WO2018095384A1

WO2018095384A1 - Deuterated fused ring compound, polymer, mixture and composition, and organic electronic device

Info

Publication number: WO2018095384A1
Application number: PCT/CN2017/112705
Authority: WO
Inventors: 潘君友; 杨曦
Original assignee: 广州华睿光电材料有限公司
Priority date: 2016-11-23
Filing date: 2017-11-23
Publication date: 2018-05-31
Also published as: CN109790087B; CN109790087A

Abstract

A deuterated fused ring compound, polymer, mixture and composition, and the application thereof in an organic electronic device, especially the application thereof in an organic electroluminescent diode. An organic electronic device, especially an organic electroluminescent diode, comprising the deuterated fused ring compound, and the application thereof in the field of technology of display and illumination. By means of device structure optimisation, a better device performance can be achieved, especially an OLED device having a high performance can be realised, thereby providing better options of materials and preparation techniques for the full-colour display and illumination application.

Description

Deuterated fused ring compounds, polymers, mixtures, compositions, and organic electronic devices

Related application

The present application claims the priority of the Chinese Patent Application No. 201611059687.1, entitled "Deuterated Fused Ring Compounds and Their Applications in Electronic Devices", which is hereby incorporated by reference in its entirety. reference.

Technical field

The present invention relates to the field of organic electroluminescence technology, and in particular to a deuterated fused ring compound, a polymer, a mixture, a composition, and an organic electronic device.

Background technique

Organic light-emitting diodes (OLEDs) have great potential for applications in optoelectronic devices such as flat panel displays and illumination due to their versatility in synthesis, relatively low manufacturing costs, and excellent optical and electrical properties.

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

In order to improve the luminous efficiency of organic electroluminescent elements, various phosphor- and phosphorescent-based luminescent material systems have been developed. Whether fluorescent materials or phosphorescent materials, the development of excellent blue light materials is a huge challenge. The organic light-emitting diodes of the currently used blue fluorescent materials are more reliable. Despite this, most of the current blue-light fluorescent materials have too broad emission spectra and poor color purity, which is not conducive to high-end display, and the synthesis of such fluorescent materials is also complicated, which is not conducive to mass production, and such blue fluorescent materials. The OLED stability needs to be further improved. Therefore, the development of a blue fluorescent material having a narrow-band emission spectrum and good stability is advantageous for obtaining a longer-life and higher-efficiency blue light device, and on the other hand, it is advantageous for the improvement of the color gamut, thereby improving the display effect.

The light-emitting layer of the conventional blue organic electroluminescent device adopts a host-guest doping structure. As a conventional blue light host material, ruthenium-based fused ring derivatives are described, for example, in the patents CN1914293B, CN102448945B, US2015287928A1, etc. However, these compounds have problems of insufficient luminous efficiency and brightness, and poor lifetime of the device. As a traditional blue light object As the compound, an arylvinylamine compound (WO 04/013073, WO 04/016575, WO 04/018587) can be used. However, these compounds have poor thermal stability and are easily decomposed, resulting in poor lifetime of the device, which is the main disadvantage of the current OLED materials in the industry. Further, these compounds have poor color purity and it is difficult to achieve dark blue light emission. In addition, US Pat. No. 7,233,019, KR 2006-0006760, and the like discloses an organic electroluminescent device using a lanthanide compound-substituted lanthanide compound, but since the color purity of blue light is low, it is difficult to realize deep blue luminescence, and thus it is natural color. There is a problem with the full color display.

Therefore, there is still a need to further improve the materials. For blue OLEDs, the host material is the key material that determines its lifetime. High-performance blue body materials have always been the focus of people's development.

Summary of the invention

Based on this, it is an object of the present invention to provide a deuterated fused ring compound, a polymer, a mixture, a composition, and an organic electronic device.

The specific technical solutions are as follows:

The present invention provides a deuterated fused ring compound of the formula (I):

among them,

R ₁₁ -R ₁₉ and R ₁₁₀ are each independently H or D, or a linear alkyl group having 1 to 20 C atoms, an alkoxy group or a thioalkoxy group, or a branch having 3 to 20 C atoms. a chain or cyclic alkyl, alkoxy or thioalkoxy group, or a substituted or unsubstituted silyl group, or a substituted ketone group having 1 to 20 C atoms, or having 2 to 20 C An alkoxycarbonyl group of an atom, or an aryloxycarbonyl group having 7 to 20 C atoms, or a cyano group (-CN), or a carbamoyl group (-C(=O)NH ₂ ), or a haloformyl group (- C(=O)-X, wherein X represents a halogen atom, or formyl (-C(=O)-H), or an isocyano group, or an isocyanate, or a thiocyanate or isothiocyanate, Or a hydroxy group, or a nitro group, or CF ₃ , or Cl, or Br, or F, or 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;

Further, at least one of R _{11 -} R ₁₉ and R ₁₁₀ contains one of the structures represented by the general formulae (II) - (IV):

among them,

In R ₂₁ -R ₂₅ , in R ₃₁ -R ₃₇ or in R ₄₁ -R ₄₇ , at least one of them is a single bond to other groups, and the others are independently H or D, or have 1 to 20 a linear alkyl, alkoxy or thioalkoxy group of a C atom, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20 C atoms, or a substitution Or an unsubstituted silyl group, or a substituted ketone group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, Or cyano (-CN), or carbamoyl (-C(=O)NH ₂ ), or haloformyl (-C(=O)-X, wherein X represents a halogen atom), or formyl (- C(=O)-H), or isocyano, or isocyanate, or thiocyanate or isothiocyanate, or hydroxy, or nitro, or CF ₃ , or Cl, or Br, or F, or 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.

In some preferred embodiments, R ₁₃ and/or R ₁₈ contain one of the structures shown in the general formulae (II)-(IV).

In some more preferred embodiments, the one deuterated fused ring compound has the structure of the formula (V-1)-(V-3):

among them,

R ₅₁₀ -R ₅₄₅ are each independently H or D, or a linear alkyl group having 1 to 20 C atoms, an alkoxy group or a thioalkoxy group, or a branch or ring having 3 to 20 C atoms. An alkyl, alkoxy or thioalkoxy group, or a substituted or unsubstituted silyl group, or a substituted ketone group having 1 to 20 C atoms, or an alkane having 2 to 20 C atoms. An oxycarbonyl group, or an aryloxycarbonyl group having 7 to 20 C atoms, or a cyano group (-CN), or a carbamoyl group (-C(=O)NH ₂ ), or a haloformyl group (-C(= O)-X, wherein X represents a halogen atom, or formyl (-C(=O)-H), or an isocyano group, or an isocyanate, or a thiocyanate or isothiocyanate, or a hydroxyl group, Or a nitro group, or CF ₃ , or Cl, or Br, or F, or 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 of 5 to 40 ring atoms, or a combination of these systems.

L represents a linking group which may be a single bond, or a substituted or unsubstituted, substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or deuterated or unsubstituted An aryloxy or heteroaryloxy group of 5 to 40 ring atoms, or a combination of these systems.

Ar ₃ and Ar ₄ are independently deuterated or undeuterated substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 40 ring atoms, or deuterated or unsubstituted having 5 to 40 An aryloxy or heteroaryloxy group of a ring atom, or a combination of these systems.

m and n are each independently an integer of 0-6.

The present invention also provides a high polymer, the repeating unit of the high polymer comprising at least one of the structures represented by the general formula (I) and the general formula (V-1) - (V-3) losing at least one hydrogen A group formed after an atom.

The invention still further provides a mixture comprising the deuterated fused ring compound or polymer, and a second organic functional material. The second organic functional material may be selected from a hole (also called a hole) injection or transport material (HIM/HTM), a hole blocking material (HBM), an electron injecting or transporting material (EIM/ETM), an electron blocking material. (EBM), organic matrix material (Host), singlet illuminant (fluorescent illuminant), triplet illuminant (phosphorescent illuminant), thermally excited delayed fluorescent material (TADF material) and At least one of organic dyes.

The present invention also provides a composition comprising a deuterated fused ring compound or polymer as described above, and an organic solvent.

The invention also provides an organic electronic device comprising the deuterated fused ring compound or polymer.

The organic electronic device can be selected from 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, and an organic spin. Electronic devices, organic sensors and organic plasmon emitting diodes (Organic Plasmon Emitting Diode).

In a preferred embodiment, the organic electronic device is an organic electroluminescent device comprising at least one luminescent layer comprising the deuterated fused ring compound or polymer.

Advantageous Effects: The deuterated fused ring compound according to the present invention can be used as a host material for preparing an organic electroluminescence element having blue luminescence, and a relatively long device life can be obtained with respect to a fused ring compound having no deuteration.

DRAWINGS

1 is a schematic structural view of an organic electronic device provided by the present invention,

In the figure, 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, and 105 is an electron injection layer (EIL) or an electron transport layer (ETL). 106 is a cathode.

detailed description

In order to facilitate the understanding of the present invention, the present invention will be described more fully hereinafter with reference to the accompanying drawings. Preferred embodiments of the invention are shown in the drawings. However, the invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that the understanding of the present disclosure will be more fully understood.

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, unless otherwise defined. The terminology used in the description of the present invention is for the purpose of describing particular embodiments and is not intended to limit 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, metal organic complexes, metal organic complexes, and organometallic complexes have the same meaning and are interchangeable.

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

among them,

R ₁₁ -R ₁₉ and R ₁₁₀ are each independently H or D, or a linear alkyl group having 1 to 20 C atoms, an alkoxy group or a thioalkoxy group, or a branch having 3 to 20 C atoms. a chain or cyclic alkyl, alkoxy or thioalkoxy group, or a substituted or unsubstituted silyl group, or a substituted ketone group having 1 to 20 C atoms, or having 2 to 20 C An alkoxycarbonyl group of an atom, or an aryloxycarbonyl group having 7 to 20 C atoms, or a cyano group (-CN), or a carbamoyl group (-C(=O)NH ₂ ), or a haloformyl group (- C(=O)-X, wherein X represents a halogen atom, or formyl (-C(=O)-H), or an isocyano group, or an isocyanate, or a thiocyanate or isothiocyanate, Or a hydroxy group, or a nitro group, or CF ₃ , or Cl, or Br, or F, or 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 single ring with each other and/or with a ring to which the group is bonded a cyclic or polycyclic aliphatic or aromatic ring system; various bases as described above One or more H may be further substituted D.

among them,

In R ₂₁ -R ₂₅ , R ₃₁ -R ₃₇ and R ₄₁ -R ₄₇ , at least one of them is a single bond to another group, the rest is H or D, or has 1 to 20 C a linear alkyl, alkoxy or thioalkoxy group of an atom, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having from 3 to 20 C atoms, or substituted or absent a substituted silyl group, or a substituted ketone group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or an aryloxycarbonyl group having 7 to 20 C atoms, or cyanide a group (-CN), or a carbamoyl group (-C(=O)NH ₂ ), or a haloformyl group (-C(=O)-X, wherein X represents a halogen atom), or a formyl group (-C ( =O)-H), or isocyano, or isocyanate, or thiocyanate or isothiocyanate, or hydroxy, or nitro, or CF ₃ , or Cl, or Br, or F, or can be crossed a 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 these a combination of systems in which one or more groups may be and/or with the group The bonded ring forms a monocyclic or polycyclic aliphatic or aromatic ring system; one or more of the various groups described above may be further substituted with D.

In some preferred embodiments, in R ₂₁ -R ₂₅ , R ₃₁ -R ₃₇ and R ₄₁ -R ₄₇ , at least one of them is a single bond to the formula (I), and the rest is H. Or D, or a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl group, alkoxy group or sulfur having 3 to 20 C atoms Alkenyloxy, either a substituted or unsubstituted silyl group, or a substituted keto group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or 7 to 20 aryloxycarbonyl C atoms, or a cyano group (-CN), or a carbamoyl group _{(-C (= O) NH 2} ), or a halogen formyl (-C (= O) -X, wherein, X represents halogen Atom), or formyl (-C(=O)-H), or isocyano, or isocyanate, or thiocyanate or isothiocyanate, or hydroxy, or nitro, or CF ₃ , or Cl , or Br, or F, or a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy group having 5 to 40 ring atoms Or a heteroaryloxy group, or a combination of these systems, wherein one or more groups are Rings bonded to each other and/or to the group form a monocyclic or polycyclic aliphatic or aromatic ring system; one or more of the various groups described above may be further substituted by D .

In certain preferred embodiments, R ₁₁ -R ₁₉ and R ₁₁₀ are each independently H or D, or a linear alkyl, alkoxy or thioalkoxy group having from 1 to 10 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 10 C atoms, or a substituted or unsubstituted silyl group, or a substituted ketone having 1 to 10 C atoms a group, or an alkoxycarbonyl group having 2 to 10 C atoms, or an aryloxycarbonyl group having 7 to 10 C atoms, or a cyano group (-CN), or a carbamoyl group (-C(=O)NH ₂ ), or a haloformyl group (-C(=O)-X, wherein X represents a halogen atom), or a formyl group (-C(=O)-H), or an isocyano group, or an isocyanate, or a thiocyanate An ester or isothiocyanate, or a hydroxy group, or a nitro group, or CF ₃ , or Cl, or Br, or F, or a crosslinkable group, or a substituted or unsubstituted group having 5 to 20 ring atoms An aromatic or heteroaromatic ring system, or an aryloxy or heteroaryloxy group having 5 to 20 ring atoms, or a combination of these systems, wherein one or more groups may be and/or The group-bonded ring forms a monocyclic or polycyclic aliphatic or aromatic group Line; various groups according to the above one or more H may be further substituted D.

In certain preferred embodiments, at least one of R ₁₁ -R ₁₉ and R ₁₁₀ , in addition to the structure of formula (II)-(IV), may be independently selected from H, D, or A substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, preferably a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 30 ring atoms, more preferably A substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 20 ring atoms. In a preferred embodiment, the aromatic ring system contains from 5 to 15 carbon atoms, more preferably from 5 to 10 carbon atoms in the ring system; the heteroaromatic ring system contains from 2 to 15 carbon atoms in the ring system. More preferably, it is 2 to 10 carbon atoms, and at least one hetero atom, provided that the total number of carbon atoms and hetero atoms is at least 4. The hetero atom is preferably selected from the group consisting of Si, N, P, O, S and/or Ge, particularly preferably selected from the group consisting of Si, N, P, O and/or S, and more particularly preferably selected from N, O or S.

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

Specifically, examples of the aromatic group are: benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, anthracene, benzopyrene, triphenylene, anthracene, anthracene, snail, and derivatives thereof.

Specifically, examples of heteroaromatic groups are: furan, benzofuran, dibenzofuran, thiophene, benzothiophene, dibenzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole , thiazole, tetrazole, anthracene, oxazole, pyrroloimidazole, pyrrolopyrrol, thienopyrrole, thienothiophene, furopyrrol, furanfuran, thienofuran, benzisoxazole, benzisothiazole , benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-naphthyridine, quinoxaline, phenanthridine, pyridine, quinazoline, quinazolinone, and Its derivatives.

In certain preferred embodiments, R ₁₁ -R ₁₉ and R ₁₁₀ may be further selected from H, D or a combination of one or more of the following structural groups:

among them,

A ¹ , A ² , A ³ , A ⁴ , A ⁵ , A ⁶ , A ⁷ , A ⁸ respectively represent CR ³ or N;

Y ¹ is selected from ^{^{^{CR 4 R 5, SiR 4 R}}} 5, NR 3, C (= O), S , or O;

R ³ , R ⁴ , and R ⁵ are each independently H, D, or a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or 3 to 20 C atoms. a branched or cyclic alkyl, alkoxy or thioalkoxy group, or a silyl group, or a substituted keto group having 1 to 20 C atoms, or having 2 to 20 C atom alkoxycarbonyl groups, or an aryloxycarbonyl group having 7 to 20 C atoms, or a cyano group (-CN), or a carbamoyl group (-C(=O) NH ₂ ), or a haloformyl group (-C(=O)-X, wherein X represents a halogen atom), or a formyl group (-C(=O)-H), or an isocyano group a group, or an isocyanate group, or a thiocyanate group or an isothiocyanate group, or a hydroxyl group, or a nitro group, or a CF ₃ group, or Cl, or Br, or F, or 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 the one or more radicals R ^3, R ^4, R ⁵ can each other and / or with the The ring to which the group is bonded forms a monocyclic or polycyclic aliphatic or aromatic ring.

In certain more preferred embodiments, R ₁₁ -R ₁₉ and R ₁₁₀ may also be selected from H, D or a combination of one or more of the following structural groups, wherein H on the ring may be optionally substituted:

In a more preferred embodiment, R ₁₃ and/or R ₁₈ in the deuterated fused ring compound contains one of the structures shown in the general formulae (II) to (IV).

In other preferred embodiments, R ₁₁ , R ₁₂ , R ₁₄ , R ₁₅ -R ₁₇ , R ₁₉ and R ₁₁₀ are each independently H or D, or substituted or unsubstituted having 5 to 40 ring atoms. An aromatic or heteroaromatic ring system, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems, wherein one or more groups may be and/or The group-bonded ring forms a monocyclic or polycyclic aliphatic or aromatic ring system; one or more of the various groups described above may be further substituted with D.

In still other more preferred embodiments, R ₁₁ , R ₁₂ , R ₁₄ , R ₁₅ -R ₁₇ , R ₁₉ and R ₁₁₀ are each independently H, or D, or have a substitution of 5 to 10 ring atoms or An unsubstituted aromatic or heteroaromatic ring system, or an aryloxy or heteroaryloxy group having 5 to 10 ring atoms, or a combination of these systems, wherein one or more of the groups may be and/or The ring bonded to the group forms a monocyclic or polycyclic aliphatic or aromatic ring system; one or more of the various groups described above may be further substituted with D.

In a most preferred embodiment, R ₁₁ , R ₁₂ , R ₁₄ , R ₁₅ -R ₁₇ , R ₁₉ and R ₁₁₀ are each independently H or D.

In some preferred embodiments, Ar ₁ and Ar ₂ are each independently selected from one of the structures shown in (II)-(IV).

In some highly preferred embodiments, the one deuterated fused ring compound has the structure shown by the general formulae (V-1)-(V-3):

among them,

R ₅₁₀ -R ₅₄₅ are each independently H or D, or a straight-chain alkyl group having 1 to 20 C atoms, alkoxy or thioalkoxy groups, or branched chain having 3-20 C atoms or cycloalkyl An alkyl, alkoxy or thioalkoxy group, or a substituted or unsubstituted silyl group, or a substituted ketone group having 1 to 20 C atoms, or an alkane having 2 to 20 C atoms. An oxycarbonyl group, or an aryloxycarbonyl group having 7 to 20 C atoms, or a cyano group (-CN), or a carbamoyl group (-C(=O)NH ₂ ), or a haloformyl group (-C(= O)-X, wherein X represents a halogen atom, or formyl (-C(=O)-H), or an isocyano group, or an isocyanate, or a thiocyanate or isothiocyanate, or a hydroxyl group, Or a nitro group, or CF ₃ , or Cl, or Br, or F, or 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 of 5 to 40 ring atoms, or a combination of these systems, wherein one or more groups may form a single ring or more with each other and/or a ring to which the group is bonded Acyclic aliphatic or aromatic ring system; among the various groups described above One or more H may be further substituted D.

In some preferred embodiments, R ₅₁₀ -R ₅₄₅ are each independently H, or D, or a linear alkyl, alkoxy or thioalkoxy group having from 1 to 10 C atoms, or having from 3 to a branched or cyclic alkyl, alkoxy or thioalkoxy group of 10 C atoms, or a substituted or unsubstituted silyl group, or a substituted keto group having 1 to 10 C atoms, or An alkoxycarbonyl group having 2 to 10 C atoms, or an aryloxycarbonyl group having 7 to 10 C atoms, or a cyano group (-CN), or a carbamoyl group (-C(=O)NH ₂ ), Or a haloformyl group (-C(=O)-X, wherein X represents a halogen atom), or a formyl group (-C(=O)-H), or an isocyano group, or an isocyanate, or a thiocyanate or Isothiocyanate, or hydroxy, or nitro, or CF ₃ , or Cl, or Br, or F, or a crosslinkable group, or a substituted or unsubstituted aromatic having 5 to 20 ring atoms Or a heteroaromatic ring system, or an aryloxy or heteroaryloxy group having 5 to 20 ring atoms, or a combination of these systems, wherein one or more groups may be bonded to each other and/or to the group Bonded rings form monocyclic or polycyclic aliphatic or aromatic rings One or more of the various groups described above may be further substituted with D.

In some more preferred embodiments, the one deuterated fused ring compound has the structure of the formula (V'-1)-(V'-3):

among them,

R ₅₁₂ -R ₅₁₇ , R ₅₁₈ -R ₅₂₂ , R ₅₃₁ -R ₅₃₅ and R ₅₄₃ -R ₅₄₇ are each independently substituted or unsubstituted substituted or unsubstituted aromatic having 5 to 20 ring atoms or A heteroaromatic ring system, or an aryloxy or heteroaryloxy group having 5 to 20 ring atoms, deuterated or undeuterated, or a combination of these systems. And adjacent substituent groups may form an aromatic or heteroaromatic ring system having 5 to 20 ring atoms with each other.

In some preferred embodiments, L represents a single bond.

In other preferred embodiments, L is a substituted or unsubstituted, substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 20 ring atoms, or deuterated or undeuterated having 5 An aryloxy or heteroaryloxy group of up to 20 ring atoms, or a combination of these systems.

Ar ₃ and Ar ₄ are each independently deuterated or deuterated substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or deuterated or deuterated having 5-40 An aryloxy or heteroaryloxy group of a ring atom, or a combination of these systems. Preferred are deuterated or undeuterated substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 20 ring atoms, or deuterated or undeuterated aryloxy groups having 5 to 20 ring atoms. Or a heteroaryloxy group, or a combination of these systems. Preferred embodiments of Ar ₃ and Ar ₄ are the same as those described above for the aromatic or heteroaromatic groups of R ₁₁ -R ₁₉ and R ₁₁₀ .

m and n are each independently an integer of 0-6, preferably an integer of 0-3, more preferably an integer of 0-2, most preferably 0 or 1.

A specific example of a deuterated fused ring compound according to the present invention is as follows, but is not limited thereto:

The present invention also relates to a method for synthesizing the above-described deuterated fused ring compound, which comprises carrying out a reaction using a raw material containing a reactive group. These active starting materials comprise structural units of the above formula and, in each case, at least one leaving group, for example bromine, iodine, boric acid or boric acid ester. Suitable reactions to form C-C linkages are well known to those skilled in the art and are described in the literature. Particularly suitable and preferred coupling reactions are SUZUKI, STILLE and HECK coupling reactions.

The present invention still further relates to a high polymer having a repeating unit comprising a group formed by losing a structure of at least one H as shown in the formula (I). In certain embodiments, the high polymer is a non-conjugated high polymer wherein the structural unit of formula (I) is on the side chain. In another preferred embodiment, the high polymer is a conjugated high polymer.

The present invention also provides a mixture comprising the above-described deuterated fused ring compound or polymer, and a second organic functional material. The second organic functional material may be selected from a hole (also called a hole) injection or transport material (HIM/HTM), a hole blocking material (HBM), an electron injecting or transporting material (EIM/ETM), an electron blocking material. (EBM), organic matrix material (Host), singlet emitter (fluorescent emitter), triplet emitter (phosphorescent emitter), thermally excited delayed fluorescent material (TADF material) and At least one of machine dyes. Various organic functional materials are described in detail in, for example, WO2010135519A1, US20090134784A1, and WO 2011110277A1, the entire disclosure of which is hereby incorporated by reference.

In a preferred embodiment, the second organic functional material is a fluorescent illuminant (or singlet illuminant) material. The deuterated fused ring compound or polymer is used as a host guest, and the fluorescent illuminant is used as a guest. The weight percentage of the guest is ≤15 wt%, preferably ≤12 wt%, more preferably ≤9 wt%, more preferably ≤8 wt%. Preferably, it is ≤ 7 wt%.

In a more preferred embodiment, the second organic functional material is a fluorescent illuminant material and a = fluorescent host material (or singlet illuminant). In such an embodiment, the deuterated fused ring compound or polymer can be used as a co-host material having a weight ratio to the fluorescent host material of from 3:7 to 7:3.

In certain embodiments, the second organic functional material is a fluorescent host material and a TADF material.

In other preferred embodiments, the second organic functional material is a fluorescent host material and an HTM material.

The HTM, singlet matrix materials, singlet emitters and TADF materials are described in more detail below (but are not limited thereto).

1.HIM/HTM/EBM

Suitable organic HIM/HTM materials may optionally comprise compounds having the following structural units: phthalocyanine, porphyrin, amine, aromatic amine, biphenyl triarylamine, thiophene, thiophene such as dithienothiophene and thiophene, pyrrole, aniline , carbazole, azide and azepine and their derivatives. In addition, suitable HIMs also include self-assembling monomers such as compounds containing phosphonic acid and sliane derivatives; metal complexes and crosslinking compounds and the like.

An electron blocking layer (EBL) is used to block electrons from adjacent functional layers, particularly the luminescent layer. In contrast to a light-emitting device without a barrier layer, the presence of an EBL typically results in an increase in luminous efficiency. The electron blocking material (EBM) of the electron blocking layer (EBL) requires a higher LUMO than an adjacent functional layer such as a light emitting layer. In a preferred embodiment, the HBM has a larger excited state level than the adjacent luminescent layer, such as a singlet or triplet, depending on the illuminant, while the EBM has a hole transport function. HIM/HTM materials that typically have high LUMO levels can be used as EBMs.

Examples of cyclic aromatic amine-derived compounds useful as HIM, HTM or EBM include, but are not limited to, the following general structures:

Each of Ar ¹ to Ar ⁹ may be independently selected from the group consisting of a cyclic aromatic hydrocarbon compound such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalrene, phenanthrene, anthracene, anthracene, fluorene, anthracene, anthracene; Heterocyclic compounds such as dibenzothiophene, dibenzofuran, furan, thiophene, benzofuran, benzothiophene, oxazole, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, evil Triazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, acesulfazine, oxadiazine, hydrazine, benzimidazole, oxazole, pyridazine, benzene And oxazole, benzoxazole, benzothiazole, quinoline, isoquinoline, o-diaza(hetero)naphthalene, quinazoline, quinoxaline, naphthalene, anthracene, pteridine, xanthene, acridine, Phenazine, phenothiazine, phenoxazine, dibenzoselenophene, benzoselenophene, benzofuranpyridine, carbazole, pyridinium, pyrrole dipyridine, furan dipyridine, benzothiophene pyridine, thiophene Pyridine, benzoselenopyridine and selenophene dipyridine; groups containing a 2 to 10 ring structure, which may be the same or different types of cyclic aromatic hydrocarbon groups or aromatic heterocyclic groups, and This directly or through at least one of the following groups joined together, such as an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, chain structural unit and the aliphatic cyclic group. Wherein each of Ar may be further substituted, and the substituent may be hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl or heteroaryl.

In one aspect, Ar ¹ to Ar ⁹ may be independently selected from the group consisting of:

n is an integer from 1 to 20; X ¹ to X ⁸ are CH or N; and Ar ^{1 is} as defined above.

Further examples of cyclic aromatic amine-derived compounds can be found in US Pat. No. 3,567,450, US Pat. No. 4,720,432, US Pat. No. 5,061,569, US Pat. No. 3,615,404, and US Pat.

Examples of metal complexes that can be used as HTM or HIM include, but are not limited to, the following general structures:

M is a metal having an atomic weight greater than 40;

(Y ¹ -Y ² ) is a two-dentate ligand, Y ¹ and Y ^{2 are} independently selected from C, N, O, P and S; L is an ancillary ligand; m is an integer from 1 to The maximum coordination number of this metal; m+n is the maximum coordination number of this metal.

In one embodiment, (Y ¹ -Y ² ) is a 2-phenylpyridine derivative.

In another embodiment, (Y ¹ -Y ² ) is a carbene ligand.

In another embodiment, M is selected from Ir, Pt, Os, and Zn.

In another aspect, the HOMO of the metal complex is greater than -5.5 eV (relative to the vacuum level).

Examples of suitable HIM/HTM compounds are listed in the table below:

2. Singlet matrix material:

The example of the singlet host material is not particularly limited, and any organic compound may be used as the host as long as its singlet energy is higher than that of the illuminant, particularly the singlet illuminant or the luminescent illuminant.

Examples of the organic compound used as the singlet host material may be selected from the group consisting of a cyclic aromatic compound such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, anthracene, phenanthrene, anthracene, anthracene, fluorene, fluorene, An aromatic heterocyclic compound such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, oxazole, carbazole, pyridine Anthraquinone, pyrrole dipyridine, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, triazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine , oxazine, oxazine, oxadiazine, hydrazine, benzimidazole, carbazole, Pyridazine, benzoxazole, benzoxazole, benzothiazole, quinoline, isoquinoline, porphyrin, quinazoline, quinoxaline, naphthalene, anthracene, pteridine, xanthene, acridine, Phenazine, phenothiazine, phenoxazine, benzofuran pyridine, furobipyridine, benzothiophene pyridine, thiophene dipyridine, benzoselenopyridine and selenophene dipyridine; groups containing a 2 to 10 ring structure They may be the same or different types of cyclic aromatic hydrocarbon groups or aromatic heterocyclic groups, and are bonded to each other directly or through at least one of the following groups, 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 aliphatic ring group.

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

Wherein R ¹ may be independently selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl; Ar ¹ is an aryl group Or a heteroaryl group, which has the same meaning as Ar ¹ defined in the above HTM; n is an integer from 0 to 20; X ¹ -X ^{8 is} selected from CH or N; X ⁹ and X ^{10 are} selected from CR ¹ R ² Or NR ¹ .

Some examples of thiol singlet host materials are listed in the table below:

3. Singlet Emitter (Singlet Emitter)

Singlet emitters tend to have longer conjugated pi-electron systems. To date, there have been many examples, such as styrylamine and its derivatives disclosed in JP 2913116 B and WO 2001021729 A1, and indenoindenes and derivatives thereof disclosed in WO 2008/006449 and WO 2007/140847.

In a preferred embodiment, the singlet emitter can be selected from the group consisting of monostyrylamine, dibasic styrylamine, and ternary benzene. Vinylamine, quaternary styrylamine, styrene phosphine, styrene ether and aromatic amine.

A monostyrylamine refers to a compound comprising an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine. A dibasic styrylamine refers to a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A ternary styrylamine refers to a compound comprising three unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A quaternary styrylamine refers to a compound comprising four unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A preferred styrene is stilbene, which may be further substituted. The corresponding phosphines and ethers are defined similarly to amines. An arylamine or an aromatic amine refers to a compound comprising three unsubstituted or substituted aromatic ring or heterocyclic systems directly bonded to a nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably selected from the fused ring system and preferably has at least 14 aromatic ring atoms. Preferred examples thereof are aromatic decylamine, aromatic quinone diamine, aromatic decylamine, aromatic quinone diamine, aromatic thiamine and aromatic quinone diamine. An aromatic amide refers to a compound in which a diaryl arylamine group is attached directly to the oxime, preferably at the position of 9. An aromatic quinone diamine refers to a compound in which two diaryl arylamine groups are attached directly to the oxime, preferably at the 9,10 position. The definitions of aromatic decylamine, aromatic quinone diamine, aromatic thiamine and aromatic quinone diamine are similar, wherein the diaryl aryl group is preferably bonded to the 1 or 1,6 position of hydrazine.

Examples of singlet emitters based on vinylamines and arylamines are also preferred examples and can be found in the following patent documents: 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 2008/0113101 A1, the entire contents of which are hereby incorporated by reference. This article is incorporated herein by reference.

An example of a singlet emitter based on a stilbene extreme derivative is US 5121029.

Further preferred singlet emitters can be selected from indenoindole-amines and indenofluorene-diamines, as disclosed in WO 2006/122630, benzoindoloindole-amines and benzoindenoindole-diamines , as disclosed in WO 2008/006449, dibenzoindolo-amine and dibenzoindeno-diamine, as disclosed in WO 2007/140847.

Other materials which can be used as singlet emitters are polycyclic aromatic hydrocarbon compounds, in particular derivatives of the following compounds: for example, 9,10-bis(2-naphthoquinone), naphthalene, tetraphenyl, xanthene, phenanthrene , 芘 (such as 2,5,8,11-tetra-t-butyl fluorene), anthracene, phenylene such as (4,4'-bis(9-ethyl-3-carbazolevinyl)-1 , 1 '-biphenyl), indenyl hydrazine, decacycloolefin, hexacene benzene, anthracene, spirobifluorene, aryl hydrazine (such as US20060222886), arylene vinyl (such as US5121029, US5130603), cyclopentane Alkene such as tetraphenylcyclopentadiene, rubrene, coumarin, rhodamine, quinacridone, pyran such as 4 (dicyanomethylidene)-6-(4-p-dimethylaminobenzene Vinyl-2-methyl)-4H-pyran (DCM), thiopyran, bis(pyridazinyl)imine boron compound (US 2007/0092753 A1), bis(pyridazinyl)methylene compound, carbostyryl Compounds, oxazinone, benzoxazole, benzothiazole, benzimidazole and pyrrolopyrroledione. Materials for some singlet illuminants can be found in the following patent documents: US 20070252517 A1, US 4769292, US 6020078, US 2007/0252517 A1, US 2007/0252517 A1. The entire contents of the above-listed patent documents are hereby incorporated by reference.

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

4. Thermally Excited Delayed Fluorescent Luminescent Materials (TADF Materials)

Traditional organic fluorescent materials can only use 25% singlet excitons formed by electrical excitation, and the internal quantum efficiency of the device is low (up to 25%). Although the phosphorescent material enhances the inter-system traversal due to the strong spin-orbit coupling of the center of the heavy atom, it can effectively utilize the singlet excitons and triplet exciton luminescence formed by electrical excitation, so that the internal quantum efficiency of the device reaches 100%. However, the problems of expensive phosphorescent materials, poor material stability, and severe roll-off of device efficiency limit their application in OLEDs. The thermally activated delayed fluorescent luminescent material is a third generation organic luminescent material developed after organic fluorescent materials and organic phosphorescent materials. Such materials generally have a small singlet-triplet energy level difference (ΔEst), and triplet excitons can be converted into singlet exciton luminescence by anti-intersystem crossing. This can make full use of the singlet excitons and triplet excitons formed under electrical excitation. The quantum efficiency in the device can reach 100%. At the same time, the material structure is controllable, the property is stable, the price is cheap, no precious metal is needed, and the application prospect in the OLED field is broad.

The TADF material needs to have a small singlet-triplet energy level difference, preferably ΔEst < 0.3 eV, and secondly ΔEst < 0.2 eV, preferably ΔEst < 0.1 eV. In a preferred embodiment, the TADF material has a relatively small ΔEst, and in another preferred embodiment, the TADF has a better 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. Mater., 25, 2013, 3707, Adachi, et. al. Chem. Mater., 25, 2013, 3038, Adachi, et. al. Chem. Mater., 25, 2013 , 3766, Adachi, et. al. J. Mater. Chem. C., 1, 2013, 4599, Adachi, et. al. J. Phys. Chem. A., 117, 2013, 5607, hereby listed above The entire contents of the patent or article file are incorporated herein by reference.

Some examples of suitable TADF luminescent materials are listed in the table below:

Publications in which the above organic functional materials are present are incorporated herein by reference for the purpose of disclosure.

In a preferred embodiment, the deuterated fused ring compound or polymer is used in an evaporated OLED device. For this purpose, the molecular weight of the deuterated fused ring compound or polymer is ≤1000 mol/kg, preferably ≤900 mol/kg, very preferably ≤850 mol/kg, more preferably ≤800 mol/kg, most preferably ≤700 mol/kg.

Another object of the invention is to provide a material solution for printing OLEDs.

For this purpose, the deuterated fused ring compound or polymer has a molecular weight of ≥ 700 mol/kg, preferably ≥ 900 mol/kg, very preferably ≥ 900 mol/kg, more preferably ≥ 1000 mol/kg, most preferably ≥ 1100 mol/kg.

In other preferred embodiments, the halo fused ring compound or polymer has a solubility in toluene of > 10 mg/ml, preferably > 15 mg/ml, most preferably > 20 mg/ml at 25 °C.

The present invention also provides a composition comprising the deuterated fused ring compound or polymer, and a first organic solvent.

In some embodiments, the deuterated fused ring compound can be used as a host material in the composition.

In other embodiments, the composition further comprises a singlet emitter material.

In a preferred embodiment, the composition further comprises a host material and a singlet emitter.

In another preferred embodiment, the composition comprises at least two host materials and a singlet emitter.

In another preferred embodiment, the composition further comprises a host material and a thermally activated delayed fluorescent luminescent material.

In other preferred embodiments, the composition further comprises a hole transporting material (HTM), and more preferably, the HTM comprises a crosslinkable group.

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 in the examples of the present invention may comprise from 0.01 to 20% by weight of a deuterated fused ring compound or polymer, preferably from 0.1 to 15% by weight, more preferably from 0.2 to 10% by weight, most preferably from 0.25 to 5 wt% deuterated fused ring compound or polymer.

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

In a further preferred embodiment, a composition according to the invention comprises at least 50% by weight of an aromatic or heteroaromatic solvent; preferably at least 80% by weight of an aromatic or heteroaromatic solvent; particularly preferably at least 90% by weight Aromatic or heteroaromatic solvents.

Examples of the aromatic or heteroaromatic-based first organic solvent according to the present invention are, but not limited to, 1-tetralone, 3-phenoxytoluene, acetophenone, 1-methoxynaphthalene, p- Diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, o-di Ethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, butylbenzene, ten Dialkylbenzene, 1-methylnaphthalene, 1,2,4-trichlorobenzene, 1,3-dipropoxybenzene, 4,4-difluorodiphenylmethane, diphenyl ether, 1,2-di Methoxy-4-(1-propenyl)benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2- Naphthyl ether, N-methyldiphenylamine, 4-isopropylbiphenyl, α,α-dichlorodiphenylmethane, 4-(3-phenylpropyl)pyridine, benzyl benzoate, 1,1- Bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, dibenzyl ether, and the like.

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

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

The first organic solvent may be a cycloalkane such as decalin.

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

In certain embodiments, the composition according to the present invention further comprises a second organic solvent, examples of which include, but are not limited to, methanol, ethanol, 2-methoxyethanol, dichloro Methane, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1,4-dioxane, acetone, A Ethyl ketone, 1,2 dichloroethane, 3-phenoxytoluene, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, ethyl acetate, butyl acetate Esters, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene, decalin, hydrazine and/or mixtures thereof.

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

δ _d (dispersion force) is in the range of 17.0 to 23.2 MPa ^1/2 , especially in the range of 18.5 to 21.0 MPa ^1/2 ;

range δ _p (polar forces) in the range of 0.2 ~ 12.5MPa ^1/2, especially in the 2.0 ~ 6.0MPa ^1/2;

δ _h (hydrogen bonding) in the range of 0.9 ~ 14.2MPa ^1/2, particularly in a range of 2.0 ~ 6.0MPa ^1/2.

According to the composition of the present invention, the organic solvent is selected in consideration of its boiling point parameter. In the present invention, the organic solvent has a boiling point of ≥ 150 ° C; preferably ≥ 180 ° C; more preferably ≥ 200 ° C; more preferably ≥ 250 ° C; optimally ≥ 275 ° C or ≥ 300 ° C. The boiling points within these ranges are beneficial for preventing nozzle clogging of the inkjet printhead. The organic solvent can be evaporated from the solvent system to form a film comprising the functional material.

In some preferred embodiments, the composition:

1) its viscosity at 25 ° C, in the range of 1 cPs (mPa·s) to 100 cPs, and / or

2) The surface tension is at 25 ° C, in the range of 19 dyne / cm (dyne / cm) to 50 dyne / cm.

According to the composition of the present invention, the organic solvent is selected in consideration of its surface tension parameter. Suitable ink surface tension parameters are suitable for a particular substrate and a particular printing method. For example, for ink jet printing, in a preferred embodiment, the organic solvent has a surface tension at 25 ° C of from about 19 dyne / cm to 50 dyne / cm; more preferably from 22 dyne / cm to 35 dyne / cm; Most preferably in the range of 25 dyne/cm to 33 dyne/cm.

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

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

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

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

Another object of the present invention is to provide the use of the above-described deuterated fused ring compounds and polymers in organic electronic devices.

The organic electronic device can be selected from 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, and an organic spintronic device. Devices, organic sensors and organic plasmon emitting diodes (Organic Plasmon Emitting Diode).

Another object of the present invention is to provide a method of preparing the above organic electronic device,

The method comprises: forming a functional layer on a substrate by evaporation of the above-mentioned deuterated fused ring compound, high polymer or mixture; or co-evaporating the deuterated fused ring compound or polymer with a co-evaporation method The two organic functional materials together form a functional layer on a substrate; or the above composition is applied to a substrate by printing or coating to form a functional layer. The method of printing or coating may be selected from, but not limited to, inkjet printing, Nozzle Printing, typography, screen printing, dip coating, spin coating, blade coating, roller printing, torsion roller Printing, lithography, flexographic printing, rotary printing, spraying, brushing or pad printing, slit-type extrusion coating, etc.

The invention further relates to the use of the composition as a printing ink in the preparation of an organic electronic device, particular preference being given to a preparation process by printing or coating.

Among them, suitable printing or coating techniques include, but are not limited to, inkjet printing, typography, screen printing, dip coating, spin coating, blade coating, roller printing, twist roll printing, lithography, flexography Printing, rotary printing, spraying, brushing or pad printing, slit-type extrusion coating, etc. Preferred are gravure, screen printing and inkjet printing. Gravure printing, ink jet printing will be applied in embodiments of the invention. The solution or suspension may additionally comprise one or more components such as surface active compounds, lubricants, wetting agents, dispersing agents, hydrophobic agents, binders and the like for adjusting viscosity, film forming properties, adhesion, and the like. For information on printing techniques and their requirements for solutions, such as solvents and concentrations, viscosity, etc., please refer to Helmut Kipphan's "Printing Media Handbook: Techniques and Production Methods" (Handbook of Print Media: Technologies and Production Methods). ), ISBN 3-540-67326-1.

In the preparation method as described above, the functional layer has a thickness of from 5 nm to 1000 nm.

The invention further relates to an organic electronic device comprising the deuterated fused ring compound or polymer. The organic electronic device can include a functional layer that is prepared using the composition. Typically, the organic electronic device comprises at least one cathode, an anode and a functional layer between the cathode and the anode, wherein the functional layer comprises a deuterated fused ring compound or polymer as described above.

In a more preferred embodiment, the organic electronic device described above is an electroluminescent device, particularly an OLED. As shown in FIG. 1, the organic electronic device includes a substrate 101, an anode 102, and at least one Light-emitting layer 104, a cathode 106.

The substrate 101 can be opaque or transparent. A transparent substrate can be used to make a transparent light-emitting component. See, for example, Bulovic et al. Nature 1996, 380, p29, and Gu et al, Appl. Phys. Lett. 1996, 68, P2606. The substrate can be rigid or elastic. The substrate can 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 ° C or higher, preferably more than 200 ° C, more preferably more than 250 ° C, preferably More than 300 ° C. Examples of suitable flexible substrates are poly(ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).

The anode 102 can 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 the valence band level of the illuminant in the luminescent layer or the p-type semiconductor material as the HIL or HTL or electron blocking layer (EBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. Examples of the anode material 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 can be deposited using any suitable technique, such as a suitable physical vapor deposition process, 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 in accordance with the present invention.

Cathode 106 can include a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the luminescent layer. In one embodiment, the work function of the cathode and the LUMO level of the illuminant or the n-type semiconductor material as an electron injection layer (EIL) or electron transport layer (ETL) or hole blocking layer (HBL) in the luminescent layer or The absolute value of the difference in conduction band energy levels is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. In principle, all materials which can be used as cathodes for OLEDs are possible as cathode materials for the devices of the invention. Examples of the cathode material include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, and the like. The cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.

The OLED may further include 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, and a hole. Barrier layer (HBL). Materials suitable for use in these functional layers are described in detail in WO2010135519A1, US20090134784A1, and WO2011110277A1, the entire disclosure of which is hereby incorporated by reference.

In a preferred embodiment, the luminescent layer 104 is by vacuum evaporation, the source of which includes the deuterated fused ring compound or polymer.

In another preferred embodiment, the luminescent layer 104 is prepared by printing the composition.

The electroluminescent device according to the invention has an emission wavelength of between 300 and 1000 nm, preferably between 350 and 900 nm, more preferably between 400 and 800 nm.

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

The invention further 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 and the like.

The present invention will be described with reference to the preferred embodiments thereof, but the present invention is not limited to the embodiments described below. It is to be understood that the scope of the invention is intended to be It is to be understood that the modifications of the various embodiments of the invention are intended to be

Example 1: Synthesis of Compound 1

2-(3-bromophenyl-5-d)naphthalene (5.7 g, 20 mmol), (10-(naphthalen-1-yl)fluoren-9-yl group was added to a 250 mL three-necked flask equipped with a condenser under a nitrogen stream. Boric acid (7.0 g, 20 mmol), potassium carbonate (8.3 g, 60 mmol), Pd(PPh ₃ ) ₄ (690 mg, 0.6 mmol), 100 mL of toluene and 30 mL of water were stirred at 90 ° C overnight. After the end of the reaction, the organic phase was washed with water and then purified to afford white crystals (yield:

Example 2: Synthesis of Compound 2

2-(3-bromophenyl-5-d)naphthalene (5.1 g, 18 mmol), (10-(d ₅ -phenyl)fluoren-9-yl group was added to a 250 mL three-necked flask equipped with a condenser under a nitrogen stream. Boric acid (5.5 g, 18 mmol), potassium carbonate (7.5 g, 54 mmol), Pd(PPh ₃ ) ₄ (624 mg, 0.54 mmol), 80 mL of toluene and 20 mL of water were stirred at 90 ° C overnight. After completion of the reaction, the organic phase was washed with water, and then evaporated tolud

Example 3: Synthesis of Compound 3

In a 250 mL three-necked flask equipped with a condenser under a nitrogen stream, 2-(3-bromophenyl-5-d)-7-d-naphthalene (7.1 g, 25 mmol), (10-(naphthalen-1-yl-)- 4-d) fluoren-9-yl)boronic acid (8.7 g, 25 mmol), potassium carbonate (10.4 g, 75 mmol), Pd(PPh ₃ ) ₄ (870 mg, 0.75 mmol), 120 mL of toluene and 30 mL of water, stirred at 90 ° C overnight . After the end of the reaction, the organic phase was washed with water and then evaporated to dryness crystals

Example 4: Synthesis of Compound 4

2-(4-bromophenyl)-6-d-naphthalene (5.7 g, 20 mmol), (10-(4-d-naphthalen-1-yl) was added to a 250 mL three-necked flask equipped with a condenser under a nitrogen stream.蒽-9-yl)boronic acid (7.0 g, 20 mmol), potassium carbonate (8.3 g, 60 mmol), Pd(PPh ₃ ) ₄ (690 mg, 0.6 mmol), 120 mL of toluene and 30 mL of water were stirred at 90 ° C overnight. After the end of the reaction, the organic phase was washed with water and then evaporated tolud

Example 5: Synthesis of Compound 5

In a 250 mL three-necked flask equipped with a condenser under a nitrogen stream, 2-(4-bromo-d ₄ -phenyl)-6-d-naphthalene (4.6 g, 16 mmol), (10-(4-d-naphthalene)- 1-yl)fluoren-9-yl)boronic acid (5.6 g, 16 mmol), potassium carbonate (6.6 g, 48 mmol), Pd(PPh ₃ ) ₄ (570 mg, 0.5 mmol), 80 mL of toluene and 20 mL of water, stirred at 90 ° C overnight . After completion of the reaction, the organic phase was washed with water and then evaporated tolulululu

Comparative Example 1: Synthesis of Comparative Compound 1

In a 250 mL three-necked flask equipped with a condenser under a nitrogen stream, 2-(4-bromophenyl)naphthalene (8.5 g, 30 mmol) and (10-(naphthalen-1-yl)fluoren-9-yl)boronic acid (10.4) were added. g, 30 mmol), potassium carbonate (12.4 g, 90 mmol), Pd(PPh ₃ ) ₄ (1.0 g, 0.9 mmol), 150 mL of toluene and 40 mL of water, and stirred at 90 ° C overnight. After completion of the reaction, the organic phase was washed with water and then evaporated to dryness crystals

Example 6: Preparation and Characterization of OLED Devices:

Materials used in each layer of the OLED device:

HIL: a triarylamine derivative;

HTL: a triarylamine derivative;

Host: Compound 1 - Compound 5, Comparative Compound.

Dopant: anthraquinone derivative.

The preparation steps of an OLED device having ITO/HIL (50 nm) / HTL (35 nm) / Host: 5% Dopant (25 nm) / ETL (28 nm) / LiQ (1 nm) / Al (150 nm) / cathode are as follows:

a, cleaning of the conductive glass substrate: when used for the first time, can be washed with a variety of solvents, such as chloroform, ketone, isopropyl alcohol, and then UV ozone plasma treatment;

b, HIL (50 nm), HTL (35 nm), EML (25 nm), ETL (28 nm): thermally evaporated in a high vacuum (1 x 10 ^-6 mbar, mbar).

c, cathode: LiQ / Al (1nm / 150nm) in a high vacuum (1 × 10 ^-6 mbar) in the thermal evaporation;

d. Package: The device is encapsulated in a nitrogen glove box with an ultraviolet curable resin.

The current-voltage (J-V) characteristics of each OLED device are characterized by characterization equipment while recording important parameters such as efficiency, lifetime and external quantum efficiency. It has been found that the color coordinates of the blue light device prepared by using Compound 1 - Compound 5 as the main body of the EML layer are better than that of Comparative Compound 1, for example, the color coordinates of the device prepared by Compound 5 are (0.149, 0.086); 5 The luminous efficiency of the blue light device prepared as the main body of the EML layer is in the range of 6-8 cd/A, which has more excellent luminous efficiency. In terms of device lifetime, the lifetime of the blue light device prepared by using Compound 1 - Compound 5 as the main body of the EML layer is further improved. A device superior to Comparative Compound 1, such as Compound 5, has a T95 of greater than 1000 hours at 1000 nits.

The technical features of the above-described embodiments may be arbitrarily combined. For the sake of brevity of description, all possible combinations of the technical features in the above embodiments are not described. However, as long as there is no contradiction between the combinations of these technical features, All should be considered as the scope of this manual.

The above-described embodiments are merely illustrative of several embodiments of the present invention, and the description thereof is more specific and detailed, but is not to be construed as limiting the scope of the invention. It should be noted that a number of variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of the invention should be determined by the appended claims.

Claims

A deuterated fused ring compound of the formula (I):

among them,

R 11 -R 19 and R 110 are each independently H, or D, or a linear alkyl group having 1 to 20 C atoms, an alkoxy group or a thioalkoxy group, or having 3 to 20 C atoms. a branched or cyclic alkyl, alkoxy or thioalkoxy group, or a substituted or unsubstituted silyl group, or a substituted ketone group having 1 to 20 C atoms, or 2 to 20 An alkoxycarbonyl group of a C atom, or an aryloxycarbonyl group having 7 to 20 C atoms, or a cyano group (-CN), or a carbamoyl group (-C(=O)NH 2 ), or a haloformyl group ( -C(=O)-X, wherein X represents a halogen atom), or formyl (-C(=O)-H), or an isocyano group, or an isocyanate, or a thiocyanate, or isothiocyanate An ester, or a hydroxy group, or a nitro group, or CF 3 , or Cl, or Br, or F, or a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic group having 5 to 40 ring atoms a ring system, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems;

And, at least one of R 11 - R 19 and R 110 contains one of the structures shown in the general formulae (II) - (IV):

among them,

In R 21 -R 25 , R 31 -R 37 and R 41 -R 47 , at least one of them is a single bond to the fused ring of the formula (I), and the rest is H, or D. Or a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl group, alkoxy group or thioalkane having 3 to 20 C atoms An oxy group, either a substituted or unsubstituted silyl group, or a substituted ketone group having 1 to 20 C atoms, or an alkoxycarbonyl group having 2 to 20 C atoms, or having 7 to 20 C atoms An aryloxycarbonyl group, or a cyano group (-CN), or a carbamoyl group (-C(=O)NH 2 ), or a haloformyl group (-C(=O)-X, wherein X represents a halogen atom) , or formyl (-C(=O)-H), or isocyano, or isocyanate, or thiocyanate, or isothiocyanate, or hydroxy, or nitro, or CF 3 , or Cl, Or Br, or F, or a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy group having 5 to 40 ring atoms or a heteroaryloxy group, or a combination of these systems.
The deuterated fused ring compound according to claim 1, wherein R 13 and/or R 18 contain one of the structures represented by the above formulas (II) to (IV).
The deuterated fused ring compound according to any one of claims 1 to 2, which has a structure represented by the general formulae (V-1) to (V-3):

among them,

R 510 -R 545 are each independently H, or D, or a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branch having 3 to 20 C atoms or a cyclic alkyl, alkoxy or thioalkoxy group, or a substituted or unsubstituted silyl group, or a substituted ketone group having 1 to 20 C atoms, or having 2 to 20 C atoms An alkoxycarbonyl group, or an aryloxycarbonyl group having 7 to 20 C atoms, or a cyano group (-CN), or a carbamoyl group (-C(=O)NH 2 ), or a haloformyl group (-C ( =O)-X, wherein X represents a halogen atom), or formyl (-C(=O)-H), or an isocyano group, or an isocyanate, or a thiocyanate, or an isothiocyanate, or a hydroxyl group, or a nitro group, or CF 3 , or Cl, or Br, or F, or 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;

L represents a single bond, or a deuterated or undeuterated substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or deuterated or undeuterated having 5 to 40 ring atoms An aryloxy or heteroaryloxy group, or a combination of these systems;

Ar 3 and Ar 4 are independently deuterated or undeuterated substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 40 ring atoms, or deuterated or unsubstituted having 5 to 40 a aryloxy or heteroaryloxy group of a ring atom, or a combination of these systems;

m and n are each independently an integer of 0-6.
The deuterated fused ring compound according to any one of claims 1 to 3, wherein H on the deuterated fused ring compound is at least partially deuterated.
A high polymer characterized in that the repeating unit comprises a group formed by the loss of at least one hydrogen atom of the deuterated fused ring compound according to any one of claims 1 to 4.
A mixture comprising the deuterated fused ring compound according to any one of claims 1 to 4 and a second organic functional material, or comprising the high polymer according to claim 5 and a second organic function The second organic functional material is a hole (also called a hole) injection or transport material (HIM/HTM), a hole blocking material (HBM), an electron injecting or transporting material (EIM/ETM), an electron blocking material. (EBM), at least one of an organic matrix material (Host), a singlet illuminant (fluorescent illuminant), a triplet illuminant (phosphorescent illuminant), a thermally excited delayed fluorescent material (TADF material), and an organic dye.
A composition comprising the deuterated fused ring compound according to any one of claims 1 to 4 and an organic solvent, or the polymer and organic solvent according to claim 5, or comprising The mixture of claim 6 and an organic solvent.
An organic electronic device comprising the deuterated fused ring compound according to any one of claims 1 to 4 or the high polymer according to claim 5 or the mixture according to claim 6.
The organic electronic device according to claim 8, wherein the organic electronic device is an organic light emitting diode, an organic photovoltaic cell, an organic light emitting battery, an organic field effect transistor, an organic light emitting field effect transistor, an organic laser, and an organic spin. Electronic devices, organic sensors or organic plasmon emitting diodes.
The organic electronic device according to claim 8, wherein the organic electroluminescent device comprises a light-emitting layer comprising the deuterated fused ring compound or a high polymer or a mixture.