CN111278813A

CN111278813A - Organic compounds, polymers, organic mixtures, compositions and their applications in organic electronic devices

Info

Publication number: CN111278813A
Application number: CN201880069730.3A
Authority: CN
Inventors: 杨曦; 潘君友; 王璞
Original assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Current assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Priority date: 2017-12-27
Filing date: 2018-12-20
Publication date: 2020-06-12
Anticipated expiration: 2038-12-20
Also published as: WO2019128849A1; CN111278813B

Abstract

The present invention relates to an organic compound and its use in organic electronic devices, in particular in organic electroluminescent diodes. The invention also relates to organic electronic components, in particular organic electroluminescent diodes, comprising the organic compounds according to the invention and to the use thereof in display and illumination technology. The invention further relates to organic electronic devices prepared using the compositions according to the invention, and to methods of preparation. Through the optimization of the device structure, better device performance can be achieved, particularly high-performance OLED devices can be realized, and better materials and preparation technical options are provided for full-color display and illumination applications.

Description

Organic compounds, polymers, organic mixtures, compositions and their use in organic electronic devices

The present application claims priority from the chinese patent office filed on 27/12/2017, entitled "organic compounds and their use in organic electronic devices" under the patent application No. 201711451356.7, the entire contents of which are incorporated herein by reference.

Technical Field

The invention relates to the technical field of organic electroluminescence, in particular to an organic compound, a mixture and a composition, and application thereof in the field of organic electroluminescence.

Background

Organic Light Emitting Diodes (OLEDs), which have excellent properties such as light weight, active light emission, wide viewing angle, high contrast, high light emitting efficiency, low power consumption, easy fabrication of flexible and large-sized panels, are considered as the most promising next-generation display technology in the industry. In order to improve the light emitting efficiency of the organic light emitting diode and promote the large-scale industrialization process of the organic light emitting diode, the key problems of the organic light emitting diode, namely the light emitting performance and the service life, are urgently needed to be solved.

To obtain a high performance organic light emitting diode, the host material is critical. Currently, a single main body material is generally adopted to prepare an OLED light-emitting device together with a light-emitting body, but the single main body material can cause different carrier transmission rates, so that the Roll-off (Roll-off) of the device efficiency is serious under high brightness, and the service life of the device is shortened. The double-main-body material can weaken some problems caused by a single main body, and particularly, the selected double-main-body material can effectively form a composite excited state (exiplex) through proper material matching, so that the luminous efficiency and the service life of the device are greatly improved. One technique achieves low Roll-off, high efficiency OLEDs by using a Co-host (Co-host) capable of forming complex excited states (exiplex), plus a metal complex as a phosphorescent emitter.

Further, in the evaporation device, by forming the double-host material into a blend or an organic alloy in advance, the evaporation process can be greatly simplified, and the service life of the device can be remarkably prolonged.

There is still a need for further improved materials, in particular host material systems suitable for forming co-hosts, especially p-type host materials with hole transport properties. And the organic electroluminescent element is matched with the n-type main body or the bipolar main body to form the common main body, so that the organic electroluminescent element has good efficiency and service life, is easy to repeat in the manufacturing and operation of the device, and has simple material synthesis.

Disclosure of Invention

Based on this, it was an object of the present invention to provide an organic compound and its use in electronic devices.

The specific technical scheme is as follows:

one embodiment of the present invention provides an organic compound represented by the general formula (I):

A——(L₁)s——B (I)

wherein,

L₁selected from substituted or unsubstituted aromatic or heteroaromatic ring systems having from 5 to 40 ring atoms, or aryloxy or heteroaryloxy groups having from 5 to 40 ring atoms, or combinations of these systems, wherein one or more of the radicals can form a mono-or polycyclic aliphatic or aromatic ring system with one another and/or with the ring to which the radicals are bonded.

S is 0 or 1.

A is a compound having a structure represented by the general formula (II), and B is a compound having a structure represented by the general formula (III):

wherein,

X₁selected from O, S, CR₁₀₅R₁₀₆、SiR₁₀₈R₁₀₉。

X₂Selected from NR₁₁₀、CR₁₁₁R₁₁₂、SiR₁₁₃R₁₁₄。

R₁₀₁-R₁₁₄Is a substituent selected, independently of one another, from D, or a straight-chain alkyl, alkoxy or thioalkoxy group having from 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having from 3 to 20C atoms, or a substituted or unsubstituted silyl group, or a substituted keto group having from 1 to 20C atoms, or an alkoxycarbonyl group having from 2 to 20C atoms, or an aryloxycarbonyl group having from 7 to 20C atoms, a cyano group (-CN), a carbamoyl group (-C (═ O) NH₂) Haloformyl (-C (═ O) -X wherein X represents a halogen atom), formyl (-C (═ O) -H), isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxy, nitro, CF₃Cl, Br, F, crosslinkable groups, or substituted or unsubstituted aromatic or unsubstituted having 5 to 40 ring atomsHeteroaromatic ring systems, or aryloxy or heteroaryloxy groups having from 5 to 40 ring atoms, or combinations of these systems, where one or more of the radicals can form a mono-or polycyclic aliphatic or aromatic ring system with one another and/or with the ring bonded to said radical.

m is an integer of 0 to 8. n is an integer of 0 to 5. p is an integer of 0 to 8. t is an integer of 0 to 8.

The invention also provides a high polymer, which comprises a repeating unit, wherein the repeating unit comprises a structure shown as the general formula (1).

The invention also provides an organic mixture, which comprises the organic compound and at least another organic functional material, wherein the another organic functional material can be selected from a hole (also called hole) injection or transmission material, a hole blocking material, an electron injection or transmission material, an electron blocking material, an organic matrix material, a singlet state light emitter (fluorescent light emitter), a triplet state light emitter (phosphorescent light emitter), a thermal excitation delayed fluorescence material (TADF material) and an organic dye.

The organic mixture as described above, comprising at least one organic compound as described above as the first organic compound (H1) and one second organic compound (H2), the at least second organic compound having an electron transporting property. Preferably, the molar ratio of the first organic compound (H1) to the second organic compound (H2) is in the range of 1:9 to 9: 1.

The invention also provides a composition comprising an organic compound or polymer as described above, or an organic mixture as described above, and at least one organic solvent.

The invention also provides an organic electronic device comprising an organic compound or polymer as described above, or an organic mixture as described in any of the above.

The organic electronic device can be selected from an organic light emitting diode, an organic photovoltaic cell, an organic light emitting cell, an organic field effect transistor, an organic light emitting field effect transistor, an organic laser, an organic spin electronic device, an organic sensor and an organic plasmon emitting diode.

The organic electronic device as described above is an organic electroluminescent device comprising a light-emitting layer comprising an organic compound or polymer as described above, or an organic mixture as described above.

The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the invention will be apparent from the description and drawings, and from the claims.

Has the advantages that:

The organic compound has excellent hole transport property and stability, and can be matched with another body with electron transport property or bipolar property to form a common body, so that the electroluminescent efficiency and the service life of a device can be improved.

drawings

For a better understanding of the description and/or illustration of embodiments and/or examples of those inventions disclosed herein, reference may be made to one or more of the drawings. The additional details or examples used to describe the figures should not be considered as limiting the scope of any of the disclosed inventions, the presently described embodiments and/or examples, and the presently understood best modes of these inventions.

Fig. 1 is a structural view of a light emitting device according to an embodiment of the present invention, in which 101 is a substrate, 102 is an anode, 103 is a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL), 104 is a light emitting layer, 105 is an Electron Injection Layer (EIL) or an Electron Transport Layer (ETL), and 106 is a cathode.

Detailed description of the invention:

to facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

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 invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

In the present invention, the Host material, the Matrix material, the Host material and the Matrix material have the same meaning and may be interchanged.

In the present invention, the metal-organic complex, and the organometallic complex have the same meanings and may be interchanged.

In the present invention, the composition, printing ink, and ink have the same meaning and may be interchanged.

The present invention provides an organic compound represented by the general formula (I):

A——(L₁)s——B (I)

wherein,

In certain embodiments, L₁Identical or different are substituted or unsubstituted aromatic or heteroaromatic ring systems having from 5 to 30 ring atoms or aryloxy or heteroaryloxy groups having from 5 to 30 ring atoms or combinations of these systems, it being possible for one or more of the radicals to form a mono-or polycyclic aliphatic or aromatic ring system with one another and/or with the ring bonded to said radical.

In certain embodiments, L₁Identical or different are substituted or unsubstituted aromatic or heteroaromatic ring systems having from 5 to 20 ring atoms or aryloxy or heteroaryloxy groups having from 5 to 20 ring atoms or combinations of these systems, it being possible for one or more of the radicals to form a single ring or a plurality of rings bonded to one another and/or to the radicalsCyclic aliphatic or aromatic ring systems.

In certain embodiments, L₁Identical or different are substituted or unsubstituted aromatic or heteroaromatic ring systems having from 5 to 15 ring atoms or aryloxy or heteroaryloxy groups having from 5 to 15 ring atoms or combinations of these systems, it being possible for one or more of the radicals to form a mono-or polycyclic aliphatic or aromatic ring system with one another and/or with the ring bonded to said radical.

In certain embodiments, L₁Identical or different are substituted or unsubstituted aromatic or heteroaromatic ring systems having from 5 to 10 ring atoms or aryloxy or heteroaryloxy groups having from 5 to 10 ring atoms or combinations of these systems, it being possible for one or more of the radicals to form a mono-or polycyclic aliphatic or aromatic ring system with one another and/or with the ring bonded to said radical.

In other preferred embodiments, L₁Is benzene, naphthalene, phenanthrene, triphenylene, biphenyl, terphenyl, or one or more carbon atoms in these structures are substituted by N atoms.

In a preferred embodiment, L₁Is biphenyl. In a preferred embodiment, L₁Is naphthalene. In a preferred embodiment, L₁Is benzene.

In a preferred embodiment, the aromatic ring system of the present invention includes

Carbon atoms, more preferably

Having carbon atoms, the heteroaromatic ring system comprising

Carbon atoms, more preferably

Carbon atoms, and at least one heteroatom, with the proviso that the total number of carbon atoms and heteroatoms is at least 4. The heteroatoms are preferably selected from Si, N, P, O, S and/or Ge, particularly preferably from Si, N, P, O and/or S, very particularly preferably from N, O or S.

The above-mentioned aromatic ring system or aromatic group means a hydrocarbon group containing at least one aromatic ring, including monocyclic groups and polycyclic ring systems. The heteroaromatic ring systems or heteroaromatic groups described above refer to hydrocarbon groups (containing heteroatoms) containing at least one heteroaromatic ring, including monocyclic groups and polycyclic ring systems. These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, i.e., fused rings. At least one of these ring species of the polycyclic ring is aromatic or heteroaromatic. For the purposes of the present invention, aromatic or heteroaromatic ring systems include not only aromatic or heteroaromatic systems, but also systems in which a plurality of aryl or heteroaryl groups may also be interrupted by short nonaromatic units (< 10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Thus, for example, systems such as 9,9' -spirobifluorene, 9, 9-diarylfluorene, triarylamines, diaryl ethers, etc., are likewise considered aromatic ring systems for the purposes of the present invention.

Specifically, examples of aromatic groups are: benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, pyrene, benzopyrene, triphenylene, acenaphthene, fluorene, spirofluorene and derivatives thereof.

Specifically, examples of heteroaromatic groups are: furan, benzofuran, dibenzofuran, thiophene, benzothiophene, dibenzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, phthalazine, quinoxaline, phenanthridine, primary pyridine, quinazoline, quinazolinone, and derivatives thereof.

S is 0 or 1.

In a more preferred embodiment, S is 0.

wherein,

X₁selected from O, S, CR₁₀₅R₁₀₆、SiR₁₀₈R₁₀₉(ii) a Preferably, X₁Selected from O or S.

X₂Selected from NR₁₁₀、CR₁₁₁R₁₁₂、SiR₁₁₃R₁₁₄(ii) a Preferably, X₂Selected from NR₁₁₀Or CR₁₁₁R₁₁₂(ii) a More preferably, X₂Selected from NR₁₁₀。

R₁₀₁-R₁₁₄Is D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20C atoms, or a substituted or unsubstituted silyl group, or a substituted 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 (-CN), a carbamoyl group (-C (═ O) NH₂) Haloformyl (-C (═ O) -X wherein X represents a halogen atom), formyl (-C (═ O) -H), isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxy, nitro, CF₃Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having from 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having from 5 to 40 ring atoms, or a combination of these systems, where one or more of the radicals can form a mono-or polycyclic aliphatic or aromatic ring system with one another and/or with the rings to which the radicals are bonded.

In certain preferred embodiments, formula (III) has at least one set of adjacent R₁₀₄May be bonded into a ring.

In some of the preferred embodimentsIn the examples, R₁₀₁-R₁₁₄Is D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 10C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 10C atoms, or a substituted or unsubstituted silyl group, or a substituted keto group having 1 to 10C atoms, or an alkoxycarbonyl group having 2 to 10C atoms, or an aryloxycarbonyl group having 7 to 10C atoms, a cyano group (-CN), a carbamoyl group (-C (═ O) NH₂) Haloformyl (-C (═ O) -X wherein X represents a halogen atom), formyl (-C (═ O) -H), isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxy, nitro, CF₃Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having from 5 to 20 ring atoms, or an aryloxy or heteroaryloxy group having from 5 to 20 ring atoms, or a combination of these systems, where one or more of the radicals can form a mono-or polycyclic aliphatic or aromatic ring system with one another and/or with the rings to which the radicals are bonded.

m is an integer of 0 to 8, preferably an integer of 0 to 6, more preferably an integer of 0 to 4, most preferably an integer of 0 to 2.

n is an integer of 0 to 5, preferably an integer of 0 to 4, more preferably an integer of 0 to 2.

p is an integer of 0 to 8, preferably an integer of 0 to 6, more preferably an integer of 0 to 4, most preferably an integer of 0 to 2.

t is an integer of 0 to 8. Preferably an integer of 0 to 6, more preferably an integer of 0 to 4, most preferably an integer of 0 to 2.

In a preferred embodiment, the organic compound according to the invention is selected from the group consisting of those having the general formula:

wherein,

x1 is selected from O, S, CR₁₀₅R₁₀₆. Preferably O or S.

Ar₁Selected from substituted or unsubstituted aromatic or heteroaromatic ring systems having from 5 to 40 ring atoms, or aryloxy or heteroaryloxy groups having from 5 to 40 ring atoms, or combinations of these systems, wherein one or more of the radicals can form a mono-or polycyclic aliphatic or aromatic ring system with one another and/or with the ring to which the radicals are bonded.

In certain preferred embodiments, Ar₁Identical or different are substituted or unsubstituted aromatic or heteroaromatic ring systems having from 5 to 30 ring atoms or aryloxy or heteroaryloxy groups having from 5 to 30 ring atoms or combinations of these systems, it being possible for one or more of the radicals to form a mono-or polycyclic aliphatic or aromatic ring system with one another and/or with the ring bonded to said radical.

In certain preferred embodiments, Ar₁Identical or different are substituted or unsubstituted aromatic or heteroaromatic ring systems having from 5 to 20 ring atoms or aryloxy or heteroaryloxy groups having from 5 to 20 ring atoms or combinations of these systems, it being possible for one or more of the radicals to form a mono-or polycyclic aliphatic or aromatic ring system with one another and/or with the ring bonded to said radical.

In certain preferred embodiments, Ar₁Identical or different are substituted or unsubstituted aromatic or heteroaromatic ring systems having from 5 to 15 ring atoms or aryloxy or heteroaryloxy groups having from 5 to 15 ring atoms or combinations of these systems, it being possible for one or more of the radicals to form a mono-or polycyclic aliphatic or aromatic ring system with one another and/or with the ring bonded to said radical.

In other preferred embodiments, Ar₁Is benzene, naphthalene, phenanthrene, triphenylene, biphenyl, terphenyl, or one or more carbon atoms in these structures are substituted by N atoms.

In a preferred embodiment, Ar₁Is biphenyl. In a preferred embodiment, Ar₁Is benzene. In other preferred embodiments, Ar₁Is dibenzofuran. In other preferred embodiments, Ar₁Is dibenzothiophene. In other preferred embodiments, Ar₁Is fluorene. In other preferred embodiments, Ar₁Is a spirofluorene.

In a preferred embodiment, the organic compounds according to the invention, said L₁Or Ar₁Each independently selected from one or more combinations of the following structural groups:

wherein,

A¹、A²、A³、A⁴、A⁵、A⁶、A⁷、A⁸each independently represents CR₅₀₁Or N;

Y¹selected from the group consisting of CR₅₀₂R₅₀₃、SiR₅₀₄R₅₀₅、NR₅₀₆C (═ O), S, or O;

R₅₀₁-R₅₀₅is H, or D or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20C atoms or is a silyl group, or a substituted 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 (-CN), a carbamoyl group (-C (═ O) NH₂) A haloformyl group (-C (═ O) -X wherein X represents a halogen atom), a formyl group (-C (═ O) -H), an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, CF₃A radical, Cl, Br, F, a crosslinkable radical or a substituted or unsubstituted aromatic or heteroaromatic ring system having from 5 to 40 ring atoms or an aryloxy or heteroaryloxy radical having from 5 to 40 ring atoms or a combination of these systems, where one or more radicals R³，R⁴，R⁵The rings which may be bonded to each other and/or to the radicals form mono-or polycyclic aliphatic or aromatic rings.

Preferably, R₅₀₁-R₅₀₅Is H, or D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 10C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 10C atoms or a silyl group, or a substituted keto group having 1 to 10C atoms, or an alkoxycarbonyl group having 2 to 10C atoms, or an aryloxycarbonyl group having 7 to 10C atoms, a cyano group (-CN), a carbamoyl group (-C (═ O) NH₂) A haloformyl group (-C (═ O) -X wherein X represents a halogen atom), a formyl group (-C (═ O) -H), an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, CF₃A radical, Cl, Br, F, a crosslinkable radical or a substituted or unsubstituted aromatic or heteroaromatic ring system having from 5 to 20 ring atoms or an aryloxy or heteroaryloxy radical having from 5 to 20 ring atoms, or a combination of these systems, where one or more radicals may form a mono-or polycyclic aliphatic or aromatic ring with one another and/or with the ring bonded to the radical.

In some preferred embodiments, L is₁Or Ar₁One or more combinations selected from the following structural groups, wherein H on the ring can be optionally substituted:

in certain highly preferred embodiments of the organic compounds according to the present invention, A depicted in formula (I) is selected from the structures shown below:

wherein the dotted line is the structure shown and L₁Connected single bond。

In other very preferred embodiments of the organic compounds according to the invention, B in formula (I) is selected from the structures shown below:

wherein the dotted line is the structure shown and L₁A single bond of attachment.

In a preferred embodiment, the compounds according to the invention are at least partially deuterated, preferably 10% H is deuterated, more preferably 20% H is deuterated, even more preferably 30% H is deuterated, and most preferably 40% H is deuterated.

Examples of organic compounds according to the invention are listed below, without being limited thereto:

the invention also relates to a method for synthesizing said organic compounds, wherein starting materials containing reactive groups are used for the reaction. These active starting materials contain at least one leaving group, for example, bromine, iodine, boronic acid or boronic ester. Suitable reactions for forming C-C linkages are well known to those skilled in the art and described in the literature, and particularly suitable and preferred coupling reactions are SUZUKI, STILLE and HECK coupling reactions.

The organic compound according to any one of the embodiments of the present invention has excellent hole transport property and stability, and can be used with another body having electron transport property or bipolar property to form a common body, thereby achieving improved electroluminescent efficiency and device lifetime. The present invention still further relates to a polymer comprising at least one repeating unit comprising a structural unit represented by the general formula (I).

In a preferred embodiment, the polymer is synthesized by a method selected from the group consisting of SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD-and ULLMAN.

In a preferred embodiment, the polymers according to the invention have a glass transition temperature (Tg) of 100 ℃ or more, preferably 120 ℃ or more, more preferably 140 ℃ or more, more preferably 160 ℃ or more, most preferably 180 ℃ or more.

In a preferred embodiment, the polymer according to the invention preferably has a molecular weight distribution (PDI) in the range of 1 to 5; more preferably 1 to 4; more preferably 1 to 3, more preferably 1 to 2, and most preferably 1 to 1.5.

In a preferred embodiment, the polymers according to the invention preferably have a weight-average molecular weight (Mw) ranging from 1 to 100 ten thousand; more preferably 5 to 50 ten thousand; more preferably 10 to 40 ten thousand, still more preferably 15 to 30 ten thousand, and most preferably 20 to 25 ten thousand.

The invention also provides an organic mixture, which comprises the organic compound or the high polymer and at least another organic functional material, wherein the another organic functional material can be selected from a hole (also called hole) injection or transmission material, a hole blocking material, an electron injection or transmission material, an electron blocking material, an organic matrix material, a singlet state light emitter (fluorescent light emitter), a triplet state light emitter (phosphorescent light emitter), a thermal excitation delayed fluorescence material (TADF material) and an organic dye. Various organic functional materials are described in detail, for example, in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of this 3 patent document being hereby incorporated by reference.

In a preferred embodiment, the organic mixture comprises at least one organic compound or polymer according to the invention and an Electron Transport Material (ETM).

In a more preferred embodiment, the organic mixture comprises at least one organic compound or polymer according to the invention and a luminescent material selected from singlet emitters (fluorescent emitters), triplet emitters (phosphorescent emitters) or TADF emitters.

In some embodiments, the organic mixture comprises at least one organic compound or polymer according to the invention and a fluorescent emitter, wherein the fluorescent emitter is present in an amount of 10 wt.% or less, preferably 9 wt.% or less, more preferably 8 wt.% or less, particularly preferably 7 wt.% or less, and most preferably 5 wt.% or less.

In a preferred embodiment, the organic mixture comprises at least one organic compound or polymer according to the invention and a phosphorescent emitter, wherein the phosphorescent emitter is present in an amount of < 25% by weight, preferably < 20% by weight, more preferably < 15% by weight.

In a further preferred embodiment, the organic mixture comprises at least one organic compound or polymer according to the invention, a phosphorescent emitter and a host material. In such embodiments, the organic compound according to the invention and the one host material as co-host in a weight ratio of from 1:9 to 9: 1; in a preferred embodiment, the organic compounds according to the invention form exciplexes with said one host material, which have an energy level higher than that of said phosphorescent emitters.

In another more preferred embodiment, said mixture comprises at least one organic compound or polymer according to the invention and a TADF material. Wherein the function of the TADF material is preferably 1) to form a phosphorescent co-host material with the organic compound according to the invention in a weight ratio of from 1:9 to 9: 1; 2) the weight percentage of the TADF material is less than or equal to 15 wt%, preferably less than or equal to 10 wt%, more preferably less than or equal to 8 wt%.

In a most preferred embodiment, the organic mixture as described above comprises at least one organic compound as described above as the first organic compound (H1) and a second organic compound (H2), the at least second organic compound (H2) having electron transport properties.

Preferably, the at least second organic compound has an electron transporting property and a hole transporting property.

Typically, the molar ratio of the first organic compound (H1) to the second organic compound (H2) is in the range of 1:9 to 9: 1.

Preferably, the molar ratio of the first organic compound (H1) to the second organic compound (H2) ranges from 3:7 to 7: 3.

More preferably, the molar ratio of the first organic compound (H1) to the second organic compound (H2) ranges from 4:6 to 6: 4.

Most preferably, the molar ratio of the first organic compound (H1) to the second organic compound (H2) is 5: 5.

In a preferred embodiment, in the above organic mixture, the second organic compound (H2) contains a fluoro group, or a cyano group or a group having any one of the following general formulas:

wherein,

a is an integer of 1 to 3; x¹–X⁸Is selected from the group consisting of CR⁸⁰¹Or N, and at least one is N; z¹-Z³Is a single bond or C (R)⁸⁰¹)₂Or O or S. R⁸⁰¹May be selected from the following groups: hydrogen, deuterium, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl, and heteroaryl.

More preferably, in the above-mentioned organic mixture, the second organic compound (H2) has a structure represented by the general formula (IV),

wherein,

Z⁴，Z⁵，Z⁶selected from N or CR⁹⁰¹And Z is⁴，Z⁵，Z⁶At least one of which is an N atom.

Ar₁₃～Ar₁₅Identical or different are aromatic or heteroaromatic ring systems having from 5 to 40 ring atoms, or aryloxy or heteroaryloxy groups having from 5 to 40 ring atoms, or nonaromatic groups having from 5 to 40 ring atoms, or combinations of these systems, where one or more radicals may further be substituted by R⁹⁰²Substituted, or R⁹⁰²May further form a ring system with the substituted group. Ar (Ar)₁₃～Ar₁₅When any one of them is plural, each Ar₁₃～Ar₁₅Each may be independently selected from the above groups.

In some preferred embodiments, Ar₁₃～Ar₁₅Identical or different are deuterated or non-deuterated substituted or unsubstituted aromatic or heteroaromatic ring systems having from 5 to 20 ring atoms or deuterated or non-deuterated aryloxy or heteroaryloxy groups having from 5 to 20 ring atoms or combinations of these systems, where one or more radicals can form mono-or polycyclic aliphatic or aromatic ring systems with one another and/or with the ring bonded to said radicals.

In some more preferred embodiments, Ar₁₃～Ar₁₅Identical or different are deuterated or non-deuterated substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 15 ring atoms or deuterated or non-deuterated aryloxy or heteroaryloxy groups having 5 to 15 ring atoms or combinations of these systems, where one or more radicals can form mono-or polycyclic aliphatic or aromatic ring systems with one another and/or with the ring bonded to said radicals.

R⁹⁰¹、R⁹⁰²On each occurrence, the same or different, is H, or D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20C atoms, orBranched or cyclic alkyl, alkoxy or thioalkoxy groups having 3 to 20C atoms or are silyl groups, or substituted keto groups having 1 to 20C atoms, or alkoxycarbonyl groups having 2 to 20C atoms, or aryloxycarbonyl groups having 7 to 20C atoms, cyano groups (-CN), carbamoyl groups (-C (═ O) NH₂) A haloformyl group (-C (═ O) -X wherein X represents a halogen atom), a formyl group (-C (═ O) -H), an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, CF₃A group, Cl, Br, F, a crosslinkable group or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems.

More preferably, R⁹⁰¹、R⁹⁰²On each occurrence, the same or different is H, or D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 10C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 10C atoms or a silyl group, or a substituted keto group having 1 to 10C atoms, or an alkoxycarbonyl group having 2 to 10C atoms, or an aryloxycarbonyl group having 7 to 10C atoms, a cyano group (-CN), a carbamoyl group (-C (═ O) NH₂) A haloformyl group (-C (═ O) -X wherein X represents a halogen atom), a formyl group (-C (═ O) -H), an isocyano group, an isocyanate group, a thiocyanate group or an isothiocyanate group, a hydroxyl group, a nitro group, CF₃A group, Cl, Br, F, a crosslinkable group or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 20 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 20 ring atoms, or a combination of these systems.

b. u, v are independently 1 or 2 or 3, preferably 1.

In certain embodiments, the organic mixture according to the present invention, Ar in formula (IV)₁₃-Ar₁₅When occurring multiple times, can be selected from the following structures, which may be the same or differentOne or a combination of groups:

wherein d is 1 or 2 or 3 or 4.

Examples of suitable second organic compounds (H2) are listed below, but are not limited to:

in a very preferred embodiment, the organic mixtures are used in the light-emitting layer in organic electroluminescent devices. There are sometimes some special requirements for H1 and H2 for stability or process considerations.

In a more preferred embodiment, the organic mixture according to the invention, wherein at least one of H1 and H2 is preferably H2, has a value ((LUMO +1) -LUMO) of ≧ 0.1eV, preferably ≧ 0.15eV, more preferably ≧ 0.20eV, still more preferably ≧ 0.25eV, most preferably ≧ 0.30 eV.

In a further preferred embodiment, the organic mixture according to the invention, wherein at least one of H1 and H2 is preferably H1, is (HOMO- (HOMO-1)). gtoreq.0.2 eV, preferably at least 0.25eV, more preferably at least 0.30eV, even more preferably at least 0.35eV, most preferably at least 0.40 eV.

In a preferred embodiment, the organic mixture wherein the molar ratio of H1 to H2 is from 2: 8 to 8: 2; preferred molar ratios are 3:7 to 7: 3; more preferably the molar ratio is from 4:6 to 6:4, most preferably 5: 5.

In a preferred embodiment, at least one of H1 and H2 in the organic mixture according to the invention has a glass transition temperature T_gMore than or equal to 100 ℃, in one excellenceIn selected embodiments, there is at least one T_gNot less than 120 ℃ and in a more preferred embodiment at least one of its T' s_g140 ℃ or more, and in a more preferred embodiment at least one of its T_g160 ℃ or more, and in a most preferred embodiment at least one of its T_g≥180℃。

In certain embodiments, the sublimation temperatures of the first organic compound (H1) and the second organic compound (H2) do not differ by more than 30K in accordance with the organic mixtures of the present invention.

Preferably, the organic mixture, the first organic compound (H1) and the second organic compound (H2) have sublimation temperatures that differ by no more than 20K.

More preferably, the organic mixture, the first organic compound (H1) and the second organic compound (H2) have sublimation temperatures that differ by no more than 10K.

Most preferably, according to an organic mixture of the present invention, the sublimation temperatures of the first organic compound (H1) and the second organic compound (H2) are the same.

In certain preferred embodiments, the molecular weights of the first organic compound (H1) and the second organic compound (H2) in the organic mixture according to the invention differ by no more than 100g/mol, preferably no more than 90g/mol, more preferably no more than 80g/mol, and most preferably no more than 60 g/mol.

The present invention also provides another organic mixture, which comprises a first organic compound (H1) and a second organic compound (H2) as described above, and at least another organic functional material, wherein the another organic functional material can be selected from hole (also called hole) injection or transport materials (HIM/HTM), Hole Blocking Materials (HBM), electron injection or transport materials (EIM/ETM), Electron Blocking Materials (EBM), organic matrix materials (Host), singlet emitters (fluorescent emitters), triplet emitters (phosphorescent emitters), thermal emission delayed fluorescence materials (TADF materials) and organic dyes; preferably selected from phosphorescent emitters and TADF materials. Various organic functional materials are described in detail, for example, in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of this 3 patent document being hereby incorporated by reference.

ETM, fluorescent light emitting materials or singlet emitters, phosphorescent light emitting materials or triplet emitters, and TADF materials are described in some more detail below (but not limited thereto).

1.ETM

Examples of the ETM material are not particularly limited, and any metal complex or organic compound may be used as the ETM as long as they can transport electrons. Preferred organic ETM materials may be selected from tris (8-hydroxyquinoline) aluminum (AlQ3), phenazine, phenanthroline, anthracene, phenanthrene, fluorene, bifluorene, spirobifluorene, paraphenylacetylene, pyridazine, pyrazine, triazine, triazole, imidazole, quinoline, isoquinoline, quinoxaline, oxazole, isoxazole, oxadiazole, thiadiazole, pyridine, pyrazole, pyrrole, pyrimidine, acridine, pyrene, perylene, anti-indenofluorene, cis-indeno, dibenzo-indenofluorene, indenonaphthalene, benzanthracene, azaphosphole, azaborole, aromatic ketones, lactams, and derivatives thereof.

In one aspect, the compounds useful as ETM are molecules comprising at least one group

R¹Groups which can be selected from: hydrogen, deuterium, halogen (F, Cl, Br, I), cyano, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl, when R is¹Selected from aryl or heteroaryl, R¹Has the same meaning as Ar₁，Ar₁～Ar₅The meaning is the same as above. n2 is an integer from 0 to 20; x¹-X⁸Is selected from CR¹Or N.

On the other hand, examples of metal complexes that can be used as ETM include, but are not limited to, the following general structures

(O-N) or (N-N) is a bidentate ligand wherein the metal is coordinated to O, N or N, N; l is an ancillary ligand; r1 is an integer having a value from 1 to the maximum coordination number of the metal. At L_3-r1In one specific example of (a), r1 is 1 or 2 or 3; when r1 is 3, the subscripts 3-r1 of L are 0, indicating that L is absent. At L_2-r1In one specific example of (a), r1 is 1 or 2; when r1 is 2, the subscripts 2-r1 of L are 0, indicating that L is absent.

Examples of suitable ETM compounds are listed in the following table:

2. triplet Host material (Triplet Host):

examples of the triplet Host material are not particularly limited, and any metal complex or organic compound may be used as the Host as long as the triplet energy level thereof is higher than that of a light emitter, particularly a triplet light emitter or a phosphorescent light emitter, and examples of the metal complex which can be used as the triplet Host (Host) include, but are not limited to, the following general structures:

m3 is a metal; (Y)₃-Y₄) Is a bidentate ligand, Y₃And Y₄Independently selected from C, N, O, P, and S; l is an ancillary ligand; r2 is an integer having a value from 1 to the maximum coordination number of the metal;

in a preferred embodiment, the metal complexes useful as triplet hosts are of the form:

(O-N) is a bidentate ligand wherein the metal is coordinated to both O and N atoms, and r2 is an integer having a value from 1 up to the maximum coordination number of the metal; in one embodiment, M3 may be selected from Ir and Pt.

Examples of the organic compound which can be a triplet host are selected from compounds containing a cyclic aromatic hydrocarbon group such as benzene, biphenyl, triphenylbenzene, benzofluorene; compounds containing aromatic heterocyclic groups, such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, dibenzocarbazole, indolocarbazole, pyridine indole, pyrrole bipyridine, pyrazole, imidazole, triazoles, oxazole, thiazole, oxadiazole, bisoxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, oxazole, dibenzooxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, phthalazine, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuran pyridine, furopyridine, benzothiophene pyridine, thiophene pyridine, benzoselenophene pyridine, and selenophene benzodipyridine; groups having 2 to 10 ring structures, which may be the same or different types of cyclic aromatic hydrocarbon groups or aromatic heterocyclic groups, are bonded to each other directly or through at least one group selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an alicyclic group. Wherein each Ar may be further substituted, and the substituents may be selected from the group consisting of hydrogen, deuterium, cyano, halogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl.

In a preferred embodiment, the triplet host material may be selected from compounds comprising at least one of the following groups:

R²-R⁷has the same meaning as R¹，X₉Is selected from CR¹R²Or NR¹Y is selected from CR¹R²Or NR¹Or O or S. R¹，n2，X¹-X⁸，Ar₁～Ar₃The meaning of (A) is as described above.

Examples of suitable triplet host materials are listed in the following table but are not limited to:

3. singlet state luminophor (Singlet Emitter)

Singlet emitters tend to have longer conjugated pi-electron systems. Hitherto, there have been many examples such as styrylamine and its derivatives disclosed in JP2913116B and WO2001021729a1, indenofluorene and its derivatives disclosed in WO2008/006449 and WO2007/140847, and triarylamine derivatives of pyrene disclosed in US7233019, KR 2006-0006760.

In a preferred embodiment, the singlet emitters may be selected from the group consisting of monostyrenes, distyrenes, tristyrenes, tetrastyrenes, styrylphosphines, styryl ethers, and arylamines.

A monostyrene amine is a compound comprising an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine. A distyrene amine refers to a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A tristyrenylamine refers to a compound comprising three unsubstituted or substituted styrene groups and at least one amine, preferably an aromatic amine. A tetrastyrene amine refers to a compound comprising four unsubstituted or substituted styrene groups and at least one amine, preferably an aromatic amine. One preferred styrene is stilbene, which may be further substituted. The corresponding phosphines and ethers are defined analogously to the amines. Arylamine or aromatic amine refers to a compound comprising three unsubstituted or substituted aromatic rings or heterocyclic systems directly linked to nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably a fused ring system and preferably has at least 14 aromatic ring atoms. Among them, preferred examples are aromatic anthracenamines, aromatic anthracenediamines, aromatic pyrenediamines, aromatic chrysenamines and aromatic chrysenediamines. An aromatic anthracylamine refers to a compound in which a diarylamine group is attached directly to the anthracene, preferably at the 9 position. An aromatic anthracenediamine refers to a compound in which two diarylamine groups are attached directly to the anthracene, preferably at the 9,10 positions. Aromatic pyrene amines, aromatic pyrene diamines, aromatic chrysene amines and aromatic chrysene diamines are similarly defined, wherein the diarylamine groups are preferably attached to the 1 or 1,6 position of pyrene.

Examples, also preferred, of singlet emitters based on vinylamines and arylamines can be found in WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549, WO 2007/115610, US 7250532B2, DE 102005058557A1, CN 1583691A, JP 08053397A, US 6251531B1, US 2006/210830A, EP 1957606A1 and US 2008/0113101A1 and the entire contents of the patent documents listed above are hereby incorporated by reference.

An example of singlet emitters based on stilbene and its derivatives is US 5121029.

Further preferred singlet emitters may be selected from indenofluorene-amines and indenofluorene-diamines, as disclosed in WO 2006/122630, benzindenofluorene-amines and benzindenofluorene-diamines, as disclosed in WO2008/006449, dibenzoindenofluorene-amines and dibenzoindenofluorene-diamines, as disclosed in WO 2007/140847.

Further preferred singlet emitters may be selected from fluorene based fused ring systems as disclosed in US2015333277a1, US2016099411a1, US2016204355a 1.

More preferred singlet emitters may be selected from pyrene derivatives, such as the structures disclosed in US2013175509a 1; triarylamine derivatives of pyrene, such as pyrene triarylamine derivatives containing dibenzofuran units as disclosed in CN 102232068B; other triarylamine derivatives of pyrene having specific structures are disclosed in CN105085334A, CN 105037173A. Other materials which can be used as singlet emitters are polycyclic aromatic compounds, in particular derivatives of anthracene, such as 9, 10-bis (2-naphthoanthracene), naphthalene, tetraphene, xanthene, phenanthrene, pyrene, such as 2,5,8, 11-tetra-t-butylperylene, indenopyrene, phenylene, such as (4,4 '-bis (9-ethyl-3-carbazolyl-vinyl) -1, 1' -biphenyl, diindenopyrene, decacycloalkene, coronene, fluorene, spirobifluorene, arylpyrene, such as U.S. 20060222886, aryleneethene, such as U.S. Pat. No. 5121029, U.S. Pat. No. 5,8803, cyclopentadiene, such as tetraphenylcyclopentadiene, rubrene, coumarin, rhodamine, quinacridone, pyrans, such as 4 (dicyanomethylene) -6- (4-p-dimethylaminostyryl-2-methyl) -4H-pyran (DCM), thiopyran, bis (azinyl) iminoboron compounds (US2007/0092753A1), bis (azinyl) methylene compounds, carbostyryl compounds, oxazinones, benzoxazoles, benzothiazoles, benzimidazoles and pyrrolopyrrolediones. Some materials for singlet emitters can be found in US20070252517a1, US4769292, US 6020078, US 2007/0252517a1, US 2007/0252517a 1. The entire contents of the above listed patent documents are hereby incorporated by reference.

Some examples of suitable singlet emitters are listed in the following table:

4. thermally activated delayed fluorescence luminescent material (TADF):

the traditional organic fluorescent material can only emit light by utilizing 25% singlet excitons formed by electric excitation, and the internal quantum efficiency of the device is low (up to 25%). Although the phosphorescence material enhances the intersystem crossing due to the strong spin-orbit coupling of the heavy atom center, the singlet excitons and the triplet excitons formed by the electric excitation can be effectively used for emitting light, so that the internal quantum efficiency of the device reaches 100 percent. However, the application of the phosphorescent material in the OLED is limited by the problems of high price, poor material stability, serious efficiency roll-off of the device and the like. The thermally activated delayed fluorescence emitting material is a third generation organic emitting material developed after organic fluorescent materials and organic phosphorescent materials. Such materials generally have a small singlet-triplet energy level difference (Δ Est), and triplet excitons may be converted to singlet excitons for emission by intersystem crossing. This can make full use of singlet excitons and triplet excitons formed upon electrical excitation. The quantum efficiency in the device can reach 100%. Meanwhile, the material has controllable structure, stable property, low price and no need of noble metal, and has wide application prospect in the field of OLED.

TADF materials need to have a small singlet-triplet level difference, preferably Δ Est <0.3eV, less preferably Δ Est <0.25eV, more preferably Δ Est <0.20eV, and most preferably Δ Est <0.1 eV. In a preferred embodiment, the TADF material has a relatively small Δ Est, and in another preferred embodiment, the TADF has a good fluorescence quantum efficiency. Some TADF luminescent materials may be found in patent documents CN103483332(a), TW201309696(a), TW201309778(a), TW201343874(a), TW201350558(a), US20120217869(a1), WO2013133359(a1), WO2013154064(a1), Adachi, et. al. adv.mater, 21,2009,4802, Adachi, et. al. appl.phys.lett.,98,2011,083302, Adachi, et. appl.phys.lett, 101,2012,093306, Adachi, chem.comm.comm, 48,2012,11392, Adachi, et. nature. natronics, 6,2012,253, Adachi, et. nature,492,2012,234, Adachi, am.j.am, Adachi, et. adochi, et. nature, adochi, et. phytol.73, adochi, et. phyton.8, Adachi, adachi.73, et. phytol.73, Adachi, et. phyton.73, et. phytol.35, Adachi, et. phytol.8, Adachi, adachi.t.t.t.

Some examples of suitable TADF phosphors are listed in the following table:

5. triplet Emitter (Triplet Emitter)

Triplet emitters are also known as phosphorescent emitters. In a preferred embodiment, the triplet emitter is a metal complex of the general formula M (L) n, where M is a metal atom, L, which may be the same or different at each occurrence, is an organic ligand which is bonded or coordinately bound to the metal atom M via one or more positions, and n is an integer greater than 1, preferably 1,2,3,4, 5 or 6. Optionally, the metal complexes are coupled to a polymer through one or more sites, preferably through organic ligands.

In a preferred embodiment, the metal atom M is chosen from transition metals or lanthanides or actinides, preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy, Re, Cu or Ag, particularly preferably Os, Ir, Ru, Rh, Re, Pd, Au or Pt.

Preferably, the triplet emitter comprises a chelating ligand, i.e. a ligand, which coordinates to the metal via at least two binding sites, particularly preferably the triplet emitter comprises two or three identical or different bidentate or polydentate ligands. Chelating ligands are advantageous for increasing the stability of the metal complex.

Examples of organic ligands may be selected from phenylpyridine derivatives, 7, 8-benzoquinoline derivatives, 2 (2-thienyl) pyridine derivatives, 2 (1-naphthyl) pyridine derivatives, or 2-phenylquinoline derivatives. All of these organic ligands may be substituted, for example, with fluorine-containing or trifluoromethyl groups. The ancillary ligand may preferably be selected from acetone acetate or picric acid.

In a preferred embodiment, the metal complexes which can be used as triplet emitters are of the form:

where M is a metal selected from the transition metals or the lanthanides or actinides, particularly preferably Ir, Pt, Au;

Ar¹each occurrence of which may be the same or different, is a cyclic group containing at least one donor atom, i.e., an atom having a lone pair of electrons, such as nitrogen or phosphorus, through which the cyclic group is coordinately bound to the metal; ar (Ar)²Each occurrence, which may be the same or different, is a cyclic group containing at least one C atom through which the cyclic group is attached to the metal; ar (Ar)¹And Ar²Linked together by a covalent bond, which may each carry one or more substituent groups, which may in turn be linked together by substituent groups; l', which may be the same or different at each occurrence, is a bidentate chelating ancillary ligand, preferably a monoanionic bidentate chelating ligand; q1 may be 0,1,2 or 3, preferably 2 or 3; q2 may be 0,1,2 or 3, preferably 1 or 0.

Examples of materials and their use for some triplet emitters can be found in WO200070655, WO 200141512, WO 200202714, WO 200215645, EP 1191613, EP 1191612, EP1191614, WO 2005033244, WO 2005019373, US 2005019373, WO2010015307, WO 2005019373, WO 2005019373, WO 2005019373, WO 2005019373, WO2010099852, WO 2005019373, US 2005019373A 2005019373, US 2005019373A 2005019373, US 2005019373A 2005019373, Baldo, Thompson et al Nature, (750) 753, US 2005019373A 2005019373, US 2005019373A 2005019373, Adachi et al Appl. Phys.Lett.78(2001), 1622. 1624, J.Kido. Appl. Phys.Lett.65 (364), Kiuch et al, WO 2005019373, US 2005019373, US 2005019373A 2005019373, US 2005019373A 2005019373, US 2005019373, US 2005019373A 3678, US 361624, US 2005019373A 361624, WO 2005019373, US 2005019373, US 2005019373, US 2005019373A 2005019373, US 2005019373A 2005019373, US 2005019373, CN 102282150a, WO 2009118087a1, WO 2013107487a1, WO2013094620a1, WO 2013174471a1, WO 2014031977a1, WO 2014112450a1, WO2014007565a1, WO 2014038456a1, WO 2014024131a1, WO 2014008982a1, WO2014023377a 1. The entire contents of the above listed patent documents and literature are hereby incorporated by reference.

Some examples of suitable triplet emitters are listed in the following table:

it is an object of the present invention to provide a material solution for evaporation type OLEDs.

In certain embodiments, the organic compounds according to the present invention have a molecular weight of 1100g/mol or less, preferably 1000g/mol or less, very preferably 950g/mol or less, more preferably 900g/mol or less, and most preferably 800g/mol or less.

It is another object of the present invention to provide a material solution for printing OLEDs.

In certain embodiments, the organic compounds according to the present invention have a molecular weight of 700g/mol or more, preferably 800g/mol or more, very preferably 900g/mol or more, more preferably 1000g/mol or more, and most preferably 1100g/mol or more.

In other embodiments, the organic compounds according to the invention have a solubility in toluene of 2mg/ml or more, preferably 3mg/ml or more, more preferably 4mg/ml or more, most preferably 5mg/ml or more at 25 ℃.

It is another object of the present invention to provide a solution for providing materials for printing OLEDs.

In a preferred embodiment, the composition according to the invention is a solution.

In another preferred embodiment, the composition according to the invention is a suspension.

The composition of the embodiment of the present invention may contain 0.01 wt% to 20 wt% of the organic compound, preferably 0.1 wt% to 15 wt%, more preferably 0.2 wt% to 10 wt%, and most preferably 0.25 wt% to 5 wt%.

In some preferred embodiments, a composition according to the present invention, wherein the solvent is selected from an inorganic ester compound such as an aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, alicyclic or olefinic compound, or borate or phosphate ester, or a mixture of two or more solvents.

In other preferred embodiments, a composition according to the present invention comprises at least 50 wt% of an aromatic or heteroaromatic solvent; preferably at least 80 wt% of an aromatic or heteroaromatic solvent; particularly preferably at least 90% by weight of an aromatic or heteroaromatic solvent.

Examples of aromatic or heteroaromatic-based solvents according to the present invention include, but are not limited to, 1-tetralone, 3-phenoxytoluene, acetophenone, 1-methoxynaphthalene, p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3, 4-tetramethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, butylbenzene, dodecylbenzene, 1-methylnaphthalene, 1,2, 4-trichlorobenzene, 1, 3-dipropoxybenzene, 4-difluorodiphenylmethane, diphenylether, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether, N-methyldiphenylamine, 4-isopropylbiphenyl, αα -dichlorodiphenylmethane, 3-phenylpropyl) ether, 1, 2-benzyldiphenyl ether, 2-phenoxytoluene, 2-dimethylbenzyl ether, benzyl benzoate, and the like.

In other embodiments, suitable and preferred solvents are aliphatic, cycloaliphatic or aromatic, amines, thiols, amides, nitriles, esters, ethers, polyethers, alcohols, diols or polyols.

In other embodiments, the alcohol represents a suitable class of solvent. Preferred alcohols include alkylcyclohexanols, particularly methylated aliphatic alcohols, naphthols, and the like.

The solvent may be a cycloalkane, such as decalin.

The solvents mentioned may be used alone or as a mixture of two or more organic solvents.

In some embodiments, the composition according to the present invention comprises an organic functional compound as described above and at least one organic solvent, and may further comprise another organic solvent, examples of which include (but are not limited to): methanol, ethanol, 2-methoxyethanol, methylene chloride, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1, 4-dioxane, acetone, methyl ethyl ketone, 1, 2-dichloroethane, 3-phenoxytoluene, 1,1, 1-trichloroethane, 1,1,2, 2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene, decalin, indene, and/or mixtures thereof.

In some preferred embodiments, particularly suitable solvents for the present invention are those having Hansen (Hansen) solubility parameters within the following ranges:

δ_d(dispersion force) of 17.0 to 23.2MPa^1/2In particular in the range of 18.5 to 21.0MPa^1/2A range of (d);

δ_p(polar force) is 0.2 to 12.5MPa^1/2In particular in the range of 2.0 to 6.0MPa^1/2A range of (d);

δ_h(hydrogen bonding force) of 0.9 to 14.2MPa^1/2In particular in the range of 2.0 to 6.0MPa^1/2The range of (1).

The compositions according to the invention, in which the organic solvent is selected taking into account its boiling point parameter. In the invention, the boiling point of the organic solvent is more than or equal to 150 ℃; 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 more than or equal to 275 ℃ or more than or equal to 300 ℃. Boiling points in these ranges are beneficial for preventing nozzle clogging in inkjet print heads. The organic solvent may be evaporated from the solvent system to form a thin film comprising the functional material.

In some preferred embodiments, a composition according to the invention,

1) having a viscosity @25 ℃ in the range of 1cPs to 100cPs, and/or

2) Its surface tension @25 ℃ is in the range of 19dyne/cm to 50 dyne/cm.

The composition according to the invention, wherein the organic solvent is selected taking into account its surface tension parameters. Suitable ink surface tension parameters are appropriate for a particular substrate and a particular printing process. For example, for ink jet printing, in a preferred embodiment, the organic solvent has a surface tension in the range of about 19dyne/cm to about 50dyne/cm at 25 ℃; more preferably in the range of 22dyne/cm to 35 dyne/cm; most preferably in the range of 25dyne/cm to 33 dyne/cm.

In a preferred embodiment, the ink according to the invention has a surface tension at 25 ℃ in the range of about 19dyne/cm to about 50 dyne/cm; more preferably in the range of 22dyne/cm to 35 dyne/cm; preferably in the range of 25dyne/cm to 33 dyne/cm.

The composition according to the invention, wherein the organic solvent is selected taking into account the viscosity parameters of the ink. The viscosity can be adjusted by different methods, such as by the selection of a suitable organic solvent and the concentration of the functional material in the ink. In a preferred embodiment, the viscosity of the organic solvent is less than 100 cps; more preferably below 50 cps; most preferably 1.5 to 20 cps. The viscosity here means the viscosity at ambient temperature at the time of printing, and is generally 15 to 30 ℃, preferably 18 to 28 ℃, more preferably 20 to 25 ℃, most preferably 23 to 25 ℃. The compositions so formulated will be particularly suitable for ink jet printing.

In a preferred embodiment, the viscosity of the composition according to the invention ranges from about 1cps to about 100cps at 25 ℃; more preferably in the range of 1cps to 50 cps; preferably in the range of 1.5cps to 20 cps.

The ink obtained from the organic solvent satisfying the above boiling point, surface tension parameter and viscosity parameter can form a functional material film having a uniform thickness and composition properties.

The invention also provides an organic electronic device comprising an organic compound or polymer as described above, or an organic mixture as described above.

The Organic electronic device as described above may be selected from Organic Light Emitting Diodes (OLEDs), Organic photovoltaic cells (OPVs), Organic light Emitting cells (OLEECs), Organic Field Effect Transistors (OFETs), Organic light Emitting field effect transistors, Organic lasers, Organic spintronic devices, Organic sensors, and Organic Plasmon Emitting diodes (Organic plasma Emitting diodes).

The organic electronic device as described above is an organic electroluminescent device comprising at least a light-emitting layer comprising an organic compound or polymer as described above, or an organic mixture as described above.

Another object of the present invention is to provide a method for manufacturing the above electronic device.

The specific technical scheme is as follows:

a preparation method comprises the steps of forming a functional layer on a substrate by using the compound or the mixture through an evaporation method, or forming a functional layer on a substrate by using a co-evaporation method and at least one other organic functional material together, or coating the composition on a substrate through a Printing or coating method to form a functional layer, wherein the Printing or coating method can be selected from (but is not limited to) ink-jet Printing, spray Printing (Nozle Printing), letterpress Printing, silk-screen Printing, dip coating, rotary coating, doctor blade coating, roller Printing, twist roller Printing, offset Printing, flexo Printing, rotary Printing, spray coating, brush coating or transfer Printing, slit extrusion coating and the like.

The invention also relates to the use of said composition as a printing ink for the production of organic electronic devices, particularly preferably by printing or coating.

Suitable printing or coating techniques include, but are not limited to, ink jet printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roll printing, twist roll printing, lithographic printing, flexographic printing, rotary printing, spray coating, brush or pad printing, slot die coating, and the like. Gravure printing, screen printing and ink jet printing are preferred. Gravure printing, ink jet printing, will be used in the examples of the present invention. The solution or suspension may additionally include one or more components such as surface active compounds, lubricants, wetting agents, dispersants, hydrophobing agents, binders, and the like, for adjusting viscosity, film forming properties, enhancing adhesion, and the like. For details on the printing technology and its requirements concerning the solutions, such as solvents and concentrations, viscosities, etc., reference is made to the Handbook of Print Media, technology and Production Methods, published by Helmut Kipphan, ISBN 3-540-67326-1.

In the above method, the thickness of the formed functional layer is 5nm-1000 nm.

The invention further relates to an organic electronic component comprising at least one organic compound or polymer according to the invention or at least one functional layer, which is produced using a composition according to the invention. Generally, such an organic electronic device comprises at least a cathode, an anode and a functional layer located between the cathode and the anode, wherein the functional layer comprises at least one organic compound as described above.

In a more preferred embodiment, the organic electronic device described above is an electroluminescent device, in particular an OLED (as shown in fig. 1), comprising a substrate (101), an anode (102), at least one light-emitting layer (104), and a cathode (106).

The substrate (101) may be opaque or transparent. A transparent substrate may be used to fabricate a transparent light emitting device. See, for example, Bulovic et al Nature 1996,380, p29, and Gu et al, appl.Phys.Lett.1996,68, p 2606. The substrate may be rigid or flexible. The substrate may be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. A substrate free of surface defects is a particularly desirable choice. In a preferred embodiment, the substrate is flexible, and may be selected from polymeric films or plastics having a glass transition temperature Tg of 150 deg.C or greater, preferably greater than 200 deg.C, more preferably greater than 250 deg.C, and most preferably greater than 300 deg.C. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).

The anode (102) may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL) or an emission layer. In one embodiment, the absolute value of the difference between the work function 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 acting as a HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. Examples of anode materials include, but are not limited to: al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like. 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 invention.

The cathode (106) may include a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the light emitting layer. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO level or conduction band level of the emitter in the light-emitting layer or of the n-type semiconductor material as Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. In principle, all materials which can be used as cathodes in OLEDs are possible as cathode materials for the device according to the invention. Examples of cathode materials include, but are not limited to: al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF₂Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magneticControlled sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.

The OLED may also comprise further functional layers, such as a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL) (103), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL) or an Electron Transport Layer (ETL) (105), a Hole Blocking Layer (HBL). Suitable materials for use in these functional layers are described in detail in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of these 3 patent documents being hereby incorporated by reference.

In a preferred embodiment, the light-emitting device according to the invention is provided with a light-emitting layer (104) by vacuum evaporation, the evaporation source comprising a compound or mixture according to the invention.

In another preferred embodiment, the light-emitting device according to the invention is a light-emitting device wherein the light-emitting layer (104) is prepared by printing a composition according to the invention.

The electroluminescent device according to the invention emits light at a wavelength of between 300 and 1000nm, preferably between 350 and 900nm, more preferably between 400 and 800 nm.

The invention also relates to the use of the organic electronic device according to the invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.

The invention also relates to electronic devices including, but not limited to, display devices, lighting devices, light sources, sensors, etc., comprising the organic electronic device according to the invention.

The present invention will be described in connection with preferred embodiments, but the present invention is not limited to the following embodiments, and it should be understood that the appended claims outline the scope of the present invention and those skilled in the art, guided by the inventive concept, will appreciate that certain changes may be made to the embodiments of the invention, which are intended to be covered by the spirit and scope of the appended claims.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

Synthesis example 1: synthesis of Compound 1

Synthesis of Compound 1.1:

adding Mg (4.6g,182.3mmol) and iodine particles into a dry three-neck flask, adding 30ml of THF, slowly dropwise adding a proper amount of bromobenzene (10g,64.1mmol) dissolved in 30ml of THF through a constant-pressure funnel under the protection of nitrogen to initiate the format, then slowly dropwise adding bromobenzene solution to keep the format in a moderate reaction state, heating to 70 ℃ and stirring at constant temperature for reaction for 2 hours after the dropwise adding of the solution is finished, slowly dropwise adding Grignard reagent into THF solution of 4-bromofluorenone (14.5g,57.69mmol) under the protection of nitrogen to heat to 70 ℃ and stirring for reaction for 5 hours after the format reaction is finished, and removing the solvent after the reaction is finished to obtain an intermediate A; a (10.0g,29.8mmol) and dibenzofuran (5.0g,29.8mmol) were placed in a three-necked flask, heated to 70 ℃ with methanesulfonic acid (200ml) as a solvent, and stirred at a constant temperature overnight, TLC and MS showed complete reaction, mainly the target product, cooled, the reaction solution was neutralized to about pH 9 with 5% Na solution, extracted three times with dichloromethane and aqueous solution, the organic phases were combined, washed with saturated brine, dried, concentrated, and the residue was purified by column chromatography with DCM/PE (1:10) to give compound 1.1 as a white solid (12.3g, 43% yield).

Synthesis of Compound 1:

a solution of the compound 1.1(12.3g,25.3mmol), N- (3-biphenylyl) carbazole-3-boronic acid (9.2g,25.3mmol) and 2.00mol/L sodium carbonate (5.4g, 50.6mmol) was charged into a three-necked flask, dissolved with 300ml toluene with stirring, protected with nitrogen, and then Pd (pph) was added₃)₄(71.3mg,0.76mmol), the reaction was stirred under reflux for 12 hours, TLC and MS showed completion of the reaction, mainly the desired product, cooled, the reaction was washed three times with 150ml of saturated brine, dried over anhydrous sodium sulfate, then the solvent was evaporated, and the residue was purified by column chromatography with DCM/PE (1:5) to give Compound 1 as a white solid (13.7g, yield 75%).

Synthesis example 2: synthesis of Compound 2

Synthesis of Compound 2.1:

adding Mg (4.6g,182.3mmol) and iodine particles into a dry three-neck flask, adding 30ml of THF, slowly dropwise adding a proper amount of bromobenzene (10g,64.1mmol) dissolved in 30ml of THF through a constant-pressure funnel under the protection of nitrogen to initiate the format, then slowly dropwise adding bromobenzene solution to keep the format in a moderate reaction state, heating to 70 ℃ and stirring at constant temperature for reaction for 2 hours after the dropwise adding of the solution is finished, slowly dropwise adding Grignard reagent into THF solution of 3-bromofluorenone (14.5g,57.69mmol) under the protection of nitrogen to heat to 70 ℃ and stirring for reaction for 5 hours after the format reaction is finished, and removing the solvent after the reaction is finished to obtain an intermediate B; placing B (10.0g,29.8mmol) and dibenzothiophene (5.5g,29.8mmol) in a three-neck flask, heating to 70 ℃ with methanesulfonic acid (200ml) as a solvent, stirring at constant temperature for reaction overnight, TLC and MS show complete reaction and mainly aim products, cooling, neutralizing the reaction solution with 5% Na solution until the pH is about 9, extracting the aqueous phase three times with dichloromethane and water, combining the organic phases, washing with saturated brine, drying, concentrating, and purifying the residue with DCM/PE (1:10) through a column to obtain a white solid compound 2.1(12.0g, yield 40%).

Synthesis of Compound 2:

a solution of the compound 2.1(12.0g,23.9mmol), N- (3-biphenyl) carbazole-3-boronic acid (8.7g,23.9mmol) and 2.00mol/L sodium carbonate (5.1g, 47.8mmol) was charged into a three-necked flask, dissolved with 300ml toluene with stirring, protected with nitrogen, and then added with Pd (pph)₃)₄(69mg,0.72mmol), the reaction was stirred under reflux for 12 hours, TLC and MS showed completion of the reaction, mainly the desired product, cooled, washed three times with 150ml of saturated brine, dried over anhydrous sodium sulfate, then evaporated to remove the solvent, and the residue was purified by column chromatography with DCM/PE (1:5) to give Compound 2 as a white solid (13g, yield 75%).

Synthesis example 3: synthesis of Compound 3

Synthesis of Compound 3.1:

adding Mg (4.6g,182.3mmol) and iodine particles into a dry three-neck flask, adding 30ml of THF, under the protection of nitrogen, slowly dropwise adding a proper amount of bromobenzene (10g,64.1mmol) dissolved in 30ml of THF through a constant-pressure funnel, initiating the format, then slowly dropwise adding bromobenzene solution to keep the format in a proper reaction state, heating to 70 ℃ after dropwise adding the solution, stirring at constant temperature for reaction for 2 hours, after the format reaction is complete, slowly dropwise adding a Grignard reagent into THF solution of 2-bromofluorenone (14.5g,57.69mmol) under the protection of nitrogen, heating to 70 ℃ and stirring for reaction for 5 hours, and after the reaction is complete, removing the solvent by rotation to obtain an intermediate C; placing C (10.0g,29.8mmol) and dibenzofuran (5.0g,29.8mmol) in a three-neck flask, heating to 70 ℃ with methanesulfonic acid (200ml) as a solvent, stirring at constant temperature for reaction overnight, TLC and MS show complete reaction and mainly aim products, cooling, neutralizing the reaction solution with 5% Na solution until pH is about 9, extracting with dichloromethane and water solution for three times, combining organic phases, washing with saturated brine, drying, concentrating, and purifying the residue with DCM/PE (1:10) through a column to obtain compound 3.1(12.3g, yield 43%) as a white solid.

Synthesis of Compound 3:

a solution of the compound 3.1(12.3g,25.3mmol), N- (3-biphenylyl) carbazole-3-boronic acid (9.2g,25.3mmol) and 2.00mol/L sodium carbonate (5.4g, 50.6mmol) was charged into a three-necked flask, dissolved with 300ml toluene with stirring, protected with nitrogen, and then Pd (pph) was added₃)₄(71.3mg,0.76mmol), the reaction was stirred under reflux for 12 hours, TLC and MS showed completion of the reaction, mainly the desired product, cooled, washed three times with 150ml of saturated brine, dried over anhydrous sodium sulfate, then evaporated to remove the solvent, and the residue was purified by column chromatography with DCM/PE (1:5) to give compound 3(12.8g, yield 70%) as a white solid.

Synthesis example 4: synthesis of Compound 4

Synthesis of Compound 4.1:

adding Mg (4.6g,182.3mmol) and iodine particles into a dry three-neck flask, adding 30ml of THF, under the protection of nitrogen, slowly dropwise adding a proper amount of bromobenzene (10g,64.1mmol) dissolved in 30ml of THF through a constant-pressure funnel, initiating the format, then slowly dropwise adding bromobenzene solution to keep the format in a proper reaction state, heating to 70 ℃ after dropwise adding the solution, stirring at constant temperature for reaction for 2 hours, after the format reaction is complete, slowly dropwise adding a Grignard reagent into THF solution of 4-bromofluorenone (14.5g,57.69mmol) under the protection of nitrogen, heating to 70 ℃ and stirring for reaction for 5 hours, and after the reaction is complete, removing the solvent by rotation to obtain an intermediate D; d (10.0g,29.8mmol) and dibenzothiophene (5.5g,29.8mmol) are placed in a three-neck flask, methanesulfonic acid (200ml) is used as a solvent, the temperature is increased to 70 ℃, the reaction is stirred at constant temperature for overnight, TLC and MS show complete reaction and mainly comprise target products, the reaction liquid is cooled, the reaction liquid is neutralized to about pH 9 by using a 5% Na solution, dichloromethane and a water solution are used for aqueous phase extraction for three times, organic phases are combined, saturated brine is used for washing, drying and concentration are carried out, and residues are purified by column chromatography by using DCM/PE (1:10) to obtain a white solid compound 4.1(12.0g, yield is 40%).

Synthesis of Compound 4.2:

a solution of the compound 4.1(12.0g,23.9mmol), carbazole-3-boronic acid (5.1g,23.9mmol) and 2.00mol/L sodium carbonate (5.1g, 47.8mmol) was charged into a three-necked flask, dissolved with 300ml toluene with stirring, protected with nitrogen, and then added with Pd (pph)₃)₄(69mg,0.72mmol), the reaction was stirred under reflux for 12 h, TLC and MS showed completion of the reaction, mainly the desired product, cooled, washed three times with 150ml of saturated brine, dried over anhydrous sodium sulfate, then evaporated to remove the solvent, and the residue was purified by column chromatography with DCM/PE (1:5) to give compound 4.2 as a white solid (9.9g, yield 70%).

Synthesis of Compound 4:

compound 4.2(9.9g,16.8mmol) and 4-bromo-dibenzothiophene (4.4g,16.8mmol) were charged in a three-necked flask, and stirred with 200ml of tolueneStirring and dissolving, protecting with nitrogen, then adding Pd (dba)₂(0.29g,0.5mmol) and sodium tert-butoxide (4.8g, 50.4mmol), followed by addition of 3.1ml of a 10% solution of tri-tert-butylphosphine in toluene, the reaction was stirred under reflux for 12 hours, cooled, washed three times with 100ml of water, dried over anhydrous sodium sulfate, then the solvent was removed by evaporation, and the residue was purified by column chromatography with DCM/PE (1:4) to give compound 4 as a white solid (8.4g, 65% yield).

Synthesis example 5: synthesis of Compound 5

Synthesis of Compound 5.1:

adding compound 1.1(10g,20.6mmol) and 3-bromocarbazole (5g,20.6mmol) into a three-neck flask, dissolving with 200ml of toluene under stirring, protecting with nitrogen, adding Pd (dba)₂(0.35g,0.62mmol) and sodium tert-butoxide (5.9g, 61.8mmol), followed by addition of 3.7ml of a 10% solution of tri-tert-butylphosphine in toluene the reaction was stirred under reflux for 12 hours, cooled, washed three times with 100ml of water, dried over anhydrous sodium sulfate, then the solvent was removed by evaporation, and the residue was purified by column chromatography with DCM/PE (1:4) to give compound 5.1 as a white solid (8g, 60% yield).

Synthesis of Compound 5:

adding compound 5.1(8g,12.3mmol) and carbazole (2g,12.3mmol) into a three-neck flask, stirring and dissolving with 150ml toluene, protecting with nitrogen, adding Pd (dba)₂(0.21g,0.37mmol) and sodium tert-butoxide (3.5g, 36.9mmol), followed by addition of 10% tri-tert-butylphosphine in toluene 2.2ml the reaction was stirred under reflux for 12 h, cooled, washed three times with 100ml water, dried over anhydrous sodium sulfate, then the solvent was removed by evaporation, and the residue was purified by column chromatography with DCM/PE (1:4) to give compound 5 as a white solid (4.5g, 50% yield).

Synthesis example 6: synthesis of Compound 6

Synthesis of Compound 6.1:

adding a solution of a compound N-phenylcarbazole-1-boric acid (10.0g,34.8mmol), o-bromonitrobenzene (7.0g,34.8mmol) and 2.00mol/L sodium carbonate (7.4g, 69.6mmol) into a three-neck flask, stirring and dissolving the solution by using 300ml of toluene, protecting the solution by nitrogen, and then adding Pd (pph)₃)₄(1.2g,1.04mmol), the reaction was stirred under reflux for 12 hours, TLC and MS showed completion of the reaction, mainly the desired product, cooled, washed three times with 150ml of saturated brine, dried over anhydrous sodium sulfate, then evaporated to remove the solvent, and the residue was purified by column chromatography with DCM/PE (1:8) to give compound 6.1 as a white solid (10.0g, yield 80%).

Synthesis of Compound 6.2:

compound 6.1(10.0g,27.5mmol) was added to a three-necked flask, 150ml of triethyl phosphite was used as a solvent, nitrogen was used as a blanket, the temperature was raised to 143 ℃ and the reaction was stirred at constant temperature for 12 hours, TLC and MS showed completion of the reaction, mainly the target product, was cooled, the solvent was distilled off under reduced pressure, the residue was dissolved with a sufficient amount of DCM and washed three times with 150ml of saturated saline, dried over anhydrous sodium sulfate, and then the solvent was evaporated off, and the residue was purified by column chromatography with DCM/PE (1:4) to give compound 6.2 as a white solid (8.2g, yield 90%).

Synthesis of Compound 6:

adding compound 6.2(8.2g,24.7mmol) and compound 4.1(12.4g,24.7mmol) into a three-neck flask, dissolving with 300ml toluene under stirring, adding Pd (dba)₂(0.43g,0.74mmol) and sodium tert-butoxide (7.1g, 74.1mmol), followed by addition of 4.5ml of a 10% solution of tri-tert-butylphosphine in toluene, the reaction was stirred under reflux for 12 hours, cooled, washed three times with 100ml of water, dried over anhydrous sodium sulfate, then the solvent was removed by evaporation, and the residue was purified by column chromatography with DCM/PE (1:3) to give compound 6 as a white solid (13.6g, 73% yield).

Synthesis example 7: synthesis of Compound 7

Synthesis of compound 7.1:

adding Mg (4.6g,182.3mmol) and iodine particles into a dry three-neck flask, adding 30ml of THF, slowly dropwise adding a proper amount of bromobenzene (10g,64.1mmol) solution dissolved in 30ml of THF through a constant-pressure funnel under the protection of nitrogen to initiate the format, then slowly dropwise adding the bromobenzene solution to keep the format in a proper reaction state, heating to 70 ℃ after dropwise adding the solution, stirring at constant temperature for reaction for 2 hours until the format reaction is complete, slowly dropwise adding a Grignard reagent into a THF solution of 3-bromofluorenone (14.5g,57.69mmol) under the protection of nitrogen, heating to 70 ℃ and stirring for reaction for 5 hours, and removing the solvent after the reaction is complete to obtain an intermediate E; e (10.0g,29.8mmol) and dibenzofuran (5.0g,29.8mmol) were placed in a three-necked flask, heated to 70 ℃ with methanesulfonic acid (200ml) as a solvent, and stirred at a constant temperature overnight, TLC and MS showed complete reaction, mainly the target product, cooled, the reaction solution was neutralized to about pH 9 with 5% Na solution, extracted three times with dichloromethane and aqueous solution, the organic phases were combined, washed with saturated brine, dried, concentrated, and the residue was purified by column chromatography with DCM/PE (1:10) to give compound 7.1 as a white solid (12.6g, yield 44%).

Synthesis of compound 7:

adding compound 7.1(12.6g,25.9mmol) and compound F (10.6g,25.9mmol) into a three-neck flask, dissolving with 300ml toluene under stirring, adding Pd (dba)₂(0.45g,0.78mmol) and sodium tert-butoxide (7.4g, 77.7mmol), followed by addition of 4.7ml of a 10% solution of tri-tert-butylphosphine in toluene the reaction was stirred under reflux for 12 hours, cooled, washed three times with 100ml of water, dried over anhydrous sodium sulfate, then the solvent was removed by evaporation, and the residue was purified by column chromatography with DCM/PE (1:3) to give compound 7 as a white solid (14.1g, 67% yield).

Synthesis example 8: synthesis of Compound 8

Synthesis of compound 8:

a solution of compound G (10.0G,20.6mmol), H (7.5G,20.6mmol) and 2.00mol/L sodium carbonate (4.4G, 41.2mmol) was charged into a three-necked flask, dissolved with 200ml toluene with stirring, protected with nitrogen, followed by addition of Pd (pph)₃)₄(0.7g,0.62mmol), the reaction was stirred under reflux for 12 hours, TLC and MS showed completion of the reaction, mainly the desired product, cooled, washed three times with 150ml of saturated brine, dried over anhydrous sodium sulfate, then evaporated to remove the solvent, and the residue was purified by column chromatography with DCM/PE (1:4) to give compound 8 as a white solid (11.3g, 76% yield).

Synthesis example 9: synthesis of Compound 9

Compound 9 Synthesis of Compound I (: 10.0G,19.9mmol) and Compound G (5.4G,19.9mmol) were charged into a three-necked flask, dissolved with 200ml of toluene under stirring, and then added with Pd (dba)₂(0.34g,0.6mmol) and sodium tert-butoxide (5.7g, 59.7mmol), followed by addition of 3.6ml of a 10% solution of tri-tert-butylphosphine in toluene the reaction was stirred under reflux for 12 hours, cooled, washed three times with 100ml of water, dried over anhydrous sodium sulfate, then the solvent was removed by evaporation, and the residue was purified by column chromatography with DCM/PE (1:3) to give compound 9 as a white solid (9.4g, 68% yield).

Synthesis example 10: synthesis of Compound 10

Synthesis of compound 10:

adding compound I (10.0g,19.9mmol) and compound K (6.6g,19.9mmol) into a three-neck flask, dissolving with 200ml toluene under stirring, adding Pd (dba)₂(0.34g,0.6mmol) and sodium tert-butoxide (5.7g, 59.7mmol), followed by 10% tri-tert-butylphosphinomethyleneSolution 3.6ml the reaction was stirred under reflux for 12 h, cooled, washed three times with 100ml water, dried over anhydrous sodium sulfate and evaporated to remove the solvent, and the residue was purified by column chromatography with DCM/PE (1:3) to give compound 10 as a white solid (10.7g, 71% yield).

Synthesis example 11: synthesis of Compound 11

In a 250mL three-necked flask equipped with a condenser under a nitrogen stream, compound 11-1(6.49g,10mmol) and 4-bromo-dibenzofuran (2.47g,10mmol) were charged in the three-necked flask, dissolved with 100mL of anhydrous toluene under stirring, and then Pd (dba) was added₂(665g,0.5mmol), NatB (1.92g, 20mmol) and 2ml of TTBP in toluene. The reaction was stirred under reflux for 12 h, cooled, washed three times with 100ml of water, dried over anhydrous sodium sulfate and then the solvent was removed by evaporation, and the residue was purified by column chromatography using DCM/PE (1:5) to give compound 11 as a white solid (4.24g, 52% yield).

Synthesis example 12: synthesis of Compound 12

In a 250mL three-necked flask equipped with a condenser under nitrogen flow, compound 12-1(4.87,10mL) and spirobifluorene-4-boronic acid (3.61g,10mmol) were charged in the three-necked flask, dissolved with stirring with 100mL of toluene and 20mL of water, and then Pd (PPh) was added₃)₄(665mg,0.05mmol) and K₂CO₃(2.76g, 20 mmol). The reaction was stirred under reflux for 12 hours, cooled, separated, and the organic phase was washed with 100ml of water 3 times, dried over anhydrous sodium sulfate, then evaporated to remove the solvent, and the residue was purified by column chromatography using DCM/PE (1:10) to give compound 12 as a white solid (5.05g, yield 70%).

Synthesis example 13: synthesis of Compound 13

In a 250mL three-necked flask equipped with a condenser under nitrogen flow, compound 13-1(6.75g,10mmol) and intermediate A (2.47g,10mmol) were charged into the three-necked flask, dissolved with 100mL of anhydrous toluene under stirring, and then Pd (dba) was added₂(665g,0.5mmol), NatB (1.92g, 20mmol) and 2ml of TTBP in toluene. The reaction was stirred under reflux for 12 hours, cooled, washed three times with 100ml of water, dried over anhydrous sodium sulfate and then the solvent was removed by evaporation, and the residue was purified by column chromatography using DCM/PE (1:5) to give compound 13 as a white solid (4.43g, yield 57%).

Comparative synthesis example 1: synthesis of comparative Compound 1

Synthesis of comparative compound 1:

adding the compounds 9-phenyl-3.3-bicarbazole (12.24g,30mmol) and (7.41g,30mmol) into a three-neck flask, stirring and dissolving with 300ml of toluene, protecting with nitrogen, and adding Pd (dba)₂862.5mg,1.5mmol) and sodium tert-butoxide (5.76g, 60mmol), followed by addition of 10ml of a 10% solution of tri-tert-butylphosphine in toluene, the reaction was stirred under reflux for 12 hours, cooled, washed three times with 100ml of water, dried over anhydrous sodium sulfate and then the solvent was removed by evaporation, and the residue was purified by column chromatography with DCM/PE (1:10) to give a white solid (10.67g, 62% yield).

Example 1-example 15, comparative example 1: preparing and characterizing an OLED device:

OLED device structure and materials used for each layer:

ITO/HIL (5nm)/HTL (50 nm)/Host: 10% Dopan (40 nm)/ETL: liq (2:1) (40 nm)/cathode

HIL：MoO₃(ii) a HTL: a triarylamine derivative; in particular NPD;

host, Compounds 1-15, comparative Compound 1 as the first Host; compound (I)A-compound C as a second host; the molar ratio is 1: 1; the volume of the Dopan: ir (ppy)₃。

ETL: TPBi; cathode: liq (1nm)/Al (100 nm).

As a second host compound a or compound B or compound C having the following structure is used:

the energy level of the organic compound material can be obtained by quantum calculation, for example, by using TD-DFT (including time density functional theory) through Gaussian09W (Gaussian Inc.), and a specific simulation method can be seen in WO 2011141110. Firstly, a Semi-empirical method of 'group State/Semi-empirical/Default Spin/AM 1' (Charge 0/Spin Singlet) is used for optimizing the molecular geometrical structure, and then the energy structure of the organic molecules is calculated by a TD-DFT (including time density functional theory) method to obtain 'TD-SCF/DFT/Default Spin/B3PW 91' and a base group of '6-31G (d)' (Charge 0/Spin Singlet). The HOMO and LUMO energy levels were calculated according to the following calibration formula, S1, T1 and resonance factor f (S1) were used directly.

HOMO(eV)＝((HOMO(G)×27.212)-0.9899)/1.1206

LUMO(eV)＝((LUMO(G)×27.212)-2.0041)/1.385

Where HOMO (G) and LUMO (G) are direct calculations of Gaussian09W in Hartree. The results are shown in the following table:

material	HOMO[eV]	LUMO[eV]	T ₁[eV]	S ₁[eV]
Compound 1	-5.73	-2.20	2.92	3.11
Compound 2	-5.63	-2.21	2.84	3.24
Compound 3	-5.56	-2.23	2.72	3.24
Compound 4	-5.72	-2.22	2.90	3.10
Compound 5	-5.51	-2.20	2.89	3.18
Compound 6	-5.50	-2.22	2.90	3.20
Compound 7	-5.60	-2.23	2.89	3.22
Compound 8	-5.71	-2.24	2.92	3.27
Compound 9	-5.56	-2.20	2.90	3.24
Compound 10	-5.57	-2.21	2.92	3.19
Compound 11	-5.50	-2.21	2.89	3.11
Compound 12	-5.54	-2.23	2.89	3.17
Compound 13	-5.60	-2.23	2.87	3.17
Comparative Compound 1	-5.42	-2.22	2.98	3.19
Compound A	-6.09	-2.84	2.71	3.28
Compound B	-6.06	-2.86	2.79	3.19
Compound C	-5.67	-2.91	2.75	2.82

Practice ofExample (b)	First main body	Second body
Example 1	Compound 1	Compound A
Example 2	Compound 2	Compound A
Example 3	Compound 3	Compound B

Example 4	Compound 4	Compound B
Example 5	Compound 5	Compound B
Example 6	Compound 6	Compound B
Example 7	Compound 7	Compound C
Example 8	Compound 8	Compound C
Example 9	Compound 9	Compound C
Example 10	Compound 10	Compound C
Example 11	Compound 11	Compound C
Example 12	Compound 12	Compound C
Example 13	Compound 13	Compound C
Comparative example 1	Comparative Compound 1	Compound A

The device structure adopted is as follows:

having an ITO/HIL (5nm)/HTL (50 nm)/Host: 10% Dopan (40 nm)/ETL: the preparation of an OLED device with Liq (2:1) (40nm)// cathode was as follows:

a. cleaning the conductive glass substrate, namely cleaning the conductive glass substrate by using various solvents such as chloroform, ketone and isopropanol when the conductive glass substrate is used for the first time, and then carrying out ultraviolet ozone plasma treatment;

b. HIL (5nm), HTL (50nm), Host: 10% Dopan (40nm), ETL (40 m): under high vacuum (1X 10)^-6Mbar, mbar).

c. Cathode Liq/Al (1nm/150nm) in high vacuum (1X 10)^-6Millibar) hot evaporation;

d. encapsulation the devices were encapsulated with uv curable resin in a nitrogen glove box.

The current-voltage (J-V) characteristics of each OLED device were characterized by a characterization device, while recording important parameters such as efficiency, lifetime, and external quantum efficiency. It was examined that the efficiency and lifetime of the resulting device were superior to those of the comparative examples, using the compounds 1 to 10 as the first host, and forming a co-host with the second host having an electron transporting property.

Examples	Voltage (V)	Efficiency (cd/A)	Lifetime (LT95, h) @1000cd/m < 2 >)
Example 1	3.5	71	12180
Example 2	3.6	73	12080
Example 3	3.6	73	12000
Example 4	3.6	70	12120
Example 5	3.7	75	11080
Example 6	3.6	73	11000
Example 7	3.6	78	12110
Example 8	3.6	71	12050
Example 9	3.6	71	11990
Example 10	3.6	75	12090
Example 11	3.6	70	12010
Example 12	3.7	70	12100
Example 13	3.6	73	12110
Comparative example 1	3.9	59	6180

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims

PCT domestic application, the claims have been published.