CN111278813B

CN111278813B - Organic compounds, polymers, organic mixtures, compositions and organic electronic devices

Info

Publication number: CN111278813B
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: 2023-05-12
Anticipated expiration: 2038-12-20
Also published as: CN111278813A; WO2019128849A1

Abstract

The invention relates to an organic compound, a high polymer, an organic mixture and a composition. The invention also relates to organic electronic devices, in particular organic electroluminescent diodes, comprising the organic compounds according to the invention. The invention further relates to organic electronic devices prepared using the composition according to the invention. Through device structure optimization, better device performance can be achieved, and particularly, a high-performance OLED device can be achieved, so that better material and preparation technical options are provided for full-color display and illumination application.

Description

Organic compounds, polymers, organic mixtures, compositions and organic electronic devices

The present application claims priority from the chinese patent office, application number 201711451356.7, entitled "organic compounds and their use in organic electronic devices," filed on date 27, 12, 2017, 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 high polymer, an organic mixture, a composition and an organic electronic device.

Background

Organic Light Emitting Diodes (OLEDs) have excellent properties of light weight, active light emission, wide viewing angle, high contrast ratio, high light emission efficiency, low power consumption, easy fabrication of flexible and large-sized panels, and the like, and are regarded 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, a large-scale industrialization process of the organic light-emitting diode is promoted, and the key problems of the organic light-emitting diode, namely the light-emitting performance and the service life, are urgently needed to be solved.

The host material is critical to obtain high performance organic light emitting diodes. At present, an OLED light-emitting device is generally prepared by adopting a single main body material and a light-emitting body, but the single main body material can cause different carrier transmission rates, so that the efficiency of the device is seriously reduced in high brightness (Roll-off), and the service life of the device is shortened. The double-main-body material can be used for weakening some problems brought by a single main body, and especially, through proper material collocation, the selected double-main-body material can effectively form a composite excited state (exciplex), 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 utilizing Co-hosts (Co-host) that form complex excited states (exciplex) in addition to a metal complex as the phosphorescent emitter.

Further, in vapor deposition devices, by preforming the dual host material into a blend or organic alloy, the vapor deposition process can be greatly simplified and the device lifetime significantly increased.

There is still a need for further improvements in materials, particularly host material systems suitable for forming co-hosts, particularly p-type host materials having hole transport properties. The co-host is formed by matching with the n-type host or the bipolar host, 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 is an object of the present invention to provide an organic compound and its use in electronic devices.

The specific technical scheme is as follows:

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

A-(L ₁ )s-B (1)

wherein,,

L ₁ selected from 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, wherein one or more groups may form a mono-or polycyclic aliphatic or aromatic ring system with each other and/or with the ring to which the groups are bonded;

S is 0 or 1;

a is a structure shown in a general formula (II), and B is a structure shown in a general formula (III):

wherein,,

X ₁ selected from O, S, CR ₁₀₅ R ₁₀₆ 、SiR ₁₀₈ R ₁₀₉ ；

X ₂ Selected from NR ₁₁₀ 、CR ₁₁₁ R ₁₁₂ 、SiR ₁₁₃ R ₁₁₄ ；

R ₁₀₁ -R ₁₁₄ Is a substituent, independently of one another, selected from D, or a linear 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, cyano (-CN), carbamoyl (-C (=O) NH) ₂ ) Haloformyl (-C (=O) -X wherein X represents a halogen atom), formyl (-C (=O) -H), isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxy, nitro, CF ₃ 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, wherein one or more groups may form a mono-or polycyclic aliphatic or aromatic ring system with each other and/or with the ring to which the groups are bonded;

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 from 0 to 8.

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

The invention also provides an organic mixture comprising an organic compound as described above and at least one further organic functional material selected from hole (also called hole) injecting or transporting materials, hole blocking materials, electron injecting or transporting materials, electron blocking materials, organic matrix materials, singlet emitters (fluorescent emitters), triplet emitters (phosphorescent emitters), thermally excited delayed fluorescent materials (TADF materials) and organic dyes.

An organic mixture as described above, comprising at least one organic compound as described above as a first organic compound (H1) and one second organic compound (H2), said at least second organic compound having electron transport properties. Preferably, the molar ratio of the first organic compound (H1) to the second organic compound (H2) ranges from 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 above.

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

The organic electronic device 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.

The beneficial effects are that:

according to the organic compound provided by the invention, the organic compound has excellent hole transmission property and stability, and can be matched with another main body with electron transmission property or bipolar property to form a co-main body, so that the electroluminescent efficiency and the service life of the device can be improved.

Drawings

For a better description and illustration of embodiments and/or examples of those inventions disclosed herein, reference may be made to one or more of the accompanying drawings. Additional details or examples used to describe the drawings should not be construed as limiting the scope of the disclosed invention, the presently described embodiments and/or examples, and any of the presently understood modes of carrying out the invention.

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:

in order that the invention may be readily understood, a more complete description of the invention will be rendered by reference to the appended 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 herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein 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 are interchangeable.

In the present invention, the metal-organic complex, and the organometallic complex have the same meaning and are interchangeable.

In the present invention, the composition, printing ink, and ink have the same meaning and are interchangeable.

The invention provides an organic compound shown as a general formula (I):

A-(L ₁ )s-B (1)

wherein,,

L ₁ selected from 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, wherein one or more groups may form a mono-or polycyclic aliphatic or aromatic ring system with each other and/or with the ring to which the groups are bonded.

In certain embodiments, L ₁ The same or different is a substituted or unsubstituted aromatic or heteroaromatic ring system having from 5 to 30 ring atoms, or an aryloxy or heteroaryloxy group having from 5 to 30 ring atoms, or a combination of these systems, wherein one or more groups may form a mono-or polycyclic aliphatic or aromatic ring system with each other and/or the ring to which the groups are bonded.

In certain embodiments, L ₁ The same or different is 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, wherein one or more groups may form a mono-or polycyclic aliphatic or aromatic ring system with each other and/or the ring to which the groups are bonded.

In certain embodiments, L ₁ The same or different is a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 15 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 15 ring atoms, or a combination of these systems, wherein one or more groups may form a mono-or polycyclic aliphatic or aromatic ring system with each other and/or with the ring to which the groups are bonded.

In certain embodiments, L ₁ The same or different is a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 10 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 10 ring atoms, or a combination of these systems, wherein one or more groups may form a mono-or polycyclic aliphatic or aromatic ring system with each other and/or the ring to which the groups are bonded.

In other preferred embodiments, L ₁ Is benzene, naphthalene, phenanthrene, benzophenanthrene, biphenyl, terphenyl, or one or more carbon atoms of these structuresThe child is substituted with an N atom.

In a preferred embodiment, L ₁ Is a biphenyl. In a preferred embodiment, L ₁ Is naphthalene. In a preferred embodiment, L ₁ Is benzene.

In a preferred embodiment, the aromatic ring system according to the invention comprises

A carbon atom, more preferably +.>

The heteroaromatic ring system comprising +.>

A carbon atom, more preferably +.>

And at least one heteroatom, provided 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, and includes 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. Polycyclic, these ring species, at least one of which 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 non-aromatic 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-diaryl fluorene, triarylamine, diaryl ether, etc., are likewise considered aromatic ring systems for the purposes of this invention.

Specifically, examples of aromatic groups are: benzene, naphthalene, anthracene, phenanthrene, perylene, naphthacene, 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,,

X ₁ selected from O, S, CR ₁₀₅ R ₁₀₆ 、SiR ₁₀₈ R ₁₀₉ The method comprises the steps of carrying out a first treatment on the surface of the Preferably X ₁ Selected from O or S.

X ₂ Selected from NR ₁₁₀ 、CR ₁₁₁ R ₁₁₂ 、SiR ₁₁₃ R ₁₁₄ The method comprises the steps of carrying out a first treatment on the surface of the Preferably X ₂ Selected from NR ₁₁₀ Or CR (CR) ₁₁₁ R ₁₁₂ The method comprises the steps of carrying out a first treatment on the surface of the More preferably X ₂ Selected from NR ₁₁₀ 。

R ₁₀₁ -R ₁₁₄ Is D, or a linear alkyl, alkoxy or thioalkoxy radical having 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy radical having 3 to 20C atoms, or a substituted or unsubstituted monosilane A group, or a substituted ketone 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) NH) ₂ ) Haloformyl (-C (=O) -X wherein X represents a halogen atom), formyl (-C (=O) -H), isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxy, nitro, CF ₃ Cl, br, F, crosslinkable groups, or 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 groups may form a mono-or polycyclic aliphatic or aromatic ring system with each other and/or with the ring to which the groups are bonded.

In certain preferred embodiments, formula (III) has at least one set of adjacent R ₁₀₄ May be bonded to form a ring.

In some preferred embodiments, R ₁₀₁ -R ₁₁₄ Is D, or a linear 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, cyano (-CN), carbamoyl (-C (=O) NH) ₂ ) Haloformyl (-C (=O) -X wherein X represents a halogen atom), formyl (-C (=O) -H), isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxy, nitro, CF ₃ Cl, br, F, crosslinkable groups, or 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, wherein one or more groups may form a mono-or polycyclic aliphatic or aromatic ring system with each other and/or with the ring to which the groups 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, and 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 from 0 to 8, preferably an integer from 0 to 6, more preferably an integer from 0 to 4, most preferably an integer from 0 to 2.

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

In a preferred embodiment, the organic compound according to the invention is selected from the group consisting of compounds having the structure according to any one of the following formulas:

wherein,,

x1 is selected from O, S, CR ₁₀₅ R ₁₀₆ O or S is preferable.

Ar ₁ Selected from 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, wherein one or more groups may form a mono-or polycyclic aliphatic or aromatic ring system with each other and/or with the ring to which the groups are bonded.

In certain preferred embodiments, ar ₁ The same or different is a substituted or unsubstituted aromatic or heteroaromatic ring system having from 5 to 30 ring atoms, or an aryloxy or heteroaryloxy group having from 5 to 30 ring atoms, or a combination of these systems, wherein one or more groups may form a mono-or polycyclic aliphatic or aromatic ring system with each other and/or the ring to which the groups are bonded.

In certain preferred embodiments, ar ₁ Identical 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, in which one or more groups may be mono-or polycyclic aliphatic or aromatic with respect to one another and/or the ring to which the groups are bondedA cycloaliphatic ring system.

In certain preferred embodiments, ar ₁ The same or different is a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 15 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 15 ring atoms, or a combination of these systems, wherein one or more groups may form a mono-or polycyclic aliphatic or aromatic ring system with each other and/or with the ring to which the groups are bonded.

In other preferred embodiments, ar ₁ Is benzene, naphthalene, phenanthrene, benzophenanthrene, biphenyl, terphenyl, or one or more carbon atoms of these structures are substituted with N atoms.

In a preferred embodiment, ar ₁ Is a biphenyl. In a preferred embodiment, ar ₁ Is benzene. In other preferred embodiments, ar ₁ Is dibenzofuran. In other preferred embodiments, ar ₁ Is dibenzothiophene. In other preferred embodiments, ar ₁ Is fluorene. In other preferred embodiments, ar ₁ Is spirofluorene.

In a preferred embodiment, the organic compounds according to the invention, L ₁ Or Ar ₁ Each independently selected from one or more of the following structural groups:

wherein,,

A ¹ 、A ² 、A ³ 、A ⁴ 、A ⁵ 、A ⁶ 、A ⁷ 、A ⁸ respectively and independently represent CR ₅₀₁ Or N;

Y ¹ selected from CR ₅₀₂ R ₅₀₃ 、SiR ₅₀₄ R ₅₀₅ 、NR ₅₀₆ C (=o), S or O;

R ₅₀₁ -R ₅₀₅ is H, or D, or a linear alkyl, alkoxy or thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkane having 3 to 20C atomsA group, an alkoxy or thioalkoxy group or 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) NH ₂ ) Haloformyl group (-C (=O) -X wherein X represents a halogen atom), formyl group (-C (=O) -H), isocyano group, isocyanate group, thiocyanate group or isothiocyanate group, hydroxy group, nitro group, CF ₃ Groups, cl, br, F, crosslinkable groups or substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 40 ring atoms, or aryloxy or heteroaryloxy groups having 5 to 40 ring atoms, or combinations of these systems, where one or more groups R ³ ，R ⁴ ，R ⁵ A ring which may be bonded to each other and/or to the group is a monocyclic or polycyclic aliphatic or aromatic ring.

Preferably, R ₅₀₁ -R ₅₀₅ Is H, or D, or a linear 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) NH) ₂ ) Haloformyl group (-C (=O) -X wherein X represents a halogen atom), formyl group (-C (=O) -H), isocyano group, isocyanate group, thiocyanate group or isothiocyanate group, hydroxy group, nitro group, CF ₃ A 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, wherein one or more groups may form a mono-or polycyclic aliphatic or aromatic ring with each other and/or the ring to which the groups are bonded.

In certain preferred embodiments, L is as described above ₁ Or Ar ₁ Selected from one or more combinations comprising the structural groups wherein the H on the ring may be optionally substituted:

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

wherein the dotted line is the structure and L ₁ And single bonds connected.

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

wherein the dotted line is the structure and L ₁ And single bonds connected.

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

The following are examples of the organic compound according to the present invention, but are not limited thereto:

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

The organic compound according to any of the embodiments of the present invention has excellent hole transport properties and stability, and can be combined with another host having electron transport properties or bipolar properties to form a co-host, thereby achieving improved electroluminescent efficiency and device lifetime. The invention 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-, STILE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD-and ULMAN.

In a preferred embodiment, the polymers according to the invention have a glass transition temperature (Tg) of not less than 100℃preferably not less than 120℃more preferably not less than 140℃more preferably not less than 160℃and most preferably not less than 180 ℃.

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

In a preferred embodiment, the polymers according to the invention have a weight average molecular weight (Mw) in the range from 1 to 100. Mu.m; more preferably 5 to 50 tens of thousands; more preferably 10 to 40 tens of thousands, still more preferably 15 to 30 tens of thousands, and most preferably 20 to 25 tens of thousands.

The invention also provides an organic mixture comprising an organic compound or polymer as described above, and at least one other organic functional material selected from hole (also called hole) injecting or transporting materials, hole blocking materials, electron injecting or transporting materials, electron blocking materials, organic matrix materials, singlet emitters (fluorescent emitters), triplet emitters (phosphorescent emitters), thermally excited delayed fluorescent materials (TADF materials) and organic dyes. Various organic functional materials are described in detail in, for example, WO2010135519A1, US20090134784A1 and WO 2011110277A1, the entire contents of which 3 patent documents are 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 preferred embodiment, the organic mixture comprises at least one organic compound or polymer according to the invention and a luminescent material selected from the group consisting of singlet emitters (fluorescent emitters), triplet emitters (phosphorescent emitters) and TADF emitters.

In certain embodiments, the organic mixture comprises at least one organic compound or polymer according to the invention and a fluorescent emitter, wherein the weight percentage of fluorescent emitter is 10 wt.% or less, preferably 9 wt.% or less, more preferably 8 wt.% or less, particularly preferably 7 wt.% or less, 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 percentage by weight of phosphorescent emitter is less than or equal to 25 wt.%, preferably less than or equal to 20 wt.%, more preferably less than or equal to 15 wt.%.

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 an embodiment, the organic compound according to the invention is co-host with said one host material in a weight ratio of from 1:9 to 9:1; in a preferred embodiment, the organic compound according to the invention forms an exciplex with said one host material, which has an energy level higher than that of said phosphorescent emitter.

In another more preferred embodiment, said one mixture comprises at least one organic compound or polymer according to the invention, and one TADF material. Wherein the TADF material functions preferably by 1) forming 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 percent, preferably less than or equal to 10 percent, more preferably less than or equal to 8 percent.

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

Preferably, the at least second organic compound has electron transport properties and also has hole transport properties.

Generally, the molar ratio of the first organic compound (H1) to the second organic compound (H2) ranges from 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.

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

In a preferred embodiment, the organic mixture comprises a fluorine group, or a cyano group, or a group having any one of the following general formulas:

wherein,,

a is an integer from 1 to 3; x is X ¹ –X ⁸ Is selected from CR ⁸⁰¹ Or N, and at least one is N; z is Z ¹ -Z ³ Is a single bond or C (R) ⁸⁰¹ ) ₂ Or O or S.

R ⁸⁰¹ May be selected from the following groups: hydrogen, deuterium, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl, and heteroaryl.

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

wherein,,

Z ⁴ ，Z ⁵ ，Z ⁶ selected from N or CR ⁹⁰¹ And Z is ⁴ ，Z ⁵ ，Z ⁶ At least one of which is an N atom.

Ar ₁₃ ～Ar ₁₅ The same or different is an 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 non-aromatic group having 5 to 40 ring atoms, or a combination of these systems, wherein one or more groups may be further substituted by R ⁹⁰² Substituted, or R ⁹⁰² May further form a ring system with the substituted group. Ar (Ar) ₁₃ ～Ar ₁₅ When any one of them is plural, ar is each ₁₃ ～Ar ₁₅ Each independently selected from the above groups.

In some preferred embodiments, ar ₁₃ ～Ar ₁₅ The same 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 wherein one or more groups may form a single or multiple ring aliphatic or aromatic ring system with each other and/or the ring to which the groups are bonded.

In some more preferred embodiments, ar ₁₃ ～Ar ₁₅ The same or different are deuterated or non-deuterated substituted or unsubstituted aromatic or heteroaromatic ring systems having from 5 to 15 ring atoms or deuterated or non-deuterated aryloxy or heteroaryloxy groups having from 5 to 15 ring atoms or combinations of these systems wherein one or more groups may form a single or multiple ring aliphatic or aromatic ring system with each other and/or the ring to which the groups are bonded.

R ⁹⁰¹ 、R ⁹⁰² At each occurrence, identical or different is H, or D, or a linear 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 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) NH) ₂ ) Haloformyl group (-C (=O) -X wherein X represents a halogen atom), formyl group (-C (=O) -H), isocyano group, isocyanate group, thiocyanate group or isothiocyanate group, hydroxy group, nitro group, CF ₃ A 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, R ⁹⁰¹ 、R ⁹⁰² At each occurrence, identical or different is H, or D, or a linear 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) NH) ₂ ) Haloformyl group (-C (=O) -X wherein X represents a halogen atom), formyl group (-C (=O) -H), isocyano group, isocyanate group, sulfur Cyanate or isothiocyanate groups, hydroxyl groups, nitro groups, CF ₃ A 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, according to the organic mixtures of the invention, ar in formula (IV) ₁₃ -Ar ₁₅ At multiple occurrences, may be the same or different selected from one or a combination of the following structural groups:

wherein d is 1 or 2 or 3 or 4.

Examples of suitable compounds that can be used as the second organic compound (H2) are listed below, but are not limited to:

in a very preferred embodiment, the organic mixture is used for a light-emitting layer in an organic electroluminescent device. There are sometimes special requirements for the first organic compound (H1) and the second organic compound (H2) for stability or process considerations.

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

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

In a preferred embodiment, the organic mixture, wherein the molar ratio of the first organic compound (H1) to the second organic compound (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, the first organic compound (H1) and the second organic compound (H2) in the organic mixture according to the invention have at least one of their glass transition temperatures T _g Not less than 100℃and in a preferred embodiment at least one of them T _g Not less than 120℃and in a preferred embodiment at least one of them T _g 140℃or more, in a more preferred embodiment, at least one of them T _g Not less than 160℃and in a most preferred embodiment at least one of its T _g ≥180℃。

In certain embodiments, the first organic compound (H1) and the second organic compound (H2) have a difference in sublimation temperature of no more than 30K in accordance with the organic mixture of the present invention.

Preferably, the difference in sublimation temperature between the first organic compound (H1) and the second organic compound (H2) is not more than 20K.

More preferably, the difference in sublimation temperature between the first organic compound (H1) and the second organic compound (H2) is not more than 10K.

Optimally, according to an organic mixture of the invention, the sublimation temperature of the first organic compound (H1) and the second organic compound (H2) is the same.

In certain preferred embodiments, the molecular weight difference between the first organic compound (H1) and the second organic compound (H2) according to the invention is not more than 100g/mol, preferably not more than 90g/mol, more preferably not more than 80g/mol, most preferably not more than 60g/mol.

The present invention also provides another organic mixture comprising a first organic compound (H1) and a second organic compound (H2) as described above, and at least another organic functional material selected from the group consisting of a hole (also called hole) injecting or transporting material (HIM/HTM), a Hole Blocking Material (HBM), an electron injecting or transporting material (EIM/ETM), an Electron Blocking Material (EBM), an organic Host material (Host), a singlet light emitter (fluorescent light emitter), a triplet light emitter (phosphorescent light emitter), a thermally excited delayed fluorescent material (TADF material) and an organic dye; preferably selected from phosphorescent emitters and TADF materials. Various organic functional materials are described in detail in, for example, WO2010135519A1, US20090134784A1 and WO 2011110277A1, the entire contents of which 3 patent documents are hereby incorporated by reference.

Some more detailed descriptions of ETM, fluorescent or singlet emitters, phosphorescent or triplet emitters, and TADF materials are provided below (but are not limited thereto).

1.ETM

Examples of ETM materials are not particularly limited, and any metal complex or organic compound may be used as ETM as long as they can transport electrons. Preferred organic ETM materials may be selected from tris (8-hydroxyquinoline) aluminum (AlQ 3), phenazine, phenanthroline, anthracene, phenanthrene, fluorene, bifluorene, spirobifluorene, tolan, 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, indenonaphthyl, benzanthracene, azaphosphole, azaborole, aromatic ketones, lactams, and derivatives thereof.

In one aspect, compounds useful as ETM are molecules comprising at least one of the following groups

R ¹ The following groups may be selected: hydrogen, deuterium, halogen atoms (F, cl, br, I), cyano, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl, when R ¹ When selected from aryl or heteroaryl, R ¹ Ar has the meaning as Ar ₁ ，Ar ₁ ～Ar ₅ The meaning is as described above. n2 is an integer from 0 to 20; x is X ¹ -X ⁸ Selected from CR ¹ Or 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 in which the metal coordinates to O, N or N, N; l is a secondary ligand; r1 is an integer having a value from 1 to the maximum coordination number of the metal. At L _3-r1 R1 is 1 or 2 or 3; when r1 is 3, the subscript 3-r1 of L is 0, representing that L is absent. At L _2-r1 R1 is 1 or 2; when r1 is 2, the subscript 2-r1 of L is 0, representing that L is absent.

Examples of suitable useful ETM compounds are listed below:

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 the light emitting body, particularly the triplet light emitting body or phosphorescent light emitting body, and examples of the metal complex that can be used as the triplet Host (Host) include, but are not limited to, the following general structures:

m3 is a metal; (Y) ₃ -Y ₄ ) Is a bidentate ligand, Y ₃ And Y ₄ Independently selected from C, N, O, P, and S; l is a secondary ligand; r2 is an integer having a value from 1 to the maximum coordination number of the metal;

in a preferred embodiment, the metal complex useful as a triplet entity has the form:

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

Examples of the organic compound which can be a triplet body are selected from compounds containing a cyclic aromatic hydrocarbon group such as benzene, biphenyl, triphenylbenzene, benzofluorene; compounds containing an aromatic heterocyclic group such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, dibenzocarbazole, indolocarbazole, pyridine indole, pyrrole bipyridine, pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, oxazole, dibenzooxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, phthalazine, quinazoline, quinoxaline, naphthalene, phthalein, pteridine, oxaanthracene, acridine, phenazine, phenothiazine, phenoxazine, benzofuran pyridine, furopyridine, benzothiophenpyridine, thiophenpyridine, benzoselenophenpyridine and selenophenedipyridine; groups containing 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 such as 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 with a substituent 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 is selected from compounds comprising at least one of the following groups:

R ² -R ⁷ is as defined for R ¹ ，X ₉ Selected from CR ¹ R ² Or NR (NR) ¹ Y is selected from CR ¹ R ² Or NR (NR) ¹ Or O or S. R is R ¹ ，n2，X ¹ -X ⁸ ，Ar ₁ ～Ar ₃ Is as defined above.

Examples of suitable triplet host materials are listed below but are not limited to:

3. singlet illuminant (Singlet Emitter)

Singlet emitters tend to have longer conjugated pi electron systems. Heretofore, 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 light emitters may be selected from the group consisting of monobasic styrenes, dibasic styrenes, tribasic styrenes, quaternary styrenes, styrenes phosphines, styrenes ethers, and aromatic amines.

A monostyramine is a compound which comprises an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine. A binary styrylamine is a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A ternary styrylamine is a compound which comprises three unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A quaternary styrylamine is a compound comprising four unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. One preferred styrene is stilbene, which may be further substituted. The definition of the corresponding phosphines and ethers is similar to that of the amines. Aryl amine or aromatic amine refers to a compound comprising three unsubstituted or substituted aromatic or heterocyclic ring 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 anthraceneamines, aromatic anthracenediamines, aromatic pyrenamines, aromatic pyrenediamines, aromatic droxylamines and aromatic Qu Eran. An aromatic anthraceneamine is a compound in which a biaryl amine group is attached directly to the anthracene, preferably in the 9 position. An aromatic anthracenediamine is a compound in which two biaryl amine groups are attached directly to the anthracene, preferably in the 9,10 position. Aromatic pyrenamines, aromatic flexoamines and aromatic flexodiamines are defined similarly, with the biaryl amine groups preferably attached to the 1 or 1,6 positions of pyrene.

Examples of singlet emitters based on vinylamines and arylamines are also preferred and can be found in WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549, WO 2007/115610,US 7250532 B2,DE 102005058557 A1,CN 1583691 A,JP 08053397 A,US 6251531 B1,US 2006/210830 A,EP 1957606 A1 and US 2008/0110101 A1, the entire contents of which are hereby incorporated by reference.

An example of a singlet light emitter based on stilbene and its derivatives is US5121029.

Further preferred singlet emitters may be selected from indenofluorene-amines and indenofluorene-diamines, as disclosed in WO 2006/122630, benzoindenofluorene-amines and benzoindenofluorene-diamines, as disclosed in WO 2008/006449, 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, US2016204355 A1.

More preferred singlet emitters may be selected from pyrene derivatives, such as the structures disclosed in US2013175509 A1; triarylamine derivatives of pyrene, such as those containing dibenzofuran units as disclosed in CN 102232068B; other triarylamine derivatives of pyrene having a specific structure are disclosed in CN105085334A, CN105037173 a. 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, tetraphenyl, xanthene, phenanthrene, pyrene (such as 2,5,8, 11-tetra-t-butylperylene), indenopyrene, phenylenes such as (4, 4 '-bis (9-ethyl-3-carbazolyl) -1,1' -biphenyl), bisindenopyrene, decacyclic olefin, hexabenzobenzene, fluorene, spirobifluorene, arylpyrene (such as US 20060222886), arylene ethylene (such as US5121029, US 5130603), 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) boron compounds (US 2007/92753A 1), bis (azinyl) methylene compounds, carbostyryl compounds, benzoxazoles, benzooxazoles, pyrroles, and benzimidazoles. Some materials for singlet emitters can be found in US20070252517 A1, US4769292, US 6020078, US 2007/0252517 A1,US 2007/0252517 A1. The entire contents of the above listed patent documents are hereby incorporated by reference.

Examples of some suitable singlet emitters are listed below:

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

the traditional organic fluorescent material can only emit light by using 25% singlet excitons formed by electric excitation, and the internal quantum efficiency of the device is low (25% at maximum). Although the phosphorescent material enhances intersystem crossing due to strong spin-orbit coupling of heavy atom center, singlet excitons and triplet excitons formed by electric excitation can be effectively utilized to emit light, so that the internal quantum efficiency of the device reaches 100%. However, the problems of expensive phosphorescent materials, poor material stability, serious roll-off of device efficiency and the like limit the application of the phosphorescent materials in OLED. The thermally activated delayed fluorescence luminescent material is a third generation organic luminescent material that develops subsequent to the organic fluorescent material and the organic phosphorescent material. Such materials typically have a small singlet-triplet energy level difference (deltaest), and triplet excitons may be converted to singlet excitons by intersystem crossing to emit light. This makes it possible to fully utilize singlet excitons and triplet excitons formed under electric excitation. The quantum efficiency in the device can reach 100%. Meanwhile, the material has controllable structure, stable property and low price, does not need noble metal, and has wide application prospect in the field of OLED.

The TADF material needs to have a small singlet-triplet energy level difference, preferably deltaest <0.3eV, next preferably deltaest <0.25eV, more preferably deltaest <0.20eV, and most preferably deltaest <0.1eV. In one preferred embodiment, the TADF material has a relatively small Δest, and in another preferred embodiment, the TADF material has a relatively good fluorescence quantum efficiency. Some TADF luminescent materials can be found in the following 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 al.appl. Phys. Lett, 101,2012,093306, adachi, et al.chem. Commun, 48,2012,11392,Adachi,et.al.Nature Photonics,6,2012,253,Adachi,et.al.Nature,492,2012,234,Adachi,et.al.J.Am.Chem.Soc,134,2012,14706,Adachi,et.al.Angew.Chem.Int.Ed,51,2012,11311,Adachi,et.al.Chem.Commun, 48,2012,9580, adachi, et al.chem. Commun, 48,2013,10385, adachi, et al.adv. Mater, 25,2013,3319, adachi, et al adv. Mate, 25,2013,3707, adachi, et al chem. Mate, 25,2013,3038, adachi, et al chem. Mate, 25,2013,3766, adachi, et al j. Mate. Chem. C.,1,2013,4599, adachi, et al j. Phys. Chem. A.,117,2013,5607, the entire contents of the above listed patent or article documents are hereby incorporated by reference.

Examples of some suitable TADF luminescent materials are listed below:

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 formula M (L) n, where M is a metal atom, L, which may be identical 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, n being an integer greater than 1, preferably 1,2,3,4,5 or 6. Optionally, the metal complexes are attached to a polymer via one or more positions, preferably via organic ligands.

In a preferred embodiment, the metal atom M is selected from the transition metal elements or the lanthanoids or actinoids, 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 emitters comprise chelating ligands, i.e. ligands, which coordinate to the metal via at least two binding sites, and particularly preferably the triplet emitters comprise two or three identical or different bidentate or polydentate ligands. Chelating ligands are beneficial for improving the stability of metal complexes.

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 by fluorine or trifluoromethyl. The auxiliary ligand may preferably be selected from the group consisting of acetone acetate and picric acid.

In a preferred embodiment, the metal complexes useful as triplet emitters are of the form:

wherein M is a metal selected from the transition metal elements or the lanthanides or actinides, with particular preference Ir, pt, au;

Ar ¹ each occurrence, 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) ² Each 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) ¹ And Ar is a group ² Are linked together by covalent bonds, may each carry one or more substituent groups, and may be linked together again by substituent groups; l' may be the same or different at each occurrence and 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 applications of triplet emitters can be found in WO 200070655,WO 200141512,WO 200202714,WO 200215645,EP 1191613,EP 1191612,EP 1191614,WO 2005033244,WO 2005019373,US 2005/0258742,WO 2009146770,WO 2010015307,WO 2010031485,WO 2010054731,WO 2010054728,WO 2010086089,WO 2010099852,WO 2010102709,US 20070087219 A1,US 20090061681 A1,US 20010053462 A1,Baldo,Thompson et al.Nature 403, (2000), 750-753,US 20090061681 A1,US 20090061681 A1,Adachi et al.Appl.Phys.Lett.78 (2001), 1622-1624,J.Kido et al.Appl.Phys.Lett.65 (1994), 2124,Kido et al.Chem.Lett.657,1990,US 2007/0252517 A1,Johnson et al, JACS 105,1983,1795,Wrighton,JACS 96,1974,998,Ma et al, synth. Metals 94,1998,245,US 6824895,US 7029766,US 6835469,US 6830828,US 20010053462 A1,WO 2007095118 A1,US 2012004407A1,WO 2012007088A1,WO2012007087A1,WO 2012007086A1,US 2008027220A1,WO 2011157339A1,CN 102282150A,WO 2009118087A1,WO 2013107487A1,WO 2013094620A1,WO 2013174471A1,WO 2014031977A1,WO 2014112450A1,WO 2014007565A1,WO 2014038456A1,WO 2014024131A1,WO 2014008982A1,WO2014023377A1. The entire contents of the above listed patent documents and literature are hereby incorporated by reference.

Examples of some suitable triplet emitters are listed below:

it is an object of the present invention to provide a material solution for an evaporated OLED.

In certain embodiments, the organic compounds according to the 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, most preferably 800g/mol or less.

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

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

In other embodiments, the organic compound according to the invention has a solubility in toluene of not less than 2mg/ml, preferably not less than 3mg/ml, more preferably not less than 4mg/ml, most preferably not less than 5mg/ml at 25 ℃.

It is another object of the invention to provide a solution for printing OLED materials.

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

In preferred embodiments, a composition according to the invention wherein the solvent is selected from the group consisting of aromatic or heteroaromatic, ester, aromatic ketone or ether, aliphatic ketone or ether, alicyclic or olefinic compounds, or inorganic esters such as borates or phosphates, or mixtures of two or more solvents.

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

Examples of solvents based on aromatic or heteroaromatic solvents according to the invention are, but are not limited to: 1-tetralone, 3-phenoxytoluene, acetophenone, 1-methoxynaphthalene, p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopyridine, 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-naphthylether, N-methyldiphenylamine, 4-isopropylbiphenyl, α -dichlorodiphenylmethane, 4- (3-phenylpropyl) pyridine, benzyl benzoate, 1, 4-bis (3, 4-dimethylpropyl) ethane, dibenzyl ether, etc.

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

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

The solvent may be a cycloalkane, such as decalin.

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

In certain embodiments, the compositions according to the present invention comprise 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-trichloroethane, 1, 2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethylsulfoxide, tetrahydronaphthalene, decalin, indene and/or mixtures thereof.

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

δ _d (dispersion force) of 17.0-23.2 MPa ^1/2 In particular in the range from 18.5 to 21.0MPa ^1/2 Is defined by the range of (2);

δ _p (polar force) is 0.2-12.5 MPa ^1/2 In particular in the range of 2.0 to 6.0MPa ^1/2 Is defined by the range of (2);

δ _h the (hydrogen bond force) is between 0.9 and 14.2MPa ^1/2 In particular in the range of 2.0 to 6.0MPa ^1/2 Is not limited in terms of the range of (a).

The composition according to the invention, wherein the organic solvent is selected taking into account its boiling point parameters. In the invention, the boiling point of the organic solvent is more than or equal to 150 ℃; preferably not less than 180 ℃; more preferably not less than 200 ℃; more preferably not less than 250 ℃; and most preferably at a temperature of 275 ℃ or more or 300 ℃ or more. Boiling points in these ranges are beneficial in preventing nozzle clogging of inkjet printheads. The organic solvent may be evaporated from the solvent system to form a film comprising the functional material.

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

1) Its 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 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; and 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 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 selection of a suitable organic solvent and concentration of functional material in the ink. In a preferred embodiment, the viscosity of the organic solvent is less than 100cps; more preferably below 50cps; and most preferably from 1.5 to 20cps. The viscosity here means the viscosity at the ambient temperature at the time of printing, generally at 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 inkjet printing.

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

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

As described above, the organic electronic device may be selected from the group consisting of an Organic Light Emitting Diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an Organic Field Effect Transistor (OFET), an organic light emitting field effect transistor, an organic laser, an organic spintronic device, an organic sensor, and an organic plasmon emitting diode (Organic Plasmon Emitting Diode).

The organic electronic device is an organic electroluminescent device and at least comprises a luminescent layer, wherein the luminescent layer comprises an organic compound or a polymer or an organic mixture.

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

The specific technical scheme is as follows:

a preparation method comprises forming a functional layer on a substrate by vapor deposition, or forming a functional layer on a substrate by co-vapor deposition together with at least one other organic functional material, or coating the composition on a substrate by Printing or coating method selected from (but not limited to) ink jet Printing, spray Printing (Nozzle Printing), letterpress Printing, screen Printing, dip coating, spin coating, doctor blade coating, roller Printing, twist roller Printing, lithographic Printing, flexography, rotary Printing, spray coating, brush coating or pad Printing, slit-type extrusion coating, etc.

The invention also relates to the use of said composition as a printing ink for the production of 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, roller printing, twist roller printing, lithographic printing, flexography, 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, inkjet printing will be applied in embodiments 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, etc., for adjusting viscosity, film forming properties, improving adhesion, etc. For details on printing techniques and their associated requirements for solutions, such as solvent and concentration, viscosity, etc., see the handbook of printing media, techniques and methods of manufacture, by Helmut Kipphan (Handbook of Print Media: technologies and Production Methods), ISBN 3-540-67326-1.

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

The invention further relates to an organic electronic device comprising at least one organic compound or polymer according to the invention or at least one functional layer, which is produced using the composition according to the invention. Generally, such an organic electronic device comprises at least one cathode, one anode and one functional layer 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 above-described organic electronic device 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, p2606. The substrate may be rigid or elastic. The substrate may be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice. In a preferred embodiment, the substrate is flexible, optionally in the form of a polymer film or plastic, having a glass transition temperature Tg of 150℃or higher, preferably over 200℃and more preferably over 250℃and most preferably over 300 ℃. 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 a light emitting 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 of the p-type semiconductor material as HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2eV. 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 patterned. 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 or conduction band level of the emitter in the light emitting layer or of the n-type semiconductor material as an Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, and most preferably less than 0.2eV. In principle, all materials which can be used as cathode of an OLED are possible as cathode materials for the device according to the invention. Yin type vagina Examples of polar materials include, but are not limited to: al, au, ag, ca, ba, mg, liF/Al, mgAg alloy and BaF ₂ /Al, 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 magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.

The OLED may also comprise other 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). Materials suitable 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 layer (104) of the light-emitting device according to the invention is produced by vacuum evaporation, the evaporation source of which comprises a compound or mixture according to the invention.

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

The electroluminescent device according to the invention has a luminescence 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 an electronic device comprising an organic electronic device according to the invention, including, but not limited to, a display device, a lighting device, a light source, a sensor, etc.

The invention will be described in connection with the preferred embodiments, but the invention is not limited thereto, and it will be appreciated that the appended claims summarize the scope of the invention and those skilled in the art who have the benefit of this disclosure will recognize certain changes that may be made to the embodiments of the invention and that 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:

mg (4.6 g,182.3 mmol) with iodine granules I ₂ Adding the solution into a dry three-neck flask, adding 30ml of tetrahydrofuran THF, slowly dropwise adding a proper amount of bromobenzene (10 g,64.1 mmol) solution dissolved in 30ml of THF through a constant pressure funnel under the protection of nitrogen, initiating a format, slowly dropwise adding the bromobenzene solution to keep the format in a moderate reaction state, heating to 70 ℃ after the dropwise adding of the solution is completed, stirring at constant temperature for 2 hours, slowly dropwise adding a Grignard reagent into a THF solution of 4-bromofluorenone (14.5 g,57.69 mmol) under the protection of nitrogen, stirring and reacting for 5 hours at 70 ℃, and completely removing the solvent after the reaction is completed, thus obtaining an intermediate A; a (10.0 g,29.8 mmol) and dibenzofuran (5.0 g,29.8 mmol) were placed in a three-neck flask, methanesulfonic acid MSA (200 ml) was used as solvent, the temperature was raised to 70℃and stirred at constant temperature overnight, TLC and MS showed complete reaction, mainly as the target product, cooled, and the reaction mixture was quenched with 5% NaHCO ₃ After neutralization of the solution to pH 9 or so, extraction with dichloromethane and water was carried out three times with aqueous phase, 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 (12.3 g, yield 43%).

Synthesis of Compound 1:

compound 1.1 (12.3 g,25.3 mmol), N- (3-biphenylyl) carbazole-3-boronic acid (9.2 g,25.3 mmol) and 2.00mol/L sodium carbonate Na ₂ CO ₃ A solution (5.4 g,50.6 mmol) was added to a three-necked flask, dissolved with 300ml of Toluene under stirring, nitrogen-blanketed, and Pd (pph) was then added ₃ ) ₄ (71.3 mg,0.76 mmol) and the reaction mixture was stirred and refluxed for 12 hours, TLC and MS showed complete reaction, the main target product, cooled, and the reaction mixture was washed with 150ml of saturated brineThree times washing, drying over anhydrous sodium sulfate, and then evaporating off the solvent, the residue was purified by column with DCM/PE (1:5) to give compound 1 as a white solid (13.7 g, 75% yield).

Synthesis example 2: synthesis of Compound 2

Synthesis of Compound 2.1:

mg (4.6 g,182.3 mmol) and iodine particles are added into a dry three-neck flask, 30ml of THF is added, a proper amount of bromobenzene (10 g,64.1 mmol) solution dissolved in 30ml of THF is slowly dripped through a constant pressure funnel under the protection of nitrogen, the format is initiated, then bromobenzene solution is slowly dripped to keep the format in a proper reaction state, when the solution is dripped, the solution is heated to 70 ℃ and stirred at constant temperature for 2 hours, after the format reaction is completed, grignard reagent is slowly dripped into a THF solution of 3-bromofluorenone (14.5 g,57.69 mmol) under the protection of nitrogen, and is heated to 70 ℃ and stirred for 5 hours, and the solvent is removed after the reaction is completed, so as to obtain an intermediate B; b (10.0 g,29.8 mmol) and dibenzothiophene (5.5 g,29.8 mmol) were placed in a three-necked flask, methanesulfonic acid (200 ml) was used as a solvent, the temperature was raised to 70℃and stirred at constant temperature overnight, TLC and MS showed complete reaction, mainly as the target product, and the reaction solution was cooled with 5% NaHCO ₃ After neutralization of the solution to pH 9 or so, extraction with dichloromethane and water was carried out three times with aqueous phase, 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 2.1 as a white solid (12.0 g, yield 40%).

Synthesis of Compound 2:

a solution of Compound 2.1 (12.0 g,23.9 mmol), N- (3-biphenylyl) carbazole-3-boronic acid (8.7 g,23.9 mmol) and 2.00mol/L sodium carbonate (5.1 g,47.8 mmol) was added to a three-necked flask, dissolved with 300ml toluene under stirring, nitrogen blanket, and Pd (pph) was then added ₃ ) ₄ (69 mg,0.72 mmol) and the reaction mixture was stirred and refluxed for 12 hours, TLC and MS showed complete reaction, the main target product, cooled, the reaction mixture 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 2 as a white solid (13 g, 75% yield).

Synthesis example 3: synthesis of Compound 3

Synthesis of Compound 3.1:

mg (4.6 g,182.3 mmol) and iodine particles are added into a dry three-neck flask, 30ml of THF is added, a proper amount of bromobenzene (10 g,64.1 mmol) solution dissolved in 30ml of THF is slowly dripped through a constant pressure funnel under the protection of nitrogen, the format is initiated, then bromobenzene solution is slowly dripped to keep the format in a proper reaction state, when the solution is dripped, the solution is heated to 70 ℃ and stirred at constant temperature for 2 hours, until the format reaction is complete, grignard reagent is slowly dripped into a THF solution of 2-bromofluorenone (14.5 g,57.69 mmol) under the protection of nitrogen, and heated to 70 ℃ and stirred for 5 hours, and the solvent is removed after the reaction is complete, thus obtaining an intermediate C; c (10.0 g,29.8 mmol) and dibenzofuran (5.0 g,29.8 mmol) were placed in a three-necked flask, methanesulfonic acid (200 ml) was used as a solvent, the temperature was raised to 70 ℃, the reaction was stirred at constant temperature overnight, TLC and MS showed complete reaction, mainly the target product, cooled, and the reaction solution was treated with 5% NaHCO ₃ After neutralization of the solution to pH 9 or so, extraction with dichloromethane and water was carried out three times with aqueous phase, 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 3.1 as a white solid (12.3 g, yield 43%).

Synthesis of Compound 3:

a solution of Compound 3.1 (12.3 g,25.3 mmol), N- (3-biphenylyl) carbazole-3-boronic acid (9.2 g,25.3 mmol) and 2.00mol/L sodium carbonate (5.4 g,50.6 mmol) was added to a three-necked flask, dissolved with 300ml toluene with stirring, nitrogen blanket, and Pd (pph) was then added ₃ ) ₄ (71.3 mg,0.76 mmol) and the reaction mixture was stirred and refluxed for 12 hours, TLC and MS showed complete reaction, the main target product, cooled, and the reaction mixture was washed three times with 150ml of saturated brine, anhydrous sulfuric acidSodium was dried and then the solvent was evaporated and the residue was purified by column with DCM/PE (1:5) to give compound 3 as a white solid (12.8 g, 70% yield).

Synthesis example 4: synthesis of Compound 4

Synthesis of Compound 4.1:

mg (4.6 g,182.3 mmol) and iodine particles are added into a dry three-neck flask, 30ml of THF is added, a proper amount of bromobenzene (10 g,64.1 mmol) solution dissolved in 30ml of THF is slowly dripped through a constant pressure funnel under the protection of nitrogen, the format is initiated, then bromobenzene solution is slowly dripped to keep the format in a proper reaction state, when the solution is dripped, the solution is heated to 70 ℃ and stirred at constant temperature for 2 hours, until the format reaction is complete, grignard reagent is slowly dripped into a THF solution of 4-bromofluorenone (14.5 g,57.69 mmol) under the protection of nitrogen, and heated to 70 ℃ and stirred for 5 hours, and the solvent is removed after the reaction is complete, thus obtaining an intermediate D; d (10.0 g,29.8 mmol) and dibenzothiophene (5.5 g,29.8 mmol) were placed in a three-necked flask, methanesulfonic acid (200 ml) was used as a solvent, the temperature was raised to 70℃and stirred at constant temperature overnight, TLC and MS showed complete reaction, mainly as the target product, and the reaction solution was cooled with 5% NaHCO ₃ After neutralization of the solution to pH 9 or so, extraction with dichloromethane and water was carried out three times with aqueous phase, 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 4.1 as a white solid (12.0 g, yield 40%).

Synthesis of Compound 4.2:

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

Synthesis of Compound 4:

into a three-necked flask, compound 4.2 (9.9 g,16.8 mmol) and 4-bromo-dibenzothiophene (4.4 g,16.8 mmol) were charged, dissolved with 200ml toluene under stirring, nitrogen-protected, and Pd (dba) was then added ₂ (0.29 g,0.5 mmol) and sodium t-butoxide (4.8 g,50.4 mmol) followed by the addition of 3.1ml of 10% solution of tri-t-butylphosphine in toluene the reaction mixture was stirred and refluxed for 12 hours, cooled, washed three times with 100ml of water, dried over anhydrous sodium sulfate, then evaporated to remove the solvent, and the residue was purified by passing DCM/PE (1:4) through the column to give compound 4 as a white solid (8.4 g, yield 65%).

Synthesis example 5: synthesis of Compound 5

Synthesis of compound 5.1:

into a three-necked flask, compound 1.1 (10 g,20.6 mmol) and 3-bromocarbazole (5 g,20.6 mmol) were charged, dissolved with 200ml toluene under stirring, nitrogen-protected, and Pd (dba) was then added ₂ (0.35 g,0.62 mmol) and sodium t-butoxide (5.9 g,61.8 mmol) followed by the addition of 3.7ml of 10% solution of tri-t-butylphosphine in toluene the reaction mixture was stirred and refluxed for 12 hours, cooled, washed three times with 100ml of water, dried over anhydrous sodium sulfate, then evaporated to remove the solvent, and the residue was purified by passing through the column with DCM/PE (1:4) to give compound 5.1 as a white solid (8 g, yield 60%).

Synthesis of Compound 5:

compound 5.1 (8 g,12.3 mmol) and carbazole (2 g,12.3 mmol) were added to a three-necked flask, dissolved with 150ml toluene under stirring, nitrogen blanketed, and then Pd (dba) was added ₂ (0.21 g,0.37 mmol) and sodium t-butoxide (3.5 g,36.9 mmol) followed by the addition of 2.2ml of 10% solution of tri-t-butylphosphine in toluene the reaction mixture was stirred and refluxed for 12 hours, cooled, washed three times with 100ml of water, dried over anhydrous sodium sulfate, then the solvent was evaporated and the residue was purified by passing through a column with DCM/PE (1:4) to giveTo compound 5 (4.5 g, yield 50%) as a white solid.

Synthesis example 6: synthesis of Compound 6

Synthesis of Compound 6.1:

a solution of the compound N-phenylcarbazole-1-boronic acid (10.0 g,34.8 mmol), o-bromonitrobenzene (7.0 g,34.8 mmol) and 2.00mol/L sodium carbonate (7.4 g,69.6 mmol) was introduced into a three-necked flask, dissolved with 300ml toluene with stirring, nitrogen protection, and Pd (pph) was then added ₃ ) ₄ (1.2 g,1.04 mmol) and the reaction stirred at reflux for 12 hours, TLC and MS showed complete reaction, mainly the target product, cooled, the reaction was washed three times with 150ml of saturated brine, dried over anhydrous sodium sulphate, then the solvent was evaporated and the residue was purified by DCM/PE (1:8) over the column to give compound 6.1 as a white solid (10.0 g, 80% yield).

Synthesis of Compound 6.2:

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

Synthesis of Compound 6:

into a three-necked flask, compound 6.2 (8.2 g,24.7 mmol) and Compound 4.1 (12.4 g,24.7 mmol) were charged, dissolved with 300ml of toluene under stirring, nitrogen-protected, and Pd (dba) was then added ₂ (0.43 g,0.74 mmol) and sodium t-butoxide (7.1 g,74.1 mmol) followed by the addition of 4.5ml of 10% solution of tri-t-butylphosphine in toluene the reaction was stirred and refluxed for 12 hours, cooled, washed three times with 100ml of water, dried over anhydrous sodium sulfate, then the solvent was evaporated, and the residue was purified by passing DCM/PE (1:3) through the columnCompound 6 (13.6 g, yield 73%) was obtained as a white solid.

Synthesis example 7: synthesis of Compound 7

Synthesis of Compound 7.1:

mg (4.6 g,182.3 mmol) and iodine particles are added into a dry three-neck flask, 30ml of THF is added, a proper amount of bromobenzene (10 g,64.1 mmol) solution dissolved in 30ml of THF is slowly dripped through a constant pressure funnel under the protection of nitrogen, the format is initiated, then bromobenzene solution is slowly dripped to keep the format in a proper reaction state, when the solution is dripped, the solution is heated to 70 ℃ and stirred at constant temperature for 2 hours, after the format reaction is completed, grignard reagent is slowly dripped into a THF solution of 3-bromofluorenone (14.5 g,57.69 mmol) under the protection of nitrogen, and is heated to 70 ℃ and stirred for 5 hours, and the solvent is removed after the reaction is completed, thus obtaining an intermediate E; e (10.0 g,29.8 mmol) and dibenzofuran (5.0 g,29.8 mmol) were placed in a three-necked flask, methanesulfonic acid (200 ml) was used as a solvent, the temperature was raised to 70℃and stirred at constant temperature overnight, TLC and MS showed complete reaction, mainly the target product, cooled, and the reaction mixture was quenched with 5% NaHCO ₃ After neutralization of the solution to pH 9 or so, extraction with dichloromethane and water was carried out three times with aqueous phase, 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 (12.6 g, yield 44%).

Synthesis of Compound 7:

into a three-necked flask, compound 7.1 (12.6 g,25.9 mmol) and Compound F (10.6 g,25.9 mmol) were charged, dissolved with 300ml of toluene under stirring, nitrogen-protected, and Pd (dba) was then added ₂ (0.45 g,0.78 mmol) and sodium t-butoxide (7.4 g,77.7 mmol) followed by the addition of a 10% solution of tri-t-butylphosphine in toluene (4.7 ml.) the reaction was stirred and refluxed for 12 hours, cooled, washed three times with 100ml of water, dried over anhydrous sodium sulfate, then the solvent was evaporated and the residue was purified by passing through the column with DCM/PE (1:3) to give compound 7 as a white solid (14.1 g, 67% yield).

Synthesis example 8: synthesis of Compound 8

Synthesis of Compound 8:

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

Synthesis example 9: synthesis of Compound 9

Synthesis of compound 9:

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

Synthesis example 10: synthesis of Compound 10

Synthesis of Compound 10:

into a three-necked flask, compound I (10.0 g,19.9 mmol) and Compound K (6.6 g,19.9 mmol) were charged, dissolved with 200ml toluene under stirring, nitrogen-protected, and Pd (dba) was then added ₂ (0.34 g,0.6 mmol) and sodium t-butoxide (5.7 g,59.7 mmol) followed by the addition of a 10% solution of tri-t-butylphosphine in toluene (3.6 ml) the reaction was stirred and refluxed for 12 hours, cooled, washed three times with 100ml of water, dried over anhydrous sodium sulfate, then evaporated to remove the solvent, and the residue was purified by passing DCM/PE (1:3) over the column to give compound 10 as a white solid (10.7 g, yield 71%).

Synthesis example 11: synthesis of Compound 11

In a 250mL three-necked flask equipped with a condenser under a nitrogen flow, compound 11-1 (6.49 g,10 mmol) and 4-bromo-dibenzofuran (2.47 g,10 mmol) were charged into the three-necked flask, dissolved with 100mL of anhydrous toluene under stirring, and Pd (dba) was then added ₂ (6615 g,0.5 mmol), natB (1.92 g,20 mmol) and 2ml TTBP toluene solution. The reaction was stirred at reflux for 12 hours, cooled, washed three times with 100ml of water, dried over anhydrous sodium sulfate, then the solvent was evaporated and the residue was purified by passing DCM/PE (1:5) through a column to give compound 11 as a white solid (4.24 g, yield 52%).

Synthesis example 12: synthesis of Compound 12

In a 250mL three-necked flask equipped with a condenser under a nitrogen stream, compound 12-1 (4.87, 10 mL) and spirobifluorene-4-boronic acid (3.61 g,10 mmol) were added to the three-necked flask, dissolved with 100mL toluene and 20mL water under stirring, and Pd (PPh) was then added ₃ ) ₄ (665 mg,0.05 mmol) and K ₂ CO ₃ (2.76 g,20 mmol). The reaction was stirred at reflux for 12 h, cooled, the organic phase separated, the reaction was dried over anhydrous sodium sulfate with 100ml of water 3 times, the solvent was then evaporated and the residue was purified by column chromatography with DCM/PE (1:10)The reaction mixture was reacted to give compound 12 (5.05 g, yield 70%) as a white solid.

Synthesis example 13: synthesis of Compound 13

In a 250mL three-necked flask equipped with a condenser under a nitrogen flow, compound 13-1 (6.75 g,10 mmol) and intermediate A (2.47 g,10 mmol) were charged into the three-necked flask, dissolved by stirring with 100mL of anhydrous toluene, and Pd (dba) was then added ₂ (6615 g,0.5 mmol), natB (1.92 g,20 mmol) and 2ml TTBP toluene solution. The reaction was stirred at reflux for 12 hours, cooled, washed three times with 100ml of water, dried over anhydrous sodium sulfate, then the solvent was evaporated and the residue was purified by passing DCM/PE (1:5) through a column to give compound 13 as a white solid (4.43 g, yield 57%).

Comparative synthesis example 1: synthesis of comparative Compound 1

Synthesis of comparative compound 1:

9-phenyl-3.3-dicarbazole (12.24 g,30 mmol) and 4-bromo-dibenzofuran (7.41 g,30 mmol) were added to a three-necked flask, dissolved in 300ml toluene with stirring, nitrogen blanketed, and then Pd (dba) was added ₂ 862.5mg,1.5 mmol) and sodium tert-butoxide NatB (5.76 g,60 mmol) were added followed by 10ml of 10% solution of tri-tert-butylphosphine in toluene. The reaction was stirred at reflux for 12 hours, cooled, washed three times with 100ml of water, dried over anhydrous sodium sulfate, then the solvent was evaporated and the residue was purified by passing DCM/PE (1:10) through a column to give a white solid (10.67 g, yield 62%).

Example 1-example 13, comparative example 1: preparation and characterization of OLED devices:

OLED device structure and materials used in each layer:

ITO/HIL (5 nm)/HTL (50 nm)/Host: 10% Dopant (40 nm)/ETL: liq (2:1) (40 nm)/cathode HIL: moO (MoO) ₃ ；HTL：A triarylamine derivative; specifically, NPD;

host, compounds 1-13, comparative Compound 1 as first Host; compound a-compound C as a second host; the molar ratio is 1:1; dopant: ir (ppy) ₃ 。

ETL: TPBi; and (3) cathode: liq (1 nm)/Al (100 nm).

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

the energy level of the organic compound material can be obtained by quantum computation, for example by means of a Gaussian09W (Gaussian inc.) using TD-DFT (time-dependent density functional theory), and specific simulation methods can be seen in WO2011141110. The molecular geometry is first optimized by the Semi-empirical method "group State/Semi-empirical/Default Spin/AM1" (Charge 0/Spin single), and then the energy structure of the organic molecule is calculated by the TD-DFT (time-Density functional theory) method as "TD-SCF/DFT/Default Spin/B3PW91" and the basis set "6-31G (d)" (Charge 0/Spin single). The HOMO and LUMO energy levels are calculated according to the following calibration formula, and S1, T1 and resonance factor f (S1) are directly used.

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

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

Wherein HOMO (G) and LUMO (G) are direct calculations of Gaussian 09W 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

The adopted device structure is as follows:

has ITO/HIL (5 nm)/HTL (50 nm)/Host: 10% Dopant (40 nm)/ETL: the OLED device of Liq (2:1) (40 nm)// cathode was prepared as follows:

a. cleaning the conductive glass substrate, namely cleaning the conductive glass substrate by using various solvents, such as chloroform, ketone and isopropanol, and then performing ultraviolet ozone plasma treatment;

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

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

d. encapsulation the device was encapsulated with an ultraviolet curable resin in a nitrogen glove box.

The current-voltage (J-V) characteristics of each OLED device were characterized by a characterization apparatus while recording important parameters such as efficiency, lifetime, and external quantum efficiency. By examination, compound 1-compound 13 was used as a first host to form a co-host with a second host having electron transport properties, and the resulting device was superior in efficiency and lifetime to the comparative example.

Examples	Voltage (V)	Efficiency (cd/A)	Lifetime (LT 95, 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 above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.

The above examples illustrate only a few embodiments of the invention, which are described in detail and are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. Accordingly, the scope of protection of the present invention is to be determined by the appended claims.

Claims

1. An organic compound represented by the general formula (I):

A-(L ₁ )s-B (I)

wherein,,

L ₁ is phenyl;

s is 0 or 1;

a in the general formula (I) is selected from the structures shown below:

Wherein the dotted line is the structure and L ₁ A single bond connected;

b in the general formula (I) is selected from the structures shown below:

wherein the dotted line is the structure and L ₁ And single bonds connected.

2. An organic compound according to claim 1, wherein at least one H atom is substituted by a D atom.

3. A polymer comprising a repeating unit derived from the organic compound according to claim 1 or 2.

4. An organic mixture comprising at least one first organic compound (H1) and a second organic compound (H2), the first organic compound (H1) being an organic compound according to claim 1 or 2, the second organic compound (H2) having electron transport properties and the molar ratio of the first organic compound (H1) to the second organic compound (H2) being in the range of 1:9 to 9:1,

the second organic compound (H2) is one selected from the group consisting of compound a, compound B, and compound C:

5. the organic mixture according to claim 4, wherein the sublimation temperatures of the first organic compound (H1) and the second organic compound (H2) differ by no more than 30K.

6. A composition comprising an organic compound according to claim 1 or 2, or a polymer according to claim 3, or an organic mixture according to claim 4 or 5, and at least one organic solvent.

7. An organic electronic device comprising an organic compound according to claim 1 or 2, or a polymer according to claim 3, or an organic mixture according to claim 4 or 5, and at least one organic solvent.

8. The organic electronic device of claim 7, wherein the organic electronic device is selected from the group consisting of 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 spintronic device, an organic sensor, and an organic plasmon emitting diode.

9. An organic electronic device according to claim 7 or 8, wherein the organic electronic device is an organic electroluminescent device comprising at least one light-emitting layer comprising an organic compound according to claim 1 or 2, or a polymer according to claim 3, or an organic mixture according to claim 4 or 5.