbital which does not participate in bonding and is occupied by a lone pair of electrons, so that the pyridine has basicity. The electronegativity of nitrogen atoms on pyridine rings is large, the density distribution of electron clouds on the rings is greatly influenced, pi electron clouds are shifted to the nitrogen atoms, the electron cloud density around the nitrogen atoms is high, the electron cloud density of other parts of the rings is reduced, pyridine is more difficult to oxidize, and the stability is better. Meanwhile, the existence of pyridine can also improve the polarizability of molecules, so that the refractive index of the molecules is improved.
According to one embodiment of the compounds of the present invention, wherein X is1-X5Each independently selected from carbon atom or nitrogen atom, and X1-X5At least two ofA nitrogen atom. In the compound, diazine, namely diazabenzene, is a six-membered heterocyclic compound containing two nitrogen atoms, is influenced by an electron-withdrawing induction effect and an electron-withdrawing conjugation effect of the nitrogen atoms, is weaker in alkalinity compared with pyridine and diazine, is more stable in diazine ring, and is difficult to generate electrophilic substitution reaction.
According to one embodiment of the compounds of the present invention, wherein X is1-X5Each independently selected from carbon atom or nitrogen atom, and X1-X5In which there are at least three nitrogen atoms.
According to one embodiment of the compounds of the present invention, wherein X is1-X5Each independently selected from carbon atom or nitrogen atom, and X1、X3、X5Are all nitrogen atoms. In the compound, the triazine structure has a symmetrical rigid structure, good chemical stability, electrochemical stability and photochemical stability, and simple synthesis, and meanwhile, the lone pair electrons on the N atom can improve the polarizability of molecules, so that the cap layer material with high refractive index is obtained by matching with the five-membered heterocyclic ring.
According to one embodiment of the compounds of the present invention, in said compounds, Y1And Y2Each independently selected from oxygen atoms. In the compound, a furan ring is easy to synthesize, and the compound has excellent electrochemical stability and thermal stability. The furan ring has stronger electron-withdrawing induction effect and smaller dipole moment. The furan rings have a rigid structure and are more likely to form a close packing. A pair of lone-pair electrons of an oxygen atom in furan form a large pi bond in a conjugated orbital plane, so that 6 electrons in total in the conjugated plane conform to a 4n +2 structure, and the furan has aromaticity (Huckel rule). While the other lone pair of electrons of the oxygen on the furan ring is stretched outward. The existence of larger electron cloud density on the furan ring enables the furan ring to have high polarizability, and the molecular structure of the difurane is easierA high index capping layer material is obtained.
According to one embodiment of the compounds of the present invention, the compounds are of the general structural formula:
Figure BDA0002382812190000061
wherein, X1-X5Each independently selected from a carbon atom or a nitrogen atom; when X1, X2, X3, X4, X5 are selected from nitrogen atoms, Ar1, Ar2, Ar3, Ar4, Ar5 attached to the nitrogen atoms are absent;
R1and R2Each independently selected from hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy;
Ar1-Ar5each independently selected from the group consisting of absent, hydrogen, biphenyl, naphthyl, phenanthryl, anthracenyl, pyrenyl, triphenylenyl; (ii) a
Ar6Selected from hydrogen atom, phenyl, pyridyl, biphenyl, naphthyl, phenanthryl, anthryl, pyrenyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C20 heteroaryl.
According to one embodiment of the compounds of the present invention, the compounds are of the general structural formula:
Figure BDA0002382812190000071
wherein, X1-X5Each independently selected from a carbon atom or a nitrogen atom; when X1, X2, X3, X4, X5 are selected from nitrogen atoms, Ar1, Ar2, Ar3, Ar4, Ar5 attached to the nitrogen atoms are absent;
R1and R2Each independently selected from hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy;
Ar1-Ar5each independently selected from the group consisting of absent, hydrogen, biphenyl, naphthyl, phenanthryl, anthracenyl, pyrenyl, triphenylenyl;
Ar6selected from the group consisting of hydrogen atoms,Phenyl, pyridyl, biphenyl, naphthyl, phenanthryl, anthracyl, pyrenyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C20 heteroaryl.
According to one embodiment of the compound, the compound has higher refractive index and optical performance, better light extraction effect on a device, higher luminous efficiency and longer device life.
According to one embodiment of the compounds of the present invention, in said compounds, Y1And Y2Each independently selected from a sulfur atom and an oxygen atom.
According to one embodiment of the compounds of the present invention, the compounds are of the general structural formula:
Figure BDA0002382812190000081
wherein, X1-X5Each independently selected from a carbon atom or a nitrogen atom; when X1, X2, X3, X4, X5 are selected from nitrogen atoms, Ar1, Ar2, Ar3, Ar4, Ar5 attached to the nitrogen atoms are absent;
R1and R2Each independently selected from hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy;
Ar1-Ar5each independently selected from the group consisting of absent, hydrogen, biphenyl, naphthyl, phenanthryl, anthracenyl, pyrenyl, triphenylenyl;
Ar6selected from hydrogen atom, phenyl, pyridyl, biphenyl, naphthyl, phenanthryl, anthryl, pyrenyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C20 heteroaryl.
The heterocyclic compound contains sulfur or oxygen, and the sulfur and the oxygen have higher electronegativity; the heterocyclic ring containing oxygen or sulfur has high electron-rich property and high polarizability, and is favorable for obtaining a material with high refractive index. The compound with thiophene structure and furan structure can be easily substituted by substituent groups to adjust the molecular volume and the molecular polarizability, thereby adjusting the refractive index of the molecule. The compound with thiophene and furan structures can form a steric hindrance effect by introducing a substituent, so that excellent film stability is obtained, the thermal stability of the compound is improved, and the long-time working life of a device is prolonged.
According to one embodiment of the compounds of the present invention, in said compounds, Y1And Y2Each independently selected from oxygen atom or-NR3，R3Selected from hydrogen, phenyl, methyl.
According to one embodiment of the compounds of the present invention, the compounds are of the general structural formula:
Figure BDA0002382812190000091
wherein, X1-X5Each independently selected from a carbon atom or a nitrogen atom; when X1, X2, X3, X4, X5 are selected from nitrogen atoms, Ar1, Ar2, Ar3, Ar4, Ar5 attached to the nitrogen atoms are absent;
R1and R2Each independently selected from hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy;
R3selected from hydrogen, phenyl, methyl;
Ar1-Ar5each independently selected from the group consisting of absent, hydrogen, biphenyl, naphthyl, phenanthryl, anthracenyl, pyrenyl, triphenylenyl;
Ar6selected from hydrogen atom, phenyl, pyridyl, biphenyl, naphthyl, phenanthryl, anthryl, pyrenyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C20 heteroaryl.
The heterocyclic compound of the present invention contains oxygen and nitrogen; the furan rings have a rigid structure and are more likely to form a close packing. A pair of lone-pair electrons of an oxygen atom in furan form a large pi bond in a conjugated orbital plane, so that 6 electrons in total in the conjugated plane conform to a 4n +2 structure, and the furan has aromaticity (Huckel rule). While the other lone pair of electrons of the oxygen on the furan ring is stretched outward. The furan ring has high polarizability due to the larger electron cloud density on the furan ring, so that a capping layer material with high refractive index can be obtained more easily. The furan ring has stronger electron-withdrawing induction effect and smaller dipole moment. The N atom on the pyrrole ring has stronger electron-donating conjugation effect and larger dipole moment. The compound containing the pyrrole structure is used for regulating the steric hindrance effect, the molecular configuration, the acting force among molecules and the arrangement mode among molecules by introducing different substituents on an N atom; thereby obtaining excellent film stability, improving the thermal stability of the compound and prolonging the service life of the device in long-time operation.
According to one embodiment of the compounds of the present invention, in said compounds, Y1And Y2Each independently selected from a sulfur atom.
According to one embodiment of the compounds of the present invention, in said compounds, Y1And Y2Each independently selected from a sulfur atom or-NR3，R3Selected from hydrogen, phenyl, methyl.
According to one embodiment of the compounds of the present invention, the compounds are of the general structural formula:
Figure BDA0002382812190000101
wherein, X1-X5Each independently selected from a carbon atom or a nitrogen atom; when X1, X2, X3, X4, X5 are selected from nitrogen atoms, Ar1, Ar2, Ar3, Ar4, Ar5 attached to the nitrogen atoms are absent;
R1and R2Each independently selected from hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy;
R3selected from hydrogen, phenyl, methyl;
Ar1-Ar5each independently selected from the group consisting of absent, hydrogen, biphenyl, naphthyl, phenanthryl, anthracenyl, pyrenyl, triphenylenyl;
Ar6selected from hydrogen atom, phenyl, pyridyl, biphenyl, naphthyl, phenanthryl, anthryl, pyrenyl, substituted or unsubstituted C6-C30 aryl,Substituted or unsubstituted C3-C20 heteroaryl.
According to one embodiment of the compounds of the present invention, the compounds are of the general structural formula:
Figure BDA0002382812190000111
wherein, X1-X5Each independently selected from a carbon atom or a nitrogen atom; when X1, X2, X3, X4, X5 are selected from nitrogen atoms, Ar1, Ar2, Ar3, Ar4, Ar5 attached to the nitrogen atoms are absent;
R1and R2Each independently selected from hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy;
R3selected from hydrogen, phenyl, methyl;
Ar1-Ar5each independently selected from the group consisting of absent, hydrogen, biphenyl, naphthyl, phenanthryl, anthracenyl, pyrenyl, triphenylenyl;
Ar6selected from hydrogen atom, phenyl, pyridyl, biphenyl, naphthyl, phenanthryl, anthryl, pyrenyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C20 heteroaryl.
According to one embodiment of the compounds represented by the invention, said compound is selected from one of the following compounds:
Figure BDA0002382812190000121
Figure BDA0002382812190000131
Figure BDA0002382812190000141
Figure BDA0002382812190000151
Figure BDA0002382812190000161
Figure BDA0002382812190000171
Figure BDA0002382812190000181
Figure BDA0002382812190000191
Figure BDA0002382812190000201
Figure BDA0002382812190000211
Figure BDA0002382812190000221
Figure BDA0002382812190000231
Figure BDA0002382812190000241
Figure BDA0002382812190000251
Figure BDA0002382812190000261
Figure BDA0002382812190000271
Figure BDA0002382812190000281
Figure BDA0002382812190000291
Figure BDA0002382812190000301
Figure BDA0002382812190000311
Figure BDA0002382812190000321
Figure BDA0002382812190000331
Figure BDA0002382812190000341
Figure BDA0002382812190000351
Figure BDA0002382812190000361
Figure BDA0002382812190000371
Figure BDA0002382812190000381
Figure BDA0002382812190000391
Figure BDA0002382812190000401
Figure BDA0002382812190000411
Figure BDA0002382812190000421
Figure BDA0002382812190000431
Figure BDA0002382812190000441
Figure BDA0002382812190000451
Figure BDA0002382812190000461
Figure BDA0002382812190000471
Figure BDA0002382812190000481
Figure BDA0002382812190000491
Figure BDA0002382812190000501
Figure BDA0002382812190000511
Figure BDA0002382812190000521
Figure BDA0002382812190000531
the invention also provides a display panel, which comprises a first electrode and a second electrode; an organic layer interposed between the first electrode and the second electrode; and a cover layer disposed outside at least one of the first electrode and the second electrode, wherein the cover layer contains the heterocyclic compound.
The invention also provides a display panel, wherein the first electrode is an anode, the second electrode is a cathode, a luminescent layer is arranged between the first electrode and the second electrode, the organic layer further comprises a hole transport region between the first electrode and the luminescent layer and an electron transport region between the luminescent layer and the second electrode, the hole transport region comprises a hole injection layer, a hole transport layer, a luminescent auxiliary layer, an electron blocking layer or any combination thereof, and the electron transport region comprises a hole blocking layer, an electron transport layer, an electron injection layer or any combination thereof; at least one material of the hole transport region and the electron transport region is the heterocyclic compound.
According to an embodiment of the display panel, the invention further provides a display device comprising the display panel.
In the display panel according to the present invention, the anode material of the organic light emitting device may be selected from metals such as copper, gold, silver, iron, chromium, nickel, manganese, palladium, platinum, etc., and alloys thereof; metal oxides such as indium oxide, zinc oxide, Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), and the like; examples of the conductive polymer include polyaniline, polypyrrole, and poly (3-methylthiophene). In addition to the above materials and combinations thereof that facilitate hole injection, the anode material may include other known materials suitable for use as an anode.
In the display panel according to the present invention, the cathode material of the organic light emitting device may be selected from metals such as aluminum, magnesium, silver, indium, tin, titanium, etc., and their compoundsAlloying; multilayer metallic materials, e.g. LiF/Al, LiO2/Al、BaF2Al, etc. In addition to the above materials and combinations thereof that facilitate electron injection, the cathode material can include other known materials suitable for use as a cathode.
In an embodiment of the present invention, the organic light emitting device in the display panel may be fabricated by: an anode is formed on a transparent or opaque smooth substrate, an organic thin layer is formed on the anode, and a cathode is formed on the organic thin layer. The organic thin layer can be formed by a known film formation method such as evaporation, sputtering, spin coating, dipping, ion plating, or the like. Finally, an organic optical cover layer CPL (cap layer) is prepared on the cathode. The material of the optical coating CPL is a compound according to the present invention. The optical coating CPL can be produced by evaporation or solution processing. Solution processing methods include ink jet printing, spin coating, doctor blade coating, screen printing, roll-to-roll printing, and the like.
Several exemplary synthetic examples of compounds are provided below.
Example 1
Synthesis of compound M001:
Figure BDA0002382812190000541
intermediate S1(1mmol) and S2(1mmol) were dissolved in 20mL of toluene under nitrogen, and Pd (PPh) was added3)4(0.05mmol) was added as a catalyst to 2mL of an aqueous potassium carbonate solution (2mol/L), and the mixture was refluxed for 12 hours. After the reaction, the mixture was extracted three times with saturated brine and ethyl acetate, and the organic phases were combined and dried over anhydrous sodium sulfate. All solvents were distilled off under reduced pressure and the crude product was collected. The crude product was purified by silica gel chromatography using a mixed solvent of n-hexane and chloroform at a volume ratio of 9:1 as an eluent, to finally purify S3(0.92mmol, 92% yield).
The structure of the target product S3 was tested: MALDI-TOF MS (m/z) is obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry: c12H8O2The calculated value was 184.0 and the test value was 184.2.
Figure BDA0002382812190000551
Intermediate S3(1mmol) and N-bromosuccinimide (NBS, 1.25mmol) were dissolved in 15mL of chloroform under nitrogen protection and stirred at room temperature for 12 h. After the reaction, the mixture was extracted three times with saturated brine and ethyl acetate, and the organic phases were combined and dried over anhydrous sodium sulfate. All solvents were distilled off under reduced pressure and the crude product was collected. The crude product was purified by silica gel chromatography using a mixed solvent of n-hexane and chloroform at a volume ratio of 8:1 as an eluent, to finally purify S4(0.98mmol, yield 98%) as a solid.
Test S4 structure: MALDI-TOF MS (m/z) is obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry: c12H7BrO2Calculated value is 262.0 and measured value is 262.3.
Figure BDA0002382812190000552
In a 50mL three-necked flask, S4(1mmol) and 12mL of tetrahydrofuran were first mixed. Stirring at a certain rotation speed, stirring the obtained mixed solution reactant at a reaction temperature of-78 ℃, dropwise adding butyl lithium (1.2mmol) into the solution, reacting for 1h, adding isopropanol pinacol borate (1.2mmol), and stirring at room temperature overnight. After the reaction was completed, 10ml of water was added, extraction was performed with ether, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was distilled off, and purification was performed using column chromatography to obtain intermediate S5(0.8mmol, 80%).
Test S5 structure: MALDI-TOF MS (m/z) is obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry: c18H19BO4The calculated value was 310.1 and the measured value was 310.3.
Figure BDA0002382812190000561
Dissolving S5(1mmol) and S6(1mmol) under nitrogen protectionDissolved in 20mL of toluene, and Pd (PPh) was added3)4(0.05mmol) was added as a catalyst to 2mL of an aqueous potassium carbonate solution (2mol/L), and the mixture was refluxed for 12 hours. After the reaction, the mixture was extracted three times with saturated brine and ethyl acetate, and the organic phases were combined and dried over anhydrous sodium sulfate. All solvents were distilled off under reduced pressure and the crude product was collected. The crude product was purified by silica gel chromatography using a mixed solvent of n-hexane and chloroform at a volume ratio of 5:1 as an eluent, to finally purify to obtain M001(0.80mmol, yield 80%) as a solid.
The structure of the target product M001 was tested: MALDI-TOF MS (m/z) is obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry: c46H28O2Calculated 612.2 and tested 612.5.
Elemental analysis test value: c, 90.14; h, 4.63.
1H-NMR(400MHz，CDCl3)：δ(ppm)6.3(s,2H),7.22(m,1H),7.32(m,2H),7.39(m,4H),7.48(m,2H),7.61(m,2H),7.66(m,3H),7.91(m,4H),7.97(m,2H),8.13(m,2H),8.31(s,4H)。
Example 2
Synthesis of compound M024:
Figure BDA0002382812190000571
intermediate S7(1mmol) and S2(1mmol) were dissolved in 20mL of toluene under nitrogen, and Pd (PPh) was added3)4(0.05mmol) was added as a catalyst to 2mL of an aqueous potassium carbonate solution (2mol/L), and the mixture was refluxed for 12 hours. After the reaction, the mixture was extracted three times with saturated brine and ethyl acetate, and the organic phases were combined and dried over anhydrous sodium sulfate. All solvents were distilled off under reduced pressure and the crude product was collected. The crude product was purified by silica gel chromatography using a mixed solvent of n-hexane and chloroform at a volume ratio of 9:1 as an eluent, to finally purify S8(0.90mmol, yield 90%).
The structure of the target product S8 was tested: MALDI-TOF MS (m/z) is obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry: c12H8S2Calculated value is 216.0 and test value is216.2。
Figure BDA0002382812190000572
Intermediate S8(1mmol) and N-bromosuccinimide (NBS, 1.25mmol) were dissolved in 15mL of chloroform under nitrogen protection and stirred at room temperature for 12 h. After the reaction, the mixture was extracted three times with saturated brine and ethyl acetate, and the organic phases were combined and dried over anhydrous sodium sulfate. All solvents were distilled off under reduced pressure and the crude product was collected. The crude product was purified by silica gel chromatography using a mixed solvent of n-hexane and chloroform at a volume ratio of 8:1 as an eluent, to finally purify S9(0.95mmol, 95% yield) as a solid.
Test S9 structure: MALDI-TOF MS (m/z) is obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry: c12H7BrS2The calculated value was 293.9, and the measured value was 293.9.
Figure BDA0002382812190000581
In a 50mL three-necked flask, S9(1mmol) and 12mL of tetrahydrofuran were first mixed. Stirring at a certain rotation speed, stirring the obtained mixed solution reactant at a reaction temperature of-78 ℃, dropwise adding butyl lithium (1.2mmol) into the solution, reacting for 1h, adding isopropanol pinacol borate (1.2mmol), and stirring at room temperature overnight. After completion of the reaction, 10ml of water was added, extraction was performed with ether, the obtained organic phase was dried over anhydrous sodium sulfate, the solvent was distilled off, and purification was performed by column chromatography to obtain S10(0.82mmol, 82%).
Test S10 structure: MALDI-TOF MS (m/z) is obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry: c18H19BO2S2Calculated value is 342.1 and measured value is 342.2.
Figure BDA0002382812190000582
Under the protection of nitrogen, S10(1 m)mol) and S11(1mmol) were dissolved in 20mL of toluene, and Pd (PPh) was added3)4(0.05mmol) was added as a catalyst to 2mL of an aqueous potassium carbonate solution (2mol/L), and the mixture was refluxed for 12 hours. After the reaction, the mixture was extracted three times with saturated brine and ethyl acetate, and the organic phases were combined and dried over anhydrous sodium sulfate. All solvents were distilled off under reduced pressure and the crude product was collected. The crude product was purified by silica gel chromatography using a mixed solvent of n-hexane and chloroform at a volume ratio of 5:1 as eluent to obtain solid M024(0.85mmol, 85% yield).
Testing the structure of a target product M024: MALDI-TOF MS (m/z) is obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry: c45H27NS2Calculated 645.2 and test 645.5.
Elemental analysis test value: c, 83.67; h, 4.23; and N, 2.19.
1H-NMR(400MHz，CDCl3)：δ(ppm)7.0(s,2H),7.22(m,1H),7.32(m,2H),7.36(m,2H),7.39(m,4H),7.48(m,2H),7.91(m,4H),8.00(m,2H),8.12(m,2H),8.31(s,4H),8.64(m,2H)。
Example 3
Synthesis of compound M041:
Figure BDA0002382812190000591
intermediate S12(1mmol) and S2(1mmol) were dissolved in 20mL of toluene under nitrogen, and Pd (PPh) was added3)4(0.05mmol) was added as a catalyst to 2mL of an aqueous potassium carbonate solution (2mol/L), and the mixture was refluxed for 12 hours. After the reaction, the mixture was extracted three times with saturated brine and ethyl acetate, and the organic phases were combined and dried over anhydrous sodium sulfate. All solvents were distilled off under reduced pressure and the crude product was collected. The crude product was purified by silica gel chromatography using a mixed solvent of n-hexane and chloroform at a volume ratio of 10:1 as an eluent, to finally purify S13(0.93mmol, 93% yield).
The structure of the target product S13 was tested: MALDI-TOF MS (m/z) is obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry: c18H13NOCalculated value is 259.1 and test value is 259.3.
Figure BDA0002382812190000592
Intermediate S13(1mmol) and N-bromosuccinimide (NBS, 1.25mmol) were dissolved in 15mL of chloroform under nitrogen protection and stirred at room temperature for 12 h. After the reaction, the mixture was extracted three times with saturated brine and ethyl acetate, and the organic phases were combined and dried over anhydrous sodium sulfate. All solvents were distilled off under reduced pressure and the crude product was collected. The crude product was purified by silica gel chromatography using a mixed solvent of n-hexane and chloroform at a volume ratio of 9:1 as an eluent, to finally purify S14(0.93mmol, 93% yield) as a solid.
Test S14 structure: MALDI-TOF MS (m/z) is obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry: c18H12BrNO, calculated 337.0, measured 337.3.
Figure BDA0002382812190000601
In a 50mL three-necked flask, S14(1mmol) and 12mL of tetrahydrofuran were first mixed. Stirring at a certain rotation speed, stirring the obtained mixed solution reactant at a reaction temperature of-78 ℃, dropwise adding butyl lithium (1.2mmol) into the solution, reacting for 1h, adding isopropanol pinacol borate (1.2mmol), and stirring at room temperature overnight. After completion of the reaction, 10ml of water was added, extraction was performed with ether, the resulting organic phase was dried over anhydrous sodium sulfate, the solvent was distilled off, and purification was performed using column chromatography to obtain S15(0.78mmol, 78%).
Test S15 structure: MALDI-TOF MS (m/z) is obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry: c24H24BNO3The calculated value was 385.2 and the measured value was 385.4.
Figure BDA0002382812190000602
In the presence of nitrogen gasS15(1mmol) and S16(1mmol) were dissolved in 20mL of toluene under stirring, and Pd (PPh) was added3)4(0.05mmol) was added as a catalyst to 2mL of an aqueous potassium carbonate solution (2mol/L), and the mixture was refluxed for 12 hours. After the reaction, the mixture was extracted three times with saturated brine and ethyl acetate, and the organic phases were combined and dried over anhydrous sodium sulfate. All solvents were distilled off under reduced pressure and the crude product was collected. The crude product was purified by silica gel chromatography using a mixed solvent of n-hexane and chloroform at a volume ratio of 5:1 as eluent to obtain M041(0.80mmol, 80% yield) as a solid.
The structure of the target product M041 was tested: MALDI-TOF MS (m/z) is obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry: c50H31N3O, calculated 689.2, test value 689.3.
Elemental analysis test value: c, 87.07; h, 4.52; and N, 6.10.
1H-NMR(400MHz，CDCl3)：δ(ppm)6.0-6.4(m,2H),7.22(m,1H),7.28-7.34(m,7H),7.39(m,4H),7.48(m,2H),7.61(m,2H),7.64(m,1H),7.91(m,4H),7.97(m,2H),8.13(m,2H),8.31(s,4H)。
Example 4
Synthesis of compound M054:
Figure BDA0002382812190000611
intermediate S17(1mmol) and S2(1mmol) were dissolved in 20mL of toluene under nitrogen, and Pd (PPh) was added3)4(0.05mmol) was added as a catalyst to 2mL of an aqueous potassium carbonate solution (2mol/L), and the mixture was refluxed for 12 hours. After the reaction, the mixture was extracted three times with saturated brine and ethyl acetate, and the organic phases were combined and dried over anhydrous sodium sulfate. All solvents were distilled off under reduced pressure and the crude product was collected. The crude product was purified by silica gel chromatography using a mixed solvent of n-hexane and chloroform at a volume ratio of 9:1 as an eluent, to finally purify S18(0.95mmol, yield 95%).
The structure of the target product S18 was tested: MALDI-TOF MS (m/z) is obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry: c24H18N2The calculated value was 334.2 and the test value was 334.5.
Figure BDA0002382812190000612
Intermediate S18(1mmol) and N-bromosuccinimide (NBS, 1.25mmol) were dissolved in 15mL of chloroform under nitrogen protection and stirred at room temperature for 12 h. After the reaction, the mixture was extracted three times with saturated brine and ethyl acetate, and the organic phases were combined and dried over anhydrous sodium sulfate. All solvents were distilled off under reduced pressure and the crude product was collected. The crude product was purified by silica gel chromatography using a mixed solvent of n-hexane and chloroform at a volume ratio of 8:1 as an eluent, to finally purify S19(0.90mmol, yield 90%) as a solid.
Test S19 structure: MALDI-TOF MS (m/z) is obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry: c24H17BrN2The calculated value was 412.1 and the measured value was 412.4.
Figure BDA0002382812190000621
In a 50mL three-necked flask, S19(1mmol) and 12mL of tetrahydrofuran were first mixed. Stirring at a certain rotation speed, stirring the obtained mixed solution reactant at a reaction temperature of-78 ℃, dropwise adding butyl lithium (1.2mmol) into the solution, reacting for 1h, adding isopropanol pinacol borate (1.2mmol), and stirring at room temperature overnight. After completion of the reaction, 10ml of water was added, extraction was performed with ether, the obtained organic phase was dried over anhydrous sodium sulfate, the solvent was distilled off, and purification was performed by column chromatography to obtain S20(0.85mmol, 85%).
Test S20 structure: MALDI-TOF MS (m/z) is obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry: c30H29BN2O2Calculated 460.2 and measured 460.5.
Figure BDA0002382812190000622
S20(1mmol) and S21(1mmol) were dissolved in 20mL of toluene under nitrogen, and Pd (PPh) was added3)4(0.05mmol) was added as a catalyst to 2mL of an aqueous potassium carbonate solution (2mol/L), and the mixture was refluxed for 12 hours. After the reaction, the mixture was extracted three times with saturated brine and ethyl acetate, and the organic phases were combined and dried over anhydrous sodium sulfate. All solvents were distilled off under reduced pressure and the crude product was collected. The crude product was purified by silica gel chromatography using a mixed solvent of n-hexane and chloroform at a volume ratio of 5:1 as an eluent, to finally purify to obtain solid M054(0.79mmol, yield 79%).
Testing the structure of the target product M054: MALDI-TOF MS (m/z) is obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry: c55H35N5Calculated value is 765.3 and test value is 765.6.
Elemental analysis test value: c, 86.28; h, 4.60; and N, 9.12.
1H-NMR(400MHz，CDCl3)：δ(ppm)6.2(s,2H),7.22(m,1H),7.28-7.34(m,12H),7.39(m,4H),7.48(m,2H),7.61(m,2H),7.91(m,4H),7.97(m,2H),8.13(m,2H),8.31(s,4H)。
Example 5
Synthesis of compound M088:
Figure BDA0002382812190000631
intermediate S22(1mmol) and S2(1mmol) were dissolved in 20mL of toluene under nitrogen, and Pd (PPh) was added3)4(0.05mmol) was added as a catalyst to 2mL of an aqueous potassium carbonate solution (2mol/L), and the mixture was refluxed for 12 hours. After the reaction, the mixture was extracted three times with saturated brine and ethyl acetate, and the organic phases were combined and dried over anhydrous sodium sulfate. All solvents were distilled off under reduced pressure and the crude product was collected. The crude product was purified by silica gel chromatography using a mixed solvent of n-hexane and chloroform at a volume ratio of 9:1 as an eluent, to finally purify S23(0.92mmol, 92% yield).
The structure of the target product S23 was tested: in flight ionization by matrix-assisted laser desorptionMALDI-TOF MS (m/z) is obtained by mass spectrum analysis: c18H13NS, calculated 275.1, test value 275.3.
Figure BDA0002382812190000632
Intermediate S23(1mmol) and N-bromosuccinimide (NBS, 1.25mmol) were dissolved in 15mL of chloroform under nitrogen protection and stirred at room temperature for 12 h. After the reaction, the mixture was extracted three times with saturated brine and ethyl acetate, and the organic phases were combined and dried over anhydrous sodium sulfate. All solvents were distilled off under reduced pressure and the crude product was collected. The crude product was purified by silica gel chromatography using a mixed solvent of n-hexane and chloroform at a volume ratio of 8:1 as an eluent, to finally purify S24(0.91mmol, 91% yield) as a solid.
Test S24 structure: MALDI-TOF MS (m/z) is obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry: c18H12BrNS, calculated 353.0, measured 353.1.
Figure BDA0002382812190000641
In a 50mL three-necked flask, S24(1mmol) and 12mL of tetrahydrofuran were first mixed. Stirring at a certain rotation speed, stirring the obtained mixed solution reactant at a reaction temperature of-78 ℃, dropwise adding butyl lithium (1.2mmol) into the solution, reacting for 1h, adding isopropanol pinacol borate (1.2mmol), and stirring at room temperature overnight. After completion of the reaction, 10ml of water was added, extraction was performed with ether, the obtained organic phase was dried over anhydrous sodium sulfate, the solvent was distilled off, and purification was performed by column chromatography to obtain S25(0.83mmol, 83%).
Test S25 structure: MALDI-TOF MS (m/z) is obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry: c24H24BNO2S, calculated 401.2, measured 401.3.
Figure BDA0002382812190000642
S25(1mmol) and S26(1mmol) were dissolved in 20mL of toluene under nitrogen, and Pd (PPh) was added3)4(0.05mmol) was added as a catalyst to 2mL of an aqueous potassium carbonate solution (2mol/L), and the mixture was refluxed for 12 hours. After the reaction, the mixture was extracted three times with saturated brine and ethyl acetate, and the organic phases were combined and dried over anhydrous sodium sulfate. After the reaction was completed, all the solvent was distilled off under reduced pressure, and the crude product was collected. The crude product was purified by silica gel chromatography using a mixed solvent of n-hexane and chloroform at a volume ratio of 5:1 as an eluent to finally purify to obtain M088(0.75mmol, yield 75%) as a solid.
The structure of the target product M088 was tested: MALDI-TOF MS (m/z) is obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry: c50H31N3S, calculated 705.2 and tested 705.3.
Elemental analysis test value: c, 85.06; h, 4.45; and N, 5.96.
1H-NMR(400MHz，CDCl3)：δ(ppm)6.2(s,1H),7.0(s,1H),7.22(m,1H),7.28-7.35(m,8H),7.48(m,2H),7.71(m,4H),7.82(m,2H),7.88(m,2H),8.04(m,2H),8.12(m,2H),8.18(m,2H),8.93(m,2H),9.15(s,2H)。
Example 6
Synthesis of compound M100:
Figure BDA0002382812190000651
s5(1mmol) and S27(1mmol) were dissolved in 20mL of toluene under nitrogen, and Pd (PPh) was added3)4(0.05mmol) was added as a catalyst to 2mL of an aqueous potassium carbonate solution (2mol/L), and the mixture was refluxed for 12 hours. After the reaction, the mixture was extracted three times with saturated brine and ethyl acetate, and the organic phases were combined and dried over anhydrous sodium sulfate. After the reaction was completed, all the solvent was distilled off under reduced pressure, and the crude product was collected. The crude product was purified by silica gel chromatography using a mixed solvent of n-hexane and chloroform at a volume ratio of 5:1 as an eluent, to finally purify to obtain a solid M100(0.83mmol, 83% yield).
Testing the structure of the target product M100: MALDI-TOF MS (m/z) is obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry: c43H25N3O2Calculated value is 615.2 and test value is 615.4.
Elemental analysis test value: c, 83.87; h, 4.08; and N, 6.84.
1H-NMR(400MHz，CDCl3)：δ(ppm)6.2(s,2H),7.22(m,1H),7.32(m,2H),7.48(m,2H),7.71(m,4H),7.82(m,2H),7.88(m,2H),8.04(m,2H),8.12(m,2H),8.18(m,2H),8.93(m,2H),9.15(s,2H)。
Example 7
Synthesis of compound M118:
Figure BDA0002382812190000661
s5(1mmol) and S28(1mmol) were dissolved in 20mL of toluene under nitrogen, and Pd (PPh) was added3)4(0.05mmol) was added as a catalyst to 2mL of an aqueous potassium carbonate solution (2mol/L), and the mixture was refluxed for 12 hours. After the reaction, the mixture was extracted three times with saturated brine and ethyl acetate, and the organic phases were combined and dried over anhydrous sodium sulfate. After the reaction was completed, all the solvent was distilled off under reduced pressure, and the crude product was collected. The crude product was purified by silica gel chromatography using a mixed solvent of n-hexane and chloroform at a volume ratio of 10:1 as an eluent to finally purify to obtain a solid M118(0.76mmol, yield 76%).
Testing the structure of the target product M118: MALDI-TOF MS (m/z) is obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry: c50H28O2Calculated value was 660.2 and test value was 660.3.
Elemental analysis test value: c, 90.87; h, 4.28.
1H-NMR(400MHz，CDCl3)：δ(ppm)6.3(s,2H),7.22(m,1H),7.32(m,2H),7.48(m,2H),7.66(m,3H),7.71(m,8H),7.82(m,2H),8.00(m,4H),8.03-8.08(m,4H)。
Example 8
Synthesis of compound M298:
Figure BDA0002382812190000671
s5(1mmol) and S29(1mmol) were dissolved in 20mL of toluene under nitrogen, and Pd (PPh) was added3)4(0.05mmol) was added as a catalyst to 2mL of an aqueous potassium carbonate solution (2mol/L), and the mixture was refluxed for 12 hours. After the reaction, the mixture was extracted three times with saturated brine and ethyl acetate, and the organic phases were combined and dried over anhydrous sodium sulfate. After the reaction was completed, all the solvent was distilled off under reduced pressure, and the crude product was collected. The crude product was purified by silica gel chromatography using a mixed solvent of n-hexane and chloroform at a volume ratio of 9:1 as an eluent to finally purify to obtain solid M298(0.80mmol, yield 80%).
The structure of the target product M298 was tested: MALDI-TOF MS (m/z) is obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry: c48H26N2O2Calculated 662.2 and tested 662.4.
Elemental analysis test value: c, 86.95; h, 3.96; and N, 4.24.
1H-NMR(400MHz，CDCl3)：δ(ppm)6.3(s,2H),7.22(m,1H),7.32(m,2H),7.48(m,2H),7.64(s,1H),7.71(m,8H),7.82(m,2H),8.00(m,4H),8.03-8.08(m,4H)。
Example 9
Synthesis of compound M307:
Figure BDA0002382812190000672
s5(1mmol) and S30(1mmol) were dissolved in 20mL of toluene under nitrogen, and Pd (PPh) was added3)4(0.05mmol) was added as a catalyst to 2mL of an aqueous potassium carbonate solution (2mol/L), and the mixture was refluxed for 12 hours. After the reaction, the mixture was extracted three times with saturated brine and ethyl acetate, and the organic phases were combined and dried over anhydrous sodium sulfate. After the reaction was completed, all the solvent was distilled off under reduced pressure, and the crude product was collected. The crude product was purified by silica gel chromatography using a mixed solvent of n-hexane and chloroform in a volume ratio of 5:1 as eluent to obtain solid M307(0.77mmol,yield 77%).
The structure of the target product M307 was tested: MALDI-TOF MS (m/z) is obtained by matrix-assisted laser desorption ionization time-of-flight mass spectrometry: c52H30N2O2Calculated 714.2 and test 714.5.
Elemental analysis test value: c, 87.36; h, 4.24; and N, 3.93.
1H-NMR(400MHz，CDCl3)：δ(ppm)6.3(s,2H),7.22(m,1H),7.32(m,2H),7.48(m,2H),7.64(s,1H),7.82(m,4H),7.88(m,4H),8.07(m,2H),8.12(m,4H),8.58(m,2H),8.74(s,2H),8.93(m,4H).
Comparative example 1
Figure BDA0002382812190000681
Comparative example 2
Figure BDA0002382812190000682
And (3) testing physical property parameters of the compounds:
band gap E was performed for the compounds used as capping layers in examples and comparative examplesgGlass transition temperature TgThe results of the refractive index n and the extinction coefficient k are shown in Table 1. Evaporating a compound film on a quartz plate, and measuring an optical band gap Eg of the compound by using an ultraviolet-visible absorption spectrometer (Perkinelmer Lambda750 ultraviolet-visible spectrophotometer); glass transition temperature TgMeasured by differential scanning calorimetry (DSC, Vorterma technologies (Shanghai) Co., Ltd., PerkinElmer DSC 8000 scanning differential calorimeter) in which the rate of temperature rise is 10 ℃/min; the refractive index n and the extinction coefficient k are measured by an ellipsometer (U.S. J.A. Woollam Co. model: ALPHA-SE) in an atmospheric environment.
TABLE 1 physical Properties of the Compounds
Figure BDA0002382812190000691
The compound of the invention has higher refractive index, generally Tg is more than 120 ℃, and the compound has almost no absorption in a visible light region, and is suitable for being used as a capping layer material. The compound has wide band gap without influence on RGB wavelength of the organic light-emitting device, and simultaneously has high refractive index, and the compound can be used as a capping layer material to improve the color purity and the external light-emitting efficiency of the organic light-emitting device.
To facilitate understanding of the present invention, examples of the organic light emitting display panel according to the present invention are as follows. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
As shown in fig. 1, another aspect of the present invention provides an organic light emitting display panel including: the structure of the organic electroluminescent device comprises a substrate 1, an anode 2(ITO), a hole injection layer 3, a first hole transport layer 4, a second hole transport layer 5, a light-emitting layer 6, an electron transport layer 7, an electron injection layer 8, a cathode 9 (a magnesium-silver electrode, the mass ratio of magnesium to silver is 9:1) and a capping layer (CPL)10, wherein the thickness of the ITO anode 2 is 15nm, the thickness of the hole injection layer 3 is 5nm, the thickness of the first hole transport layer 4 is 100nm, the thickness of the second hole transport layer 5 is 5nm, the thickness of the light-emitting layer 6 is 30nm, the thickness of the electron transport layer 7 is 30nm, the thickness of the electron injection layer 8 is 5nm, the thickness of the magnesium-silver electrode 9 is 10nm and the thickness of the capping layer (CPL)10 is 80 nm.
Application example 1
The embodiment provides an organic light emitting display panel, which is specifically prepared by the following steps:
1) the glass substrate was cut into a size of 50mm × 50mm × 0.7mm, sonicated in isopropanol and deionized water for 30 minutes, respectively, and then exposed to ozone for about 10 minutes to clean, resulting in substrate 1. Mounting the resulting glass substrate with Indium Tin Oxide (ITO) anode on a vacuum deposition apparatus;
2) on the ITO anode layer 2, a hole injection layer material compound 2 and a p-doped material compound 1 are evaporated together in a vacuum evaporation mode, and the doping proportion is 3 percent (mass ratio); a thickness of 5nm, this layer serving as a hole injection layer 3;
3) vacuum evaporating a hole transport layer material compound 3 on the hole injection layer 3, wherein the thickness of the hole transport layer material compound 3 is 100nm and is used as a first hole transport layer 4;
4) vacuum evaporating a hole-transport type material compound 4 on the first hole-transport layer 4, wherein the thickness of the hole-transport type material compound 4 is 5nm and the hole-transport type material compound is taken as a second hole-transport layer 5;
4) a luminescent layer 6 is vacuum-evaporated on the second hole transport layer 5, wherein the compound 5 is used as a main material, the compound 6 is used as a doping material, the doping proportion is 3% (mass ratio), and the thickness is 30 nm;
5) an electron transport type material compound 7 is vacuum-evaporated on the light emitting layer 6, and the thickness of the electron transport type material compound 7 is 30nm to form an electron transport layer 7;
6) an electron transport material compound 8 and an n-doped material compound 9 are evaporated on the electron transport layer 7 in a vacuum manner together, and the doping mass ratio is 1: 1; 5nm in thickness as an electron injection layer 8;
7) a magnesium silver electrode is evaporated on the electron injection layer 8 in vacuum, wherein the ratio of Mg to Ag is 1:9, the thickness of the Mg to Ag is 10nm, and the Mg to Ag is used as a cathode 9;
8) compound M001 was vacuum-deposited on cathode 9 to a thickness of 80nm, and used as cap layer 10.
Figure BDA0002382812190000711
Application example 2
The difference from application example 1 is that compound M001 was replaced with M024.
Application example 3
The difference from application example 1 is that compound M001 is replaced by M041.
Application example 4
The difference from application example 1 is that compound M001 is replaced by M054.
Application example 5
The difference from application example 1 is that compound M001 is replaced by M088.
Application example 6
The difference from application example 1 is that compound M001 is replaced by M100.
Application example 7
The difference from application example 1 is that compound M001 is replaced by M118.
Application example 8
The difference from application example 1 is that compound M001 is replaced by M298.
Application example 9
The difference from application example 1 is that compound M001 is replaced by M307.
Application comparative example 1
The difference from application example 1 is that compound M001 is replaced with compound C1.
Comparative application example 2
The difference from application example 1 is that compound M001 is replaced with compound C2.
Performance evaluation of organic light emitting display panel
The current at different voltages of the display panels manufactured according to the application examples and the application comparative examples was measured using a Keithley 2365A digital nano-meter, and then the current was divided by the light emitting area to obtain the current density at different voltages of the display panels. The luminance and radiant flux density of the display panels manufactured according to the application examples and the application comparative examples were measured at different voltages using a Konicaminolta CS-2000 spectroradiometer. According to the current density and the brightness of the display panel under different voltages, the current density (10 mA/cm) under the same current density is obtained2) Operating voltage V ofonCurrent efficiency (Cd/A) and external quantum efficiency EQE; the lifetime T95 (at 50 mA/cm) was obtained by measuring the time when the luminance of the organic light emitting device reached 95% of the initial luminance2Test conditions) results.
The results of the performance tests are shown in table 2.
TABLE 2
Figure BDA0002382812190000731
Compared with a comparative compound, the compound provided by the invention can be used as a cap layer material, so that the efficiency of a device can be obviously improved, and the service life of the device can be prolonged.
The compound has stable structure and excellent film forming performance, can be used as a light extraction material on an OLED device, can improve the transmittance of a semi-transmission electrode, reduce the surface plasma effect of a metal electrode, simultaneously can adjust the light emitting direction and the light emitting efficiency, and improve the external quantum efficiency of the OLED device, thereby effectively improving the light emitting efficiency of the device and enabling the transmittance in a visible light range to reach more than 80%.
The compound for a cap layer of the present invention is excellent in molecular arrangement and can form a stable thin film with increasing bulk density. Further, the high Tg and Td suppresses recrystallization, and thus, the organic light emitting device is not affected by heat generated when the organic light emitting device is driven, and the organic light emitting device can be improved in lifetime by reducing contamination inside the organic light emitting device due to external air and moisture.
Still another aspect of the present invention also provides a display device including the organic light emitting display panel as described above. As shown in fig. 3, fig. 3 is a schematic structural diagram of a display device according to an embodiment of the present invention, where 100 is the display device and 200 is a display panel.
In the present invention, the organic light emitting device may be an OLED, which may be used in an organic light emitting display device, wherein the organic light emitting display device may be a display screen of a mobile phone, a computer display screen, a display screen of a liquid crystal television, a display screen of a smart watch, a display panel of a smart car, a display screen of a VR or AR helmet, a display screen of various smart devices, and the like.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the scope of protection of the present application.

Claims (15)

1. A heterocyclic compound having a general structure represented by [ chemical formula 1 ]:
Figure FDA0002382812180000011
wherein, X1-X5Each independently selected from carbon atom or nitrogenAn atom; when X1, X2, X3, X4, X5 are selected from nitrogen atoms, Ar1, Ar2, Ar3, Ar4, Ar5 attached to the nitrogen atoms are absent;
Y1and Y2Each independently selected from a sulfur atom, an oxygen atom or-NR3，R3Selected from hydrogen, phenyl, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C20 heteroaryl;
R1and R2Each independently selected from hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C20 heteroaryl;
Ar1-Ar5each independently selected from the group consisting of absent, hydrogen, biphenyl, naphthyl, phenanthryl, anthracenyl, pyrenyl, triphenylenyl;
Ar6selected from hydrogen atom, phenyl, pyridyl, biphenyl, naphthyl, phenanthryl, anthryl, pyrenyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C20 heteroaryl;
Ar1-Ar5wherein up to three substituents are simultaneously hydrogen atoms.
2. The heterocyclic compound according to claim 1, wherein in the compound, X1-X5Each independently selected from carbon atom or nitrogen atom, and X1-X5At least one nitrogen atom.
3. The heterocyclic compound according to claim 2, wherein in the compound, X1-X5Each independently selected from carbon atom or nitrogen atom, and X1-X5In which there are at least two nitrogen atoms.
4. The heterocyclic compound according to claim 3, wherein in the compound, X1-X5Each independently selected from carbon atom or nitrogen atom, and X1-X5ToThere are three fewer nitrogen atoms.
5. The heterocyclic compound according to claim 4, wherein in the compound, X1-X5Each independently selected from carbon atom or nitrogen atom, and X1、X3、X5Are all nitrogen atoms.
6. The heterocyclic compound according to claim 1, wherein in the compound, Y is1And Y2Each independently selected from oxygen atoms.
7. The heterocyclic compound according to claim 6, characterized in that the compound is of the following general structural formula:
Figure FDA0002382812180000021
wherein, X1-X5Each independently selected from a carbon atom or a nitrogen atom; when X1, X2, X3, X4, X5 are selected from nitrogen atoms, Ar1, Ar2, Ar3, Ar4, Ar5 attached to the nitrogen atoms are absent;
R1and R2Each independently selected from hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy;
Ar1-Ar5each independently selected from the group consisting of absent, hydrogen, biphenyl, naphthyl, phenanthryl, anthracenyl, pyrenyl, triphenylenyl;
Ar6selected from hydrogen atom, phenyl, pyridyl, biphenyl, naphthyl, phenanthryl, anthryl, pyrenyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C20 heteroaryl.
8. The heterocyclic compound according to claim 1, wherein in the compound, Y is1And Y2Each independently selected from a sulfur atom and an oxygen atom.
9. The heterocyclic compound of claim 8, which is of the following general structural formula:
Figure FDA0002382812180000031
wherein, X1-X5Each independently selected from a carbon atom or a nitrogen atom; when X1, X2, X3, X4, X5 are selected from nitrogen atoms, Ar1, Ar2, Ar3, Ar4, Ar5 attached to the nitrogen atoms are absent;
R1and R2Each independently selected from hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy;
Ar1-Ar5each independently selected from the group consisting of absent, hydrogen, biphenyl, naphthyl, phenanthryl, anthracenyl, pyrenyl, triphenylenyl;
Ar6selected from hydrogen atom, phenyl, pyridyl, biphenyl, naphthyl, phenanthryl, anthryl, pyrenyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C20 heteroaryl.
10. The heterocyclic compound according to claim 1, wherein in the compound, Y is1And Y2Each independently selected from a sulfur atom.
11. The heterocyclic compound according to claim 10, characterized in that the compound is of the following general structural formula:
Figure FDA0002382812180000041
wherein, X1-X5Each independently selected from a carbon atom or a nitrogen atom; when X1, X2, X3, X4, X5 are selected from nitrogen atoms, Ar1, Ar2, Ar3, Ar4, Ar5 attached to the nitrogen atoms are absent;
R1and R2Each independently selected from hydrogen, substituted or unsubstituted C1-C20 alkyl, substituted or unsubstituted C1-C20 alkoxy;
Ar1-Ar5each independently selected from the group consisting of absent, hydrogen, biphenyl, naphthyl, phenanthryl, anthracenyl, pyrenyl, triphenylenyl;
Ar6selected from hydrogen atom, phenyl, pyridyl, biphenyl, naphthyl, phenanthryl, anthryl, pyrenyl, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C20 heteroaryl.
12. The heterocyclic compound according to claim 1, characterized in that the compound is selected from one of the following compounds:
Figure FDA0002382812180000051
Figure FDA0002382812180000061
Figure FDA0002382812180000071
Figure FDA0002382812180000081
Figure FDA0002382812180000091
Figure FDA0002382812180000101
Figure FDA0002382812180000111
Figure FDA0002382812180000121
Figure FDA0002382812180000131
Figure FDA0002382812180000141
Figure FDA0002382812180000151
Figure FDA0002382812180000161
Figure FDA0002382812180000171
Figure FDA0002382812180000181
Figure FDA0002382812180000191
Figure FDA0002382812180000201
Figure FDA0002382812180000211
Figure FDA0002382812180000221
Figure FDA0002382812180000231
Figure FDA0002382812180000241
Figure FDA0002382812180000251
Figure FDA0002382812180000261
Figure FDA0002382812180000271
Figure FDA0002382812180000281
Figure FDA0002382812180000291
Figure FDA0002382812180000301
Figure FDA0002382812180000311
Figure FDA0002382812180000321
Figure FDA0002382812180000331
Figure FDA0002382812180000341
Figure FDA0002382812180000351
Figure FDA0002382812180000361
Figure FDA0002382812180000371
Figure FDA0002382812180000381
Figure FDA0002382812180000391
Figure FDA0002382812180000401
Figure FDA0002382812180000411
Figure FDA0002382812180000421
Figure FDA0002382812180000431
Figure FDA0002382812180000441
Figure FDA0002382812180000451
Figure FDA0002382812180000461
13. a display panel is characterized by comprising a first electrode and a second electrode; an organic layer interposed between the first electrode and the second electrode; and a cover layer disposed outside at least one of the first electrode and the second electrode, wherein the cover layer contains the heterocyclic compound according to any one of claims 1 to 12.
14. The display panel according to claim 13, wherein the first electrode is an anode, the second electrode is a cathode, a light emitting layer is further provided between the first electrode and the second electrode, the organic layer further comprises a hole transport region between the first electrode and the light emitting layer and an electron transport region between the light emitting layer and the second electrode, the hole transport region comprises a hole injection layer, a hole transport layer, a light emission auxiliary layer, an electron blocking layer, or any combination thereof, and the electron transport region comprises a hole blocking layer, an electron transport layer, an electron injection layer, or a combination thereof; at least one material of the hole transport region and the electron transport region is the heterocyclic compound according to any one of claims 1 to 12.
15. A display device comprising the display panel of claim 13 or 14.
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