CN114605425A

CN114605425A - Organic compound, and mixture, composition and organic electronic device comprising the same

Info

Publication number: CN114605425A
Application number: CN202210380329.XA
Authority: CN
Inventors: 夏泽铭; 周国富; 宋晶尧
Original assignee: South China Normal University; Guangzhou Chinaray Optoelectronic Materials Ltd
Current assignee: South China Normal University; Guangzhou Chinaray Optoelectronic Materials Ltd
Priority date: 2022-04-08
Filing date: 2022-04-08
Publication date: 2022-06-10

Abstract

The application discloses an organic compound having the following structure:

Description

Organic compound, and mixture, composition and organic electronic device comprising the same

Technical Field

The present application relates to the field of luminescent materials, and more particularly, to an organic compound, and a mixture, a composition and an organic electronic device including the organic compound.

Background

Organic semiconductor materials are versatile in synthesis, relatively low in manufacturing cost, and excellent in optical and electrical properties. Organic Light Emitting Diodes (OLEDs) have the advantages of wide viewing angle, fast response time, low operating voltage, thin panel thickness, etc., in the application of optoelectronic devices, such as flat panel displays and lighting, and thus have a wide potential for development.

The organic electroluminescence phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic substance. An organic electroluminescent element utilizing an organic electroluminescent phenomenon generally has a structure including a positive electrode and a negative electrode and an organic layer therebetween. In order to improve the efficiency and lifetime of the organic electroluminescent element, the organic layer has a multi-layer structure, each layer containing a different organic substance. Specifically, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like may be included. In such an organic electroluminescent element, when a voltage is applied between the two electrodes, holes are injected from the positive electrode into the organic layer, electrons are injected from the negative electrode into the organic layer, and when the injected holes and electrons meet each other, excitons are formed, which emit light when the excitons transition back to the ground state. The organic electroluminescent element has the characteristics of self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, high responsiveness and the like.

In order to improve the light emitting efficiency of the organic electroluminescent device, various fluorescent and phosphorescent light emitting material systems have been developed, and the development of excellent blue light emitting materials, whether fluorescent materials or phosphorescent materials, is a great challenge, and in general, the organic light emitting diode using the currently used blue light emitting materials has higher reliability. However, most of the blue fluorescent materials have too wide emission spectrum, poor color purity, and are not suitable for high-end display, and the synthesis of such fluorescent materials is also complicated, which is not suitable for large-scale mass production, and simultaneously, the stability of the OLED of such blue fluorescent materials needs to be further improved. Therefore, the development of the blue fluorescent material with narrow-band emission spectrum and good stability is beneficial to obtaining a blue light device with longer service life and higher efficiency on the one hand, and is beneficial to improving the color gamut on the other hand, thereby improving the display effect.

A light emitting layer of the existing blue light organic electroluminescent element adopts a host-guest doped structure, most blue light host materials adopt anthracene-based condensed ring derivatives, but the stability of the material of the light emitting layer is poor, so that the service life of the device is short. Meanwhile, these materials are difficult to realize deep blue emission and to satisfy the requirements for full color display.

Therefore, there is still a need for further improvement of materials to improve the performance of organic electroluminescent devices.

Disclosure of Invention

In view of the above, the present application provides a blue-light fluorescent organic compound, which aims to solve the problems of low light-emitting efficiency and short lifetime of the existing blue-light fluorescent organic electronic device.

The application is realized by the following technical scheme:

an organic compound having a structure represented by general formula (1):

Ar₁selected from a substituted or unsubstituted aromatic group containing 6 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group containing 5 to 60 ring atoms, or a combination of these groups;

correspondingly, the application also provides a mixture comprising the organic compound and at least one organic functional material, wherein the organic functional material is selected from a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a light emitting material, a host material, a guest material or an organic dye.

Correspondingly, the application also provides a composition which comprises the organic compound or the mixture and at least one organic solvent.

Correspondingly, the application also provides an organic electronic device which comprises at least one functional layer, wherein the functional layer contains the organic compound or the mixture, or the functional layer is prepared from the composition.

Compared with the prior art, the organic compound has the following beneficial effects:

the anthracene derivative containing the heterocyclic fused ring can be used as a host material and used in a light-emitting layer of an organic electronic device. The organic matter has fluorescence emission at blue light wavelength, so the organic matter can be used in a blue light organic light-emitting electronic device, and has higher device light-emitting efficiency and longer device service life.

Drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.

FIG. 1 is a schematic view of an OLED device shown in example 1 of the device of the present application;

here, 101 denotes a substrate, 102 denotes an anode, 103 denotes a Hole Injection Layer (HIL), 104 denotes a Hole Transport Layer (HTL), 105 denotes an emission layer, 106 denotes an Electron Transport Layer (ETL), and 107 denotes a cathode.

Detailed Description

The technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all of the 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. Furthermore, it should be understood that the detailed description and specific examples, while indicating exemplary embodiments of the invention, are given by way of illustration and explanation only, and are not intended to limit the scope of the invention.

In the description of the present application, the term "comprising" means "including but not limited to", and the term "plurality" means "two or more". Various embodiments of the present application may exist in a range of forms; it should be understood that the description in range format is merely for convenience and brevity and should not be construed as an inflexible limitation on the scope of the application; accordingly, the described range descriptions should be considered to have specifically disclosed all the possible sub-ranges as well as individual numerical values within that range. For example, it is contemplated that the description of a range from 1 to 6 has specifically disclosed sub-ranges, such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., as well as single numbers within the stated range, such as 1, 2,3, 4,5, and 6, as applicable regardless of the range. In addition, whenever a numerical range is indicated herein, it is meant to include any number (fractional or integer) recited within the indicated range.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description 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 herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

In the present application, the compositions, printing inks and inks have the same meaning and can be interchanged.

In the present application, aromatic groups, aromatic rings and aromatic ring systems have the same meaning and can be interchanged.

In the present application, heteroaromatic groups, heteroaromatic and heteroaromatic ring systems have the same meaning and can be interchanged.

In the present application, "substituted" means that a hydrogen atom in a substituent is substituted by a substituent.

In the present application, "substituted or unsubstituted" means that the defined group may or may not be substituted. When a defined group is substituted, it is understood that the defined group may be substituted with one or more substituents R selected from, but not limited to, deuterium atoms, cyano groups, isocyano groups, nitro groups, halogens, alkyl groups containing 1 to 20C atoms, heterocyclic groups containing 3 to 20 ring atoms, aromatic groups containing 6 to 20 ring atoms, heteroaromatic groups containing 5 to 20 ring atoms, -NR' R ", silane groups, carbonyl groups, alkoxycarbonyl groups, aryloxycarbonyl groups, carbamoyl groups, haloformyl groups, formyl groups, isocyanate groups, thiocyanate groups, isothiocyanate groups, hydroxyl groups, and trifluoromethyl groups, and the above groups may also be further substituted with art-acceptable substituents; it is understood that R 'and R "in-NR' R" are each independently selected from, but not limited to, H, deuterium atoms, cyano groups, isocyano groups, nitro groups or halogens, alkyl groups containing 1 to 10C atoms, heterocyclic groups containing 3 to 20 ring atoms, aromatic groups containing 6 to 20 ring atoms, heteroaromatic groups containing 5 to 20 ring atoms. Preferably, R is selected from, but not limited to, deuterium atom, cyano group, isocyano group, nitro group or halogen, alkyl group containing 1 to 10C atoms, heterocyclic group containing 3 to 10 ring atoms, aromatic group containing 6 to 20 ring atoms, heteroaromatic group containing 5 to 20 ring atoms, silane group, carbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, haloformyl group, formyl group, isocyanate group, thiocyanate group, isothiocyanate group, hydroxyl group and trifluoromethyl group, and the above groups may be further substituted with art-acceptable substituents.

In the present application, the "number of ring atoms" refers to the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, and a heterocyclic compound) in which atoms are bonded in a ring shape. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The "number of ring atoms" described below is the same unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.

"aryl or aromatic group" means an aromatic hydrocarbon group derived by removing one hydrogen atom from an aromatic ring compound, and may be a monocyclic aryl group, or a condensed ring aryl group, or a polycyclic aryl group, at least one of which in the polycyclic ring is an aromatic ring system. For example, "substituted or unsubstituted aryl group having 6 to 40 ring atoms" means an aryl group containing 6 to 40 ring atoms, preferably a substituted or unsubstituted aryl group having 6 to 30 ring atoms, more preferably a substituted or unsubstituted aryl group having 6 to 18 ring atoms, particularly preferably a substituted or unsubstituted aryl group having 6 to 14 ring atoms, and the aryl group is optionally further substituted; suitable examples include, but are not limited to, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluoranthenyl, triphenylenyl, pyrenyl, perylenyl, tetracenyl, fluorenyl, perylenenyl, acenaphthenyl, and derivatives thereof. It is understood that multiple aryl groups may also be interrupted by short non-aromatic units (e.g. < 10% of non-H atoms, such as C, N or O atoms), such as in particular acenaphthene, fluorene, 9-diarylfluorene, triarylamine or diarylether systems should also be included in the definition of aryl groups.

"heteroaryl or heteroaromatic group" means that on the basis of an aryl group at least one carbon atom is replaced by a non-carbon atom which may be a N atom, an O atom, an S atom, etc. For example, "substituted or unsubstituted heteroaryl having 5 to 40 ring atoms" means a heteroaryl having 5 to 40 ring atoms, preferably a substituted or unsubstituted heteroaryl having 6 to 30 ring atoms, more preferably a substituted or unsubstituted heteroaryl having 6 to 18 ring atoms, particularly preferably a substituted or unsubstituted heteroaryl having 6 to 14 ring atoms, and the heteroaryl is optionally further substituted, suitable examples include, but are not limited to, thienyl, furyl, pyrrolyl, oxadiazolyl, triazolyl, imidazolyl, pyridyl, bipyridyl, pyrimidinyl, triazinyl, acridinyl, pyridazinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, benzothienyl, benzofuryl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, pyrrolopyrrolylpyrrolylpyrrolyl, and the like, Thienopyrrolyl, thienothiophenyl, furopyrrolyl, furofuranyl, thienofuranyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, o-dinitrogen naphthyl, phenanthridinyl, primidinyl, quinazolinone, dibenzothiophenyl, dibenzofuranyl, carbazolyl, and derivatives thereof.

In the present application, "alkyl" may mean a linear, branched and/or cyclic alkyl group. The carbon number of the alkyl group may be 1 to 50, 1 to 30, 1 to 20, 1 to 10, or 1 to 6. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, adamantyl and the like.

In this application, "halogen" or "halo" refers to F, Cl, Br, or I.

In the present application, the term "alkoxy" refers to a group having an-O-alkyl group, i.e. an alkyl group as defined above is attached to the parent core structure via an oxygen atom. Phrases encompassing this term, suitable examples include, but are not limited to: methoxy (-O-CH)₃or-OMe), ethoxy (-O-CH)₂CH₃or-OEt) and tert-butoxy (-O-C (CH)₃)₃or-OtBu).

In this application, "+" indicates a connection site.

In the present application, when a plurality of substituents of the same symbol are contained on the same group, the substituents may be the same as or different from each other, for example

6R in the benzene ring¹May be the same as or different from each other.

In this application, a single bond connecting substituents through the corresponding ring means that the substituent may be attached to an optional position of the ring, e.g.

Wherein R is connected with any substitutable site of the benzene ring; such as

To represent

Can be combined with

On the middle benzene ringOptionally forming a fused ring.

The cyclic alkyl or cycloalkyl groups described herein have the same meaning and are interchangeable.

The technical scheme of the application is as follows:

an organic compound having a structure represented by general formula (1):

Ar₁selected from substituted or unsubstituted aromatic groups containing from 6 to 60 ring atoms, or substituted or unsubstituted heteroaromatic groups containing from 5 to 60 ring atoms, or combinations of these groups;

in some embodiments, Ar is₁Selected from the structures shown in any one of:

wherein:

x is independently selected from CR at each occurrence₁Or N;

y is selected from NR₂、CR₃R₄、SiR₃R₄O, S, S ═ O or SO₂；

R₁、R₂、R₃、R₄Independently at each occurrence is selected from-H, -D, or a linear alkyl group having 1 to 20C atoms, a linear alkoxy group having 1 to 20C atoms, or a linear thioalkoxy group having 1 to 20C atoms, or a branched alkyl group having 3 to 20C atoms, or a branched alkoxy group having 3 to 20C atoms, or a branched thioalkoxy group having 3 to 20C atoms, or a cyclic alkyl group having 3 to 20C atoms, or a cyclic alkoxy group having 3 to 20C atoms, or a cyclic thioalkoxy group having 3 to 20C atoms, or a silyl group, or a keto group having 1 to 20C atoms, or an alkoxycarbonyl group having 2 to 20C atoms, or an aryloxycarbonyl group having 7 to 20C atoms, a cyano group, a carbamoyl groupRadicals, haloformyl, formyl, isocyano, isocyanate, thiocyanate, or isothiocyanate, hydroxyl, nitro, amine, -CF₃-Cl, -Br, -F, -I, or a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or a substituted or unsubstituted aryloxy group having 5 to 60 ring atoms, or a substituted or unsubstituted heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups;

R₃and R₄With or without rings formed therebetween.

It is understood that in the present application, when X is a linking site, X is C; when Y is the attachment site, Y is N.

By way of example, the organic compound may be selected from, but is not limited to, any of the following structures:

in some embodiments, the organic compounds of the present application may be applied as organic functional materials in functional layers of organic electronic devices, in particular OLED devices. The functional material may be, but is not limited to, a Hole Injection Material (HIM), a Hole Transport Material (HTM), an Electron Transport Material (ETM), an Electron Injection Material (EIM), an Electron Blocking Material (EBM), a Hole Blocking Material (HBM), an Emitter (Emitter), a Host material (Host), or an organic dye.

In some embodiments, the organic compounds of the present application can be used as light emitting materials in the light emitting layer of organic electronic devices. In some preferred embodiments, the organic compounds of the present application are used as host materials in the emissive layer of organic electronic devices.

The application also relates to a mixture comprising at least one organic compound as defined above, and at least one further organic functional material. The other organic functional material may be, but is not limited to, a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a light emitting material, a host material, a guest material, and an organic dye, which are known in the art for use in organic electronic devices.

In some embodiments, the further organic functional material is selected from guest materials. Further, the another organic functional material is selected from a blue light guest material. Further, the blue guest is represented by the following general formula (5).

The present application also relates to a composition comprising at least one organic compound or mixture as described above, and at least one organic solvent.

In particular, the at least one organic solvent is selected from aromatic or heteroaromatic-based solvents, ester-based solvents, aromatic ketone-based solvents, aromatic ether-based solvents, aliphatic ketones, aliphatic ethers, cycloaliphatic compounds, olefinic compounds, borate compounds or phosphate compounds.

It is to be understood that the organic solvent may be used alone or as a mixed solvent of two or more organic solvents.

In some embodiments, the compositions herein comprise at least one organic compound or mixture as described above, and at least one organic solvent, and may further comprise another organic solvent.

In some preferred embodiments, the organic solvent suitable for the present application is a solvent having Hansen (Hansen) solubility parameters in the following ranges:

δ d (dispersion force) in the range of 17.0-23.2MPa1/2, especially in the range of 18.5-21.0MPa 1/2;

δ p (polar force) in the range of 0.2-12.5MPa1/2, especially in the range of 2.0-6.0MPa 1/2;

delta h (hydrogen bonding force) is in the range of 0.9-14.2MPa1/2, especially in the range of 2.0-6.0MPa 1/2.

In some embodiments, the organic solvent is selected with a boiling point in mind, in accordance with the compositions herein. In at least some embodiments, the organic solvent has a boiling point of 150 ℃ or higher; preferably equal to or more than 180 ℃; more preferably more than or equal to 200 ℃; more preferably more than or equal to 250 ℃; most preferably at least 300 ℃. Boiling points in these ranges are beneficial for preventing nozzle clogging in inkjet print heads.

It is understood that the organic solvent can be evaporated from the composition system to form a thin film comprising the organic compound of the present application.

In some embodiments, the composition is a solution. In other embodiments, the composition is a suspension.

The content of the organic compound or the mixture in the composition may be 0.01 to 10 wt%, preferably 0.1 to 8 wt%, more preferably 0.2 to 5 wt%, and still more preferably 0.25 to 3 wt%.

The application also relates to the use of said composition as a coating or printing ink for the preparation of organic electronic devices. In some embodiments, the composition is used to prepare organic electronic devices by a printing or coating preparation method. The printing or coating may be prepared by, but is not limited to, ink jet printing, gravure printing, jet printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roll printing, twist roll printing, offset printing, flexographic printing, rotary printing, spraying, brushing, pad printing, slot die coating, and the like. Gravure printing, jet printing and ink-jet printing are preferred.

The solution or suspension may additionally include additives for adjusting viscosity, adjusting film-forming properties, improving adhesion, and the like. The additive may be selected from, but is not limited to, at least one of a surface active compound, a lubricant, a wetting agent, a dispersant, a hydrophobic agent, and a binder. The requirements for the coating or printing ink may differ for different printing or coating modes, and the concentration, viscosity, etc. of the solution or suspension may be adjusted accordingly to accommodate different printing or coating modes.

The present application also provides the use of an organic compound, mixture or composition as described above in an organic electronic device. The technical scheme is as follows:

an organic electronic device comprising an organic compound or mixture as described above, or prepared from the composition.

Further, an organic electronic device comprising a first electrode, a second electrode, one or more organic functional layers located between the first electrode and the second electrode, said organic functional layers comprising an organic compound, mixture or prepared from a composition as described above.

The organic functional layer is selected from a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emission layer (EML), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL) and a Hole Blocking Layer (HBL).

The Organic electronic device may be, but is not limited to, an Organic light Emitting Diode (OLED device), an Organic photovoltaic cell (OPV), an Organic light Emitting cell (OLEEC), an Organic Field Effect Transistor (OFET), an Organic light Emitting field effect transistor (oelt), an Organic laser, an Organic spintronic device, an Organic sensor, an Organic Plasmon Emitting Diode (Organic plasma Emitting Diode), and the like. The organic electronic device is preferably an OLED device. Further, in an embodiment, the organic compound is preferably used in a light emitting layer of an OLED device, the light emitting layer comprising the organic compound or mixture as described above, or prepared from the composition.

In some embodiments, the one or more organic functional layers of the organic electronic device include at least a light emitting layer. The material of the light-emitting layer comprises a host material and a guest material. The host material comprises the organic compound and the guest material comprises a pyrene organic compound.

The present application further relates to an organic electronic device comprising: the organic light-emitting diode comprises a cathode, an anode and one or more organic functional layers positioned between the cathode and the anode, wherein the organic functional layers at least comprise a light-emitting layer, the light-emitting layer material comprises a host material and a guest material, the host material comprises the organic compound shown in the general formula (1), and the guest material is the pyrene organic compound shown in the compound (5).

It is understood that the organic electronic device may further add some functional layers that are conventionally used in organic electronic devices and contribute to the performance of the device, such as an electron transport layer, an electron injection layer, an electron blocking layer, a hole transport layer, a hole injection layer, a hole blocking layer, a light extraction layer, and the like.

In one embodiment, the organic electronic device comprises a cathode, an anode, a hole transport layer, a light emitting layer, and an electron transport layer.

In one embodiment, the organic electronic device comprises a cathode, an anode, a hole transport layer, a hole injection layer, a light emitting layer, and an electron transport layer.

In one embodiment, the organic electronic device comprises a cathode, an anode, a hole transport layer, a hole injection layer, a light emitting layer, an electron blocking layer and an electron transport layer.

Suitable materials for use in these functional layers are described in detail above and in WO2010135519A1, US20090134784A1 and WO2011110277A1, the entire contents of which 3 are hereby incorporated by reference.

In some embodiments, the organic electronic device further comprises a substrate. The substrate may be located on a side of the anode away from the light-emitting layer, or may be located on a side of the cathode away from the light-emitting layer. The substrate may be opaque or transparent. It is understood that when the substrate is transparent, the organic electronic device is a transparent light emitting device. The substrate may also be rigid or flexible, for example the material of the substrate may be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface, and a substrate free of surface defects is particularly desirable. In a preferred embodiment, the substrate is a flexible substrate. The material of the flexible substrate may be a polymer film or plastic. The glass transition temperature Tg of the flexible substrate is 150 ℃ or higher, preferably more than 200 ℃, more preferably more than 250 ℃, and most preferably more than 300 ℃. As an example, the material of the flexible substrate may be poly (ethylene terephthalate) (PET) or polyethylene glycol (2, 6-naphthalene) (PEN).

The material of the anode is an anode material known in the art for organic electronic devices, such as a conductive metal, a conductive metal oxide, or a conductive polymer. In some embodiments, the absolute value of the difference between the work function of the material of the anode and the HOMO level or valence band level of the emitter in the light emitting layer or the p-type semiconductor material as hole injection layer or hole transport layer or electron blocking layer is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. As an example, the material of the anode may be selected from, but not limited to, at least one of Al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, and aluminum-doped zinc oxide (AZO). Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is pattern structured. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present application.

The material of the cathode is a cathode material known in the art for organic electronic devices, such as a conductive metal or a conductive metal oxide. In some embodiments, the absolute value of the difference between the work function of the material of the cathode and the LUMO level or conduction band level of the emitter in the light emitting layer or the n-type semiconductor material as an electron injecting layer or an electron transporting layer or a hole blocking layer is less than 0.5eV, preferably less than 0.3eV, and most preferably less than 0.2 eV. In principle, all materials that can be used as cathodes for OLEDs are possible as cathode materials for the devices of the present application. By way of example, the material of the cathode may be selected from, but is not limited to, at least one of Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, and ITO. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.

The material of the hole transport layer is a material known in the art for hole transport layer materials, and may be selected from, for example, but not limited to, poly [ bis (4-phenyl) (2,4, 6-trimethylphenyl) amine ] (PTXX), 2',7,7' -tetrakis [ N, N-bis (4-methoxyphenyl) amino ] -9,9 '-spirobifluorene (spiro-omeTXD), 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ] (TXPC), N '-bis (1-naphthyl) -N, N' -diphenyl-1, 1 '-diphenyl-4, 4' -diamine (NPB), 4 '-bis (N-carbazole) -1,1' -biphenyl (CBP), poly [ (9, 9-dioctylfluorenyl-2, 7-diyl) -co- (4,4'- (N- (p-butylphenyl)) diphenylamine) ] (TFB), Poly (9-vinylcarbazole) (PVK), polytriphenylamine (Poly-TPD), Poly (3, 4-ethylenedioxythiophene) -Poly (styrenesulfonic acid) (PEDOT: PSS) and 4,4' -tris (carbazol-9-yl) triphenylamine (TCTX).

The material of the electron transport layer is a material known in the art for electron transport layers, and may be selected from, for example, but not limited to, ET and Liq, PBD (2- (4-biphenyl) -5-phenyl oxadiazole), 8-hydroxyquinoline aluminum (Xlq)₃) And graphene.

Wherein the chemical structural formulas of ET and Liq are as follows:

the material of the hole injection layer is a material known in the art for hole injection layers, and may be selected from, for example, but not limited to, 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylene (HXT-CN), PEDOT (polyethylenedioxythiophene), PEDOT: PSS, and s-MoO doped therewith₃(PEDOT: PSS: s-MoO)₃) At least one of (1).

In at least one preferred embodiment, the organic electronic device is an OLED device. More preferably, the organic electronic device is a solution-type OLED.

The organic electronic device has a light emission wavelength of 300nm to 1000nm, preferably 350nm to 900nm, more preferably 400nm to 800 nm.

The application also relates to an electronic device comprising said organic electronic device. The electronic device may be, but is not limited to, a display device, a lighting device, a light source, a sensor, and the like.

The present application will be specifically described below with reference to specific examples, which are only some examples of the present application and are not intended to limit the present application.

Example 1

The synthetic route for compound 1 of this example is as follows:

synthesis of intermediate 1-1:

2, 7-dihydroxynaphthalene (16g, 100mmol) was dissolved in DMF (100ml), bromine (32g, 200mmol) was dissolved in DMF (50ml), and slowly added dropwise to the 2, 7-dihydroxynaphthalene solution. Stir at room temperature for 2 h. After the reaction is finished, adding sodium thiosulfate aqueous solution to remove the residual bromine, removing most of the solvent by rotary evaporation, then extracting, washing the separated liquid by water, and performing organic phase column chromatography (eluent is PE: DCM ═ 1:1) and recrystallization to obtain an intermediate 1-1, wherein the yield is as follows: 95 percent. Ms (asap) ═ 317.9.

Synthesis of intermediates 1-2:

intermediate 1-1(10g, 32mmol), 2-fluorobenzeneboronic acid (13.2g, 95mmol) were dissolved in a mixed solvent of 1, 4-dioxane and water (100ml/10ml), and Pd (PPh) was added₃)₄(1.8g, 1.6mmol) and potassium carbonate (22g, 160 mmol). Stirring at 100 ℃ for 12h under nitrogen atmosphere. After cooling, most of the solvent was removed by rotary evaporation, then the fractions were extracted and washed with water, column chromatographed on organic phase (eluent PE: DCM ═ 1:1) and recrystallized to give intermediate 1-2, yield: 61 percent. Ms (asap) ═ 348.1.

Synthesis of intermediates 1 to 3:

intermediate 1-2(8g, 23mmol) was placed in a 100ml two-necked flask, N-methylpyrrolidone (30ml) was added to complete dissolution, cesium carbonate (37g, 115mmol) was added, and stirring was carried out at 180 ℃ for 12h under a nitrogen atmosphere. After cooling, the solvent was distilled off under reduced pressure, followed by addition of dichloromethane, washing of the separated liquid with water, organic phase column chromatography (eluent PE: DCM ═ 5:1) and recrystallization to give intermediates 1 to 3 in 44% yield. Ms (asap) ═ 308.1.

Synthesis of intermediates 1 to 4:

the intermediates 1 to 3(10g,32mmol) were placed in a 250ml two-necked flask, 100ml of DMF was added until the solid was completely dissolved, NBS (5.8g,32mmol) was weighed out and placed in an isobaric dropping funnel, dissolved in 50ml of DMF and slowly added dropwise, and the reaction was carried out at room temperature for 12 hours. Spin-drying, washing with water, and performing column chromatography (eluent PE) to obtain white solid with yield of 91%. Ms (asap) ═ 386.0

Synthesis of Compound 1:

the intermediate 1-4(3.9g, 10mmol), 10-phenyl-9-anthraceneboronic acid (5.4g, 14mmol) were dissolved in a mixed solvent of 1, 4-dioxane and water (100ml/10ml), and Pd (PPh) was added₃)₄(0.18g, 0.2mmol) and potassium carbonate (6.9g, 50 mmol). Stirring at 100 ℃ for 12h under nitrogen atmosphere. After cooling, most of the solvent was removed by rotary evaporation, followed by extraction and washing of the separated liquid with water, organic phase column chromatography (eluent PE: DCM ═ 5:1) and recrystallization to give compound 1, yield: 53 percent. Ms (asap) ═ 560.2.

Example 2

The synthetic route for compound 2 of this example is as follows:

synthesis of Compound 2:

the intermediate 1-4(3.9g, 10mmol) and 10- (1-naphthyl) -9-anthraceneboronic acid (4.9g, 14mmol) are dissolved in a mixed solvent of 1, 4-dioxane and water (100ml/10ml), and Pd is added₂(dba)₃(0.18g, 0.2mmol), s-phos (0.16g, 0.4mmol) and potassium carbonate (6.9g, 50 mmol). Stirring at 100 ℃ for 12h under nitrogen atmosphere. After cooling, most of the solvent was removed by rotary evaporation, followed by extraction and washing of the separated liquid with water, organic phase column chromatography (eluent PE: DCM ═ 5:1) and recrystallization to give compound 2, yield: 84 percent. Ms (asap) ═ 610.2.

Example 3

The synthetic route for compound 3 of this example is as follows:

synthesis of intermediate 3-1:

intermediate 9, 10-dibromoanthracene (6.7g, 20mmol) and dibenzo [ b, d ]]Furan-2-boronic acid (4.3g, 20mmol) was dissolved in a mixed solvent of 1, 4-dioxane and water (100/10ml), and Pd (PPh) was added₃)₄(1.2g, 1mmol) and potassium carbonate (14g, 100 mmol). Stirring was carried out at 100 ℃ for 12h under a nitrogen atmosphere. After cooling, most of the solvent is removed by rotary evaporation, then liquid is extracted and washed by water, and the intermediate 3-1 is obtained by organic phase column chromatography and recrystallization, and the yield is as follows: 58 percent. Ms (asap) ═ 422.0

Synthesis of intermediate 3-2

Preparing a dry 250mL three-neck flask, building a reaction device, vacuumizing, and introducing nitrogen; keeping nitrogen circulation in a reaction bottle, weighing 3-1(5.0g,11.8mmol), adding THF (100ml), vacuumizing, circulating for three times by introducing nitrogen, and cooling to-78 ℃; an n-butyllithium solution (4.7ml,11.8mmol) was slowly dropped into the reaction flask, and after reacting at-78 ℃ for 60min, triethyl borate (1.7g,11.8mmol) was slowly dropped. The reaction was allowed to slowly warm to room temperature and allowed to react for 12 h. Adding dilute hydrochloric acid, stirring for 30 min, extracting with EA, spin-drying the solvent, and pulping with PE to obtain white solid. The yield thereof was found to be 88%. Ms (asap) ═ 388.1 synthesis of compound 3:

intermediate 3-2(3.9g, 10mmol) and intermediate 1-4(3.9g, 10mmol) were dissolved in a mixed solvent of 1, 4-dioxane and water (100ml/10ml), and Pd (PPh) was added₃)₄(0.18g, 0.2mmol) and potassium carbonate (6.9g, 50 mmol). Stirring at 100 ℃ for 12h under nitrogen atmosphere. After cooling, most of the solvent was removed by rotary evaporation, followed by extraction and washing of the separated liquid with water, organic phase column chromatography (eluent PE: DCM ═ 5:1) and recrystallization to give compound 3, yield: 76 percent. Ms (asap) ═ 650.2.

Example 4

The synthetic route for compound 4 of this example is as follows:

synthesis of intermediate 4-1:

9, 10-dibromoanthracene (3.4g, 10mmol) and fluoranthene-3-boronic acid (2.5g, 10mmol) were dissolved in a mixed solvent of 1, 4-dioxane and water (100ml/10ml), and Pd (PPh) was added₃)₄(1.15g, 1mmol) and potassium carbonate (8.3g, 60 mmol). Stirring was carried out at 100 ℃ for 12h under a nitrogen atmosphere. After cooling, most of the solvent is removed by rotary evaporation, then liquid is extracted and washed by water, and the intermediate 4-1 is obtained by organic phase column chromatography and recrystallization, and the yield is as follows: and 64 percent. Ms (asap) ═ 456.1.

Synthesis of intermediate 4-2

Preparing a dry 250mL three-neck flask, building a reaction device, vacuumizing, and introducing nitrogen; keeping nitrogen circulation in a reaction bottle, weighing 4-1(4.6g,10mmol), adding THF (100ml), vacuumizing, circulating for three times by introducing nitrogen, and cooling to-78 ℃; an n-butyllithium solution (4.8ml,12mmol) was slowly dropped into the reaction flask, and after reacting at-78 ℃ for 60min, triethyl borate (1.8g,12mmol) was slowly dropped. The reaction was allowed to slowly warm to room temperature and allowed to react for 12 h. Adding dilute hydrochloric acid, stirring for 30 min, extracting with EA, spin-drying the solvent, and pulping with PE to obtain white solid. The yield thereof was found to be 82%. Ms (asap) ═ 422.2 synthesis of compound 4:

intermediate 4-2(4.2g, 10mmol) and intermediate 1-4(3.9g, 10mmol) were dissolved in a mixed solvent of 1, 4-dioxane and water (100ml/10ml), and Pd (PPh) was added₃)₄(0.18g, 0.2mmol) and potassium carbonate (6.9g, 50 mmol). Stirring was carried out at 100 ℃ for 12h under a nitrogen atmosphere. After cooling, most of the solvent was removed by rotary evaporation, followed by extraction and washing of the separated liquid with water, organic phase column chromatography (eluent PE: DCM ═ 5:1) and recrystallization to give compound 4, yield: 84 percent. Ms (asap) ═ 684.2.

Example 5

The synthetic route for compound 5 of this example is as follows:

synthesis of intermediate 5-1:

9, 10-dibromoanthracene (3.4g, 10mmol), 1-pyreneboronic acid (2.5g, 10mmol) were dissolved in a mixed solvent of 1, 4-dioxane and water (100ml/10ml), and Pd (PPh) was added₃)₄(1.15g, 1mmol) and potassium carbonate (8.3g, 60 mmol). Stirring was carried out at 100 ℃ for 12h under a nitrogen atmosphere. After cooling, most of the solvent is removed by rotary evaporation, then liquid is extracted and washed by water, and the intermediate 5-1 is obtained by organic phase column chromatography and recrystallization, and the yield is as follows: 73 percent. Ms (asap) ═ 456.1.

Synthesis of intermediate 5-2:

preparing a dry 250mL three-neck flask, building a reaction device, vacuumizing, and introducing nitrogen; keeping nitrogen circulation in a reaction bottle, weighing 5-1(4.6g,10mmol), adding THF (100ml), vacuumizing, circulating for three times by introducing nitrogen, and cooling to-78 ℃; an n-butyllithium solution (4.9ml,12mmol) was slowly dropped into the reaction flask, and after reacting at-78 ℃ for 60min, triethyl borate (1.8g,12mmol) was slowly dropped. The reaction was allowed to slowly warm to room temperature and allowed to react for 12 h. Adding dilute hydrochloric acid, stirring for 30 min, extracting with EA, spin-drying the solvent, and pulping with PE to obtain white solid. The yield thereof was found to be 87%. Ms (asap) ═ 422.2

Synthesis of Compound 5:

intermediate 5-2(4.2g, 10mmol) and intermediate 1-4(3.9g, 10mmol) were dissolved in a mixed solvent of 1, 4-dioxane and water (100/10ml), and Pd (PPh) was added₃)₄(0.18g, 0.2mmol) and potassium carbonate (6.2g, 45 mmol). Stirring was carried out at 100 ℃ for 12h under a nitrogen atmosphere. After cooling, most of the solvent was removed by rotary evaporation, followed by extraction and water washing of the separated liquid, organic phase column chromatography and recrystallization to give compound 5, yield: 66 percent. Ms (asap) ═ 684.2.3

Comparative example

The organic compound of this comparative example was BH-Ref, and its chemical formula was as follows:

the preparation of an OLED device comprising the above compound is described in detail below by means of specific examples. The OLED device has the structure that: ITO/HIL/HTL/EML/ETL/cathode, a schematic diagram of the OLED device is shown in fig. 1, where 101 is a substrate, 102 is an anode, 103 is a Hole Injection Layer (HIL), 104 is a Hole Transport Layer (HTL), 105 is an emission layer, 106 is an Electron Transport Layer (ETL), and 107 is a cathode.

The structural formulas of Liq, ET and BD-1 of compounds that may be involved in the OLED preparation are as follows:

the preparation steps of the OLED-1 are as follows:

a. cleaning an ITO (indium tin oxide) conductive glass substrate: washing with various solvents (e.g., one or more of chloroform, acetone, or isopropyl alcohol), followed by ultraviolet ozone treatment.

b. HIL (hole injection layer, 40 nm): 40nm PEDOT (polyethylenedioxythiophene, Clevios)^TMAI4083) was spin coated as HIL in a clean room and treated on a hot plate at 180 ℃ for 10 minutes.

c. HTL (hole transport layer, 20 nm): 20nm of PVK (Sigma Aldrich, average Mn 25,000-50,000) was spin-coated in a nitrogen glove box using PVK added to toluene solvent at a solution solubility of 5mg/ml, followed by treatment on a hot plate at 180 ℃ for 60 minutes.

d. EML (organic light emitting layer, 40 nm): the EML was prepared by spin coating in a nitrogen glove box using solutions of methyl benzoate with 15mg/ml solubility in a solution of different host and guest materials (95: 5 by weight) selected from BD-1, Compound 1 of example 1, followed by treatment on a hot plate at 140 ℃ for 10 minutes.

e. Electron transport layer and cathode: the heat treated substrates were transferred to a vacuum chamber, followed by placing ET and Liq in different evaporation units under high vacuum (1 × 10)^-6Mbar) was co-deposited at a rate of 50 wt% each, to form an electron transport layer of 20nm on the light-emitting layer, followed by deposition of an Al cathode having a thickness of 100 nm.

f. Packaging: the devices were encapsulated with ultraviolet curable resin in a nitrogen glove box.

The fabrication schemes for devices OLED-2-OLED-5 and OLED-Ref are the same as OLED-1, except that compound 1 in example OLED-1 is replaced with the compound corresponding to the host material in Table one.

The current-voltage (J-V) characteristics of each OLED device were characterized by a characterization instrument, while recording the color efficiency (CE @1knits) and lifetime (LT90@1knits), the results of which are given in Table one below.

Table one:

device embodiments	Host material	CE@1knits[cd/A]	LT90@1knits[h]
				OLED-1	Compound 1	5.8	322
OLED-2	Compound 2	6.2	385
				OLED-3	Compound 3	6.5	356
OLED-4	Compound 4	7.1	338
				OLED-5	Compound 5	6.7	352
OLED-Ref	BH-ref	5.1	251

From table one, it can be seen that: the OELD devices prepared using the organic compounds 1 to 5 of examples 1 to 5 as host materials in the emission layer have better color coordinates and longer life than blue OELD devices prepared using the organic compounds of comparative examples as host materials in the emission layer.

In addition, the light-emitting efficiency of the blue-light OELD devices prepared by using the compounds 1-5 of examples 1-5 as host materials in the light-emitting layer is in the range of 5-8cd/A, and the light-emitting efficiency is more excellent.

The anthracene organic compound containing the heterocyclic fused ring has fluorescence emission at blue light wavelength, can be used as a main material for a light emitting layer of an organic electronic device, and the organic electronic device prepared from the organic compound has good light emitting efficiency and long device service life.

The organic compounds, mixtures, compositions and organic electronic devices provided in the examples of the present application are described in detail, and the principles and embodiments of the present application are described herein using specific examples, which are merely provided to help understand the method and core concepts of the present application; meanwhile, for those skilled in the art, according to the idea of the present application, there may be variations in the specific embodiments and the application scope, and in summary, the content of the present specification should not be construed as a limitation to the present application.

Claims

1. An organic compound having a structure represented by general formula (1):

Ar₁selected from substituted or unsubstituted aromatic groups containing from 6 to 60 ring atoms, or substituted or unsubstituted heteroaromatic groups containing from 5 to 60 ring atoms, or combinations of these groups.

2. The organic compound of claim 1, wherein Ar is Ar₁A structure selected from any one of:

wherein:

x is independently selected from CR at each occurrence₁Or N;

y is selected from NR₂、CR₃R₄、SiR₃R₄O, S, S ═ O or SO₂；

R₁、R₂、R₃、R₄Independently at each occurrence is selected from-H, -D, or a linear alkyl group having 1 to 20C atoms, a linear alkoxy group having 1 to 20C atoms, or a linear thioalkoxy group having 1 to 20C atoms, or a branched alkyl group having 3 to 20C atoms, or a branched alkoxy group having 3 to 20C atoms, or a branched thioalkoxy group having 3 to 20C atoms, or a cyclic alkyl group having 3 to 20C atoms, or a cyclic alkoxy group having 3 to 20C atoms, or a cyclic thioalkoxy group having 3 to 20C atoms, or a silyl group, or a keto group having 1 to 20C atomsAlkoxycarbonyl of 2 to 20C atoms or aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanate, thiocyanate, or isothiocyanate, hydroxyl, nitro, amine, -CF₃-Cl, -Br, -F, -I, or a substituted or unsubstituted aromatic group having 6 to 60 ring atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, or a substituted or unsubstituted aryloxy group having 5 to 60 ring atoms, or a substituted or unsubstituted heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups;

R₃and R₄With or without rings formed therebetween.