CN109790087B - Deuterated fused-ring compounds, polymers, mixtures, compositions, and organic electronic devices - Google Patents

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

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CN109790087B
CN109790087B CN201780059202.5A CN201780059202A CN109790087B CN 109790087 B CN109790087 B CN 109790087B CN 201780059202 A CN201780059202 A CN 201780059202A CN 109790087 B CN109790087 B CN 109790087B
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CN109790087A (en
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潘君友
杨曦
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Guangzhou Chinaray Optoelectronic Materials Ltd
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Abstract

The invention discloses a deuterated fused ring compound, a high polymer, a composition, a mixture and application thereof in an organic electronic device, in particular application in an organic electroluminescent diode. The invention also discloses an organic electronic device, in particular an organic electroluminescent diode, comprising the deuterated fused ring compound and application of the deuterated fused ring compound in display and illumination technologies. According to the invention, through the optimization of the device structure, better device performance can be achieved, particularly a high-performance OLED device can be realized, and better materials and preparation technical options are provided for full-color display and illumination application.

Description

Deuterated fused-ring compounds, polymers, mixtures, compositions, and organic electronic devices
RELATED APPLICATIONS
The present application claims priority from chinese patent application No. 201611059687.1 entitled "deuterated fused ring compounds and their use in electronic devices," filed 2016, 11, 23, which is incorporated herein by reference in its entirety.
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to a deuterated fused ring compound, a high polymer, a mixture, a composition and an organic electronic device.
Background
Organic Light Emitting Diodes (OLEDs) have great potential for applications in optoelectronic devices such as flat panel displays and lighting due to the versatility of organic semiconductor materials in synthesis, relatively low manufacturing costs, and excellent optical and electrical properties.
The organic electroluminescence phenomenon refers to a phenomenon of converting electric energy into light energy using an organic substance. An organic electroluminescent element utilizing an organic electroluminescent phenomenon generally has a structure including a positive electrode and a negative electrode and an organic layer therebetween. In order to improve the efficiency and lifetime of the organic electroluminescent element, the organic layer has a multi-layer structure, each layer containing a different organic substance. Specifically, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like may be included. In such an organic electroluminescent element, when a voltage is applied between the two electrodes, holes are injected from the positive electrode into the organic layer, electrons are injected from the negative electrode into the organic layer, excitons are formed when the injected holes and electrons meet, and light is emitted when the excitons transition back to the ground state. The organic electroluminescent element has the characteristics of self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, high responsiveness and the like.
In order to improve the light emitting efficiency of the organic electroluminescent device, various fluorescent and phosphorescent light emitting material systems have been developed, and the development of excellent blue light emitting materials, whether fluorescent materials or phosphorescent materials, is a great challenge, and in general, the organic light emitting diode using the currently used blue light emitting materials has higher reliability. However, most of the blue fluorescent materials have too wide emission spectrum, poor color purity, and are not suitable for high-end display, and the synthesis of such fluorescent materials is complicated, which is not suitable for mass production, and the OLED stability of such blue fluorescent materials needs to be further improved. Therefore, the development of the blue fluorescent material with narrow-band emission spectrum and good stability is beneficial to obtaining a blue light device with longer service life and higher efficiency on the one hand, and is beneficial to improving the color gamut on the other hand, thereby improving the display effect.
The light emitting layer of the traditional blue light organic electroluminescent element adopts a host-guest doped structure. As conventional blue light host materials, anthracene-based fused ring derivatives are used, as described in patents CN1914293B, CN102448945B, U82015287928A1 and the like, but these compounds have problems of insufficient luminous efficiency and luminance, and poor device lifetime. As a traditional blue light emitting guest
Figure GPA0000264407260000041
However, these compounds have poor thermal stability and are easily decomposed, which results in a short device lifetime, and are the major drawbacks of the OLED materials in the industry at present. Further, these compounds have poor color purity, and it is difficult to realize deep blue light emission. Further, although patent nos. US 7233019 and KR 2006-0006760 disclose organic electroluminescent elements using pyrene compounds having arylamine substituents, they have a problem in full-color displays that exhibit natural colors because deep blue light emission is difficult to achieve due to low color purity of blue light.
Therefore, further improvements in the materials are still needed. For blue OLEDs, the host material is the key material determining its lifetime. High performance blue host materials have been the focus of development.
Disclosure of Invention
Based on this, the object of the present invention is to provide a deuterated fused ring compound, a polymer, a mixture, a composition, and an organic electronic device.
The specific technical scheme is as follows:
the invention provides a deuterated fused ring compound shown as a general formula (I):
Figure GPA0000264407260000042
wherein the content of the first and second substances,
R11-R19and R110Each independently is H or D, or a straight-chain alkyl, alkoxy or thioalkoxy group having from 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having from 3 to 20C atoms, or a substituted or unsubstituted silyl group, or a substituted keto group having from 1 to 20C atoms, or an alkoxycarbonyl group having from 2 to 20C atoms, or an aryloxycarbonyl group having from 7 to 20C atoms, or a cyano group (-CN), or a carbamoyl group (-C (═ O) NH2) Or haloformyl (-C (═ O) -X, where X represents a halogen atom), or formyl (-C (═ O) -H), or isocyano, or isocyanate, or thiocyanate or isothiocyanate, or hydroxy, or nitro, or CF3Or 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;
and, R11-R19And R110At least one of which contains one of the structures represented by the general formulae (II) to (IV):
Figure GPA0000264407260000051
wherein the content of the first and second substances,
R21-R25middle and R31-R37In or R41-R47In which at least one is a single bond to another group and the others are each independently H or D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20C atoms, or 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, or a cyano group (-CN), or a carbamoyl group (-C (═ O) NH2) Or haloformyl (-C (═ O) -X, where X represents a halogen atom), or formyl (-C (═ O) -H), or isocyano, or isocyanate, or thiocyanate or isothioCyanate ester, or hydroxy, or nitro, or CF3Or 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, R13And/or R18Containing one of the structures shown in the general formulas (II) to (IV).
In some more preferred embodiments, one of the deuterated fused ring compounds has a structure represented by one of formulas (V-1) to (V-3):
Figure GPA0000264407260000052
Figure GPA0000264407260000061
wherein the content of the first and second substances,
R510-R545each independently is H or D, or a straight-chain alkyl, alkoxy or thioalkoxy group having from 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having from 3 to 20C atoms, or a substituted or unsubstituted silyl group, or a substituted keto group having from 1 to 20C atoms, or an alkoxycarbonyl group having from 2 to 20C atoms, or an aryloxycarbonyl group having from 7 to 20C atoms, or a cyano group (-CN), or a carbamoyl group (-C (═ O) NH2) Or haloformyl (-C (═ O) -X, where X represents a halogen atom), or formyl (-C (═ O) -H), or isocyano, or isocyanate, or thiocyanate or isothiocyanate, or hydroxy, or nitro, or CF3Or 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 linking group, which may be a single bond, or a deuterated or non-deuterated substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or a deuterated or non-deuterated aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems.
Ar3And Ar4Independently of one another, are deuterated or non-deuterated substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 40 ring atoms or deuterated or non-deuterated aryloxy or heteroaryloxy groups having 5 to 40 ring atoms, or combinations of these systems.
m and n are each independently an integer of 0 to 6.
The invention also provides a high polymer, wherein the repeating unit of the high polymer comprises a group formed by losing at least one hydrogen atom in at least one of the structures shown as the general formula (I) and the general formulae (V-1) to (V-3).
The invention further provides a mixture which comprises the deuterated fused ring compound or the polymer and a second organic functional material. The second organic functional material can be selected from hole (also called hole) injection or transport materials (HIM/HTM), Hole Blocking Materials (HBM), electron injection or transport materials (EIM/ETM), Electron Blocking Materials (EBM), organic matrix materials (Host), singlet emitters (fluorescent emitters), triplet emitters (phosphorescent emitters), thermal excitation delayed fluorescent materials (TADF materials) and
Figure GPA0000264407260000071
the invention also provides a composition comprising the deuterated fused ring compound or the polymer and an organic solvent.
The invention also provides an organic electronic device comprising the deuterated fused ring compound or the polymer.
The Organic electronic device can be selected from Organic Light Emitting Diodes (OLEDs), Organic photovoltaic cells (OPVs), Organic light Emitting cells (OLEECs), Organic Field Effect Tubes (OFETs), Organic light Emitting field effect tubes (OFETs), Organic lasers, Organic spinning electronic devices, Organic sensors and Organic Plasmon Emitting diodes (Organic plasma Emitting diodes).
In a preferred embodiment, the organic electronic device is an organic electroluminescent device comprising at least one light-emitting layer, wherein the light-emitting layer comprises the deuterated fused ring compound or polymer.
Has the advantages that: the deuterated fused ring compound can be used as a host material for preparing an organic electroluminescent element with blue luminescence, and can obtain longer device life compared with a non-deuterated fused ring compound.
Drawings
FIG. 1 is a schematic structural view of an organic electronic device provided by the present invention,
in the drawing, 101 denotes a substrate, 102 denotes an anode, 103 denotes a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL), 104 denotes a light-emitting layer, 105 denotes an Electron Injection Layer (EIL) or an Electron Transport Layer (ETL), and 106 denotes a cathode.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
In the present invention, the Host material, the Matrix material, the Host material and the Matrix material have the same meaning and may be interchanged.
In the present invention, the metal-organic complex, and the organometallic complex have the same meanings and may be interchanged.
In the present invention, the composition, printing ink, and ink have the same meaning and may be interchanged.
The invention provides a deuterated fused ring compound shown as a general formula (I):
Figure GPA0000264407260000081
wherein the content of the first and second substances,
R11-R19and R110Each independently is H or D, or a straight-chain alkyl, alkoxy or thioalkoxy group having from 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having from 3 to 20C atoms, or a substituted or unsubstituted silyl group, or a substituted keto group having from 1 to 20C atoms, or an alkoxycarbonyl group having from 2 to 20C atoms, or an aryloxycarbonyl group having from 7 to 20C atoms, or a cyano group (-CN), or a carbamoyl group (-C (═ O) NH2) Or haloformyl (-C (═ O) -X, where X represents a halogen atom), or formyl (-C (═ O) -H), or isocyano, or isocyanate, or thiocyanate or isothiocyanate, or hydroxy, or nitro, or CF3Or Cl, or Br, or F, or a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having from 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having from 5 to 40 ring atoms, or a combination of these systems, where one or more of the radicals can form a mono-or polycyclic aliphatic or aromatic ring system with one another and/or with the ring bonded to said radicals; one or more of the H's of the various groups described above may also be further substituted by D.
And, R11-R19And R110At least one of which contains one of the structures represented by the general formulae (II) to (IV):
Figure GPA0000264407260000082
wherein the content of the first and second substances,
R21-R25middle and R31-R37Neutralization of R41-R47In which in each case at least one is a single bond to another radical and the remainder are H or D, or a straight-chain alkyl, alkoxy or thioalkoxy group having from 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having from 3 to 20C atoms, or a substituted or unsubstituted silyl group, or a substituted keto group having from 1 to 20C atoms, or an alkoxycarbonyl group having from 2 to 20C atoms, or an aryloxycarbonyl group having from 7 to 20C atoms, or a cyano group (-CN), or a carbamoyl group (-C (═ O) NH2) Or haloformyl (-C (═ O) -X, where X represents a halogen atom), or formyl (-C (═ O) -H), or isocyano, or isocyanate, or thiocyanate or isothiocyanate, or hydroxy, or nitro, or CF3Or Cl, or Br, or F, or a crosslinkable group, or have 5 to
Figure GPA0000264407260000091
Oxy groups, or combinations of these systems, wherein one or more of the groups may form a mono-or polycyclic aliphatic or aromatic ring system with each other and/or with the rings to which the groups are bonded; one or more of the H's of the various groups described above may also be further substituted by D.
In some preferred embodiments, R21-R25Middle and R31-R37Neutralization of R41-R47In which in each case at least one is a single bond to the general formula (I) and the remainder are H or D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 20C atoms, or 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, or a cyano group (-CN), or a carbamoyl group (-C (═ O) NH2) Or haloformyl (-C (═ O) -X, where X represents a halogen atom), or formyl (-C (═ O) -H), or isocyano, or isocyanate, or thiocyanate or isothiocyanate, or hydroxy, or nitro, or CF3Or Cl, or Br, or F, orCrosslinkable 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, where one or more of the groups may form a mono-or polycyclic aliphatic or aromatic ring system with one another and/or with the ring bonded to the said group; one or more of the H's of the various groups described above may also be further substituted by D.
In certain preferred embodiments, R11-R19And R110Each independently is H or D, or a straight-chain alkyl, alkoxy or thioalkoxy group having 1 to 10C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 10C atoms, or a 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, or a cyano group (-CN), or a carbamoyl group (-C (═ O) NH2) Or haloformyl (-C (═ O) -X, where X represents a halogen atom), or formyl (-C (═ O) -H), or isocyano, or isocyanate, or thiocyanate or isothiocyanate, or hydroxy, or nitro, or CF3Or Cl, or Br, or F, or a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having from 5 to 20 ring atoms, or an aryloxy or heteroaryloxy group having from 5 to 20 ring atoms, or a combination of these systems, where one or more of the radicals can form a mono-or polycyclic aliphatic or aromatic ring system with one another and/or with the ring bonded to said radicals; one or more of the H's of the various groups described above may also be further substituted by D.
In some preferred embodiments, R11-R19And R110In which, in addition to at least one structure comprising a structure of the general formulae (II) to (IV), they are selected, independently of one another, from H, D, or a substituted or unsubstituted aromatic or heteroaromatic ring system having from 5 to 40 ring atoms, preferably from 5 to 30 ring atoms, more preferably from 5 to 20 ring atoms. Is better at oneIn the first embodiment, the aromatic ring system contains 5 to 15 carbon atoms, preferably 5 to 10 carbon atoms; the heteroaromatic ring system contains 2 to 15 carbon atoms, more preferably 2 to 10 carbon atoms, and at least one heteroatom in the ring system, 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 Si
Figure GPA0000264407260000101
The above-mentioned aromatic ring system or aromatic group means a hydrocarbon group containing at least one aromatic ring, including monocyclic groups and polycyclic ring systems. The heteroaromatic ring systems or heteroaromatic groups described above refer to hydrocarbon groups (containing heteroatoms) containing at least one heteroaromatic ring, including monocyclic groups and polycyclic ring systems. These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, i.e., fused rings. At least one of these ring species of the polycyclic ring is aromatic or heteroaromatic. For the purposes of the present invention, aromatic or heteroaromatic ring systems include not only aromatic or heteroaromatic systems, but also systems in which a plurality of aryl or heteroaryl groups may also be interrupted by short nonaromatic units (< 10% of non-H atoms, preferably less than 5% of non-H atoms, such as C, N or O atoms). Thus, for example, systems such as 9, 9' -spirobifluorene, 9, 9-diarylfluorene, triarylamines, diaryl ethers, etc., are likewise considered aromatic ring systems for the purposes of the present invention.
Specifically, examples of aromatic groups are: benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, pyrene, benzopyrene, triphenylene, acenaphthene, fluorene, spirofluorene and derivatives thereof.
Specifically, examples of heteroaromatic groups are: furan, benzofuran, dibenzofuran, thiophene, benzothiophene, dibenzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrole, furofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, phthalazine, quinoxaline, phenanthridine, primary pyridine, quinazoline, quinazolinone, and derivatives thereof.
In certain preferred embodiments R11-R19And R110Can be further selected from H, D or one or more combination of the following structural groups:
Figure GPA0000264407260000102
wherein the content of the first and second substances,
A1、A2、A3、A4、A5、A6、A7、A8each independently represents CR3Or N;
Y1selected from the group consisting of CR4R5、SiR4R5、NR3C (═ O), S, or O;
R3、R4、R5each independently is H, D, or a straight-chain alkyl, alkoxy or thioalkoxy group having from 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having from 3 to 20C atoms, or a silyl group, or a substituted keto group having from 1 to 20C atoms, or an alkoxycarbonyl group having from 2 to 20C atoms, or an aryloxycarbonyl group having from 7 to 20C atoms, or a cyano group (-CN), or a carbamoyl group (-C (═ O) NH2) 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 group, or a thiocyanate group or an isothiocyanate group, or a hydroxyl group, or a nitro group, or CF3A group, or Cl, or Br, or F, or a crosslinkable group, or having 5 to 40
Figure GPA0000264407260000111
Groups, or combinations of these systems, in which one or more radicals R3，R4，R5Can be bonded to each other and/or to said groupsForm a mono-or polycyclic aliphatic or aromatic ring.
In some more preferred embodiments R11-R19And R110Also can be selected from H, D or one or more combination of the following structural groups, wherein H on the ring can be optionally substituted:
Figure GPA0000264407260000112
in a preferred embodiment, R in the deuterated fused ring compound13And/or R18Containing one of the structures shown in the general formulas (II) to (IV).
In other preferred embodiments, R11、R12、R14、R15-R17、R19And R110Each independently of the other being H or D, or a substituted or unsubstituted aromatic or heteroaromatic ring system having from 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having from 5 to 40 ring atoms, or a combination of these systems, where one or more of the radicals can form a mono-or polycyclic aliphatic or aromatic ring system with one another and/or with the rings to which the radicals are bonded; one or more of the H's of the various groups described above may also be further substituted by D.
In other more preferred embodiments, R11、R12、R14、R15-R17、R19And R110Each independently of the other being H, or D, or a substituted or unsubstituted aromatic or heteroaromatic ring system having from 5 to 10 ring atoms, or an aryloxy or heteroaryloxy group having from 5 to 10 ring atoms, or a combination of these systems, where one or more of the radicals can form a mono-or polycyclic aliphatic or aromatic ring system with one another and/or with the rings to which the radicals are bonded; one or more of the H's of the various groups described above may also be further substituted by D.
In a most preferred embodiment, R11、R12、R12、R15-R17、R19And R110Each independently is H or D.
In some preferred embodiments, Ar1And Ar2Each independently selected from one of the structures shown in (II) - (IV).
In some preferred embodiments, one of the deuterated fused ring compounds has a structure represented by one of formulas (V-1) through (V-3):
Figure GPA0000264407260000121
wherein the content of the first and second substances,
R510-R545each independently is H or D, or a straight-chain alkyl, alkoxy or thioalkoxy group having from 1 to 20C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having from 3 to 20C atoms, or a substituted or unsubstituted silyl group, or a substituted keto group having from 1 to 20C atoms, or an alkoxycarbonyl group having from 2 to 20C atoms, or an aryloxycarbonyl group having from 7 to 20C atoms, or a cyano group (-CN), or a carbamoyl group (-C (═ O) NH2) Or haloformyl (-C (═ O) -X, where X represents a halogen atom), or formyl (-C (═ O) -H), or isocyano, or isocyanate, or thiocyanate or isothiocyanate, or hydroxy, or nitro, or CF3Or Cl, or Br, or F, or a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having from 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having from 5 to 40 ring atoms, or a combination of these systems, where one or more of the radicals can form a mono-or polycyclic aliphatic or aromatic ring system with one another and/or with the ring bonded to said radicals; one or more of the H's of the various groups described above may also be further substituted by D.
In some preferred embodiments, R510-R545Each independently is H, or D, or a straight chain alkyl, alkoxy or thioalkoxy group having 1 to 10C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 10C atoms, or a substituted or unsubstituted silyl group, or a linear alkyl, alkoxy or thioalkoxy group having 1 to 10C atomsSubstituted keto groups of atoms, or alkoxycarbonyl groups having 2 to 10C atoms, or aryloxycarbonyl groups having 7 to 10C atoms, or cyano (-CN), or carbamoyl (-C (═ O) NH2) Or haloformyl (-C (═ O) -X, where X represents a halogen atom), or formyl (-C (═ O) -H), or isocyano, or isocyanate, or thiocyanate or isothiocyanate, or hydroxy, or nitro, or CF3Or Cl, or Br, or F, or a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic radical having from 5 to 20 ring atoms
Figure GPA0000264407260000131
One or more radicals may form a mono-or polycyclic, aliphatic or aromatic ring system with one another and/or with the rings to which said radicals are bonded; one or more of the H's of the various groups described above may also be further substituted by D.
In some more preferred embodiments, one of the deuterated fused ring compounds has a structure represented by one of formulae (V '-1) to (V' -3):
Figure GPA0000264407260000132
wherein the content of the first and second substances,
R512-R517、R518-R522、R531-R535and R543-R547Independently of one another, are deuterated or non-deuterated substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 20 ring atoms or deuterated or non-deuterated aryloxy or heteroaryloxy groups having 5 to 20 ring atoms, or combinations of these systems. And adjacent substituents may form an aromatic or heteroaromatic ring system having from 5 to 20 ring atoms with one another.
L represents a linking group, which may be a single bond, or a deuterated or non-deuterated substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or a deuterated or non-deuterated aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems.
In some preferred embodiments, L represents a single bond.
In further preferred embodiments, L is a deuterated or non-deuterated substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 20 ring atoms, or a deuterated or non-deuterated aryloxy or heteroaryloxy group having 5 to 20 ring atoms, or a combination of these systems.
Ar3And Ar4Independently of one another, are deuterated or non-deuterated substituted or unsubstituted aromatic or heteroaromatic ring systems having 5 to 40 ring atoms or deuterated or non-deuterated aryloxy or heteroaryloxy groups having 5 to 40 ring atoms, or combinations of these systems. Preferably a deuterated or non-deuterated substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 20 ring atoms or a deuterated or non-deuterated aryloxy or heteroaryloxy group having 5 to 20 ring atoms or a combination of these systems. Ar (Ar)3And
Figure GPA0000264407260000141
m and n are each independently an integer of 0 to 6, preferably 0 to 3, more preferably 0 to 2, and most preferably 0 or 1. Specific examples of the deuterated fused ring compound according to the invention include, but are not limited to:
Figure GPA0000264407260000142
Figure GPA0000264407260000151
Figure GPA0000264407260000161
Figure GPA0000264407260000171
the invention also relates to a synthesis method of the deuterated fused ring compound, which comprises the step of carrying out reaction by using raw materials containing active groups. These active starting materials comprise structural units of the above-mentioned formulae and in each case at least one leaving group, for example bromine, iodine, boric acid or boric acid esters. Suitable reactions for forming C-C linkages are well known to those skilled in the art and described in the literature, and particularly suitable and preferred coupling reactions are SUZUKI, STILLE and HECK coupling reactions.
The invention further relates to a high polymer, the repeating unit of which comprises a group formed by the structure shown in the general formula (I) after at least one H is lost. In certain embodiments, the polymer is a non-conjugated polymer, wherein the structural unit of formula (I) is in a side chain. In another preferred embodiment, the polymer is a conjugated polymer.
The invention also provides a mixture comprising the deuterated fused ring compound or the polymer and a second organic functional material. The second organic functional material can be selected from hole (also called hole) injection or transport materials (HIM/HTM), Hole Blocking Materials (HBM), electron injection or transport materials (EIM/ETM), Electron Blocking Materials (EBM), organic matrix materials (Host), singlet emitters (fluorescent emitters), triplet emitters (phosphorescent emitters), thermal excitation delayed fluorescent materials (TADF materials) and organic electroluminescent materials (OLED materials)
Figure GPA0000264407260000181
Various organic functional materials are described in detail and are hereby incorporated by reference in their entirety in this 3 patent document.
In a preferred embodiment, the second organic functional material is a fluorescent emitter (or singlet emitter) material. The deuterated fused ring compound or the deuterated high polymer is used as a host object, and the fluorescent luminophor is used as an object, wherein the weight percentage of the object is less than or equal to 15 wt%, preferably less than or equal to 12 wt%, more preferably less than or equal to 9 wt%, more preferably less than or equal to 8 wt%, and most preferably less than or equal to 7 wt%.
In a preferred embodiment, the second organic functional material is a fluorescent emitter material and a fluorescent host material (or singlet emitter). In such embodiments, the deuterated fused ring compound or polymer can act as a co-host material in 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.
Some more details are given below (but not limited to) HTM, singlet host material, singlet emitter and TADF material.
1.HIM/HTM/EBM
Suitable organic HIM/HTM materials may be selected from compounds comprising the following structural units: phthalocyanines, porphyrins, amines, aromatic amines, biphenyl triarylamines, thiophenes, bithiophenes such as dithienothiophene and bithiophenes, pyrroles, anilines, carbazoles, azaindenoazafluorenes and derivatives thereof. In addition, suitable HIMs also include self-assembling monomers, such as compounds containing phosphonic acids and sliane derivatives; metal complexes, crosslinking compounds, and the like.
The Electron Blocking Layer (EBL) serves to block electrons from adjacent functional layers, in particular the light-emitting layer. The presence of an EBL generally results in an increase in luminous efficiency compared to a light emitting device without a barrier layer. The Electron Blocking Material (EBM) of the Electron Blocking Layer (EBL) needs to have a higher LUMO than the adjacent functional layer, such as the light emitting layer. In a preferred embodiment, the HBM has a larger excited state energy level, such as singlet or triplet, than the adjacent light-emitting layer, depending on the emitter, while the EBM has hole transport function. HIM/HTM materials that generally have high LUMO levels can be used as EBMs.
Examples of cyclic aromatic amine derivative compounds that may be used as a HIM, HTM or EBM include, but are not limited to, the following general structures:
Figure GPA0000264407260000182
each Ar1To Ar9Can be independently selected from cyclic aromatic hydrocarbon compounds, such as benzeneBiphenyl, triphenyl, benzo, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; heteroaromatic compounds, e.g. dibenzothiophene, dibenzofuran, furan, thiophene, benzofuran, benzothiophene, carbazole, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, oxatriazole, bisoxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, indolizine, benzoxazole, benzisoxazole, benzothiazole, quinoline, isoquinoline, benzodiazepine, quinazoline, and their derivatives,
Figure GPA0000264407260000191
Benzofuran pyridines, indole carbazoles, pyridine indoles, pyrrole bipyridines, furan bipyridines, benzothiophene pyridines, thiophenopyridines, benzoselenophene pyridines and selenophene bipyridines; groups having 2 to 10 ring structures, which may be the same or different types of cyclic aromatic hydrocarbon groups or aromatic heterocyclic groups, are bonded to each other directly or through at least one group selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an alicyclic group. Wherein each Ar may be further substituted, and the substituents may be selected from the group consisting of hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl, and heteroaryl.
In one aspect, Ar1To Ar9May be independently selected from the group comprising:
Figure GPA0000264407260000192
n is an integer from 1 to 20; x1To X8Is CH or N; ar (Ar)1As defined above.
Further examples of cyclic aromatic amine derivative compounds can be found in US3567450, US4720432, US5061569, US3615404, and US5061569.
Examples of metal complexes that may be used as HTMs or HIMs include, but are not limited to, the following general structures:
Figure GPA0000264407260000193
m is a metal having an atomic weight greater than 40;
(Y1-Y2) Is a bidentate ligand, Y1And Y2Independently selected from C, N, O, P and S; l is an ancillary ligand; m is an integer having a value from 1 to the maximum coordination number of the metal; m + n is the maximum coordination number of the metal.
In one embodiment, (Y)1-Y2) Is a 2-phenylpyridine derivative.
In another embodiment, (Y)1-Y2) 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 vacuum level).
Examples of suitable HIM/HTM compounds are listed in the following table:
Figure GPA0000264407260000201
2. singlet Host material (Singlet Host):
examples of the singlet host material are not particularly limited, and any organic compound may be used as the host as long as the singlet energy thereof is higher than that of the light emitter, particularly, the singlet light emitter or the fluorescent light emitter.
Examples of the organic compound used as the singlet host material may be selected from the group consisting of cyclic aromatic hydrocarbon-containing compounds such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, phenalene, phenanthrene, fluorene, pyrene, chrysene, perylene, azulene; aromatic heterocyclic compounds, e.g. dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, indolocarbazole, pyridine indole, pyrrole bipyridine, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, oxatriazole, dioxazoleOxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxathiazine, oxadiazine, indole, benzimidazole, indazole, triazine, and triazine,
Figure GPA0000264407260000211
Pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranpyridine, furanbipyridine, benzothiophene pyridine, thiophendipyridine, benzoselenophene pyridine, and selenophene dipyridine; groups having 2 to 10 ring structures, which may be the same or different types of cyclic aromatic hydrocarbon groups or aromatic heterocyclic groups, are bonded to each other directly or through at least one group selected from the group consisting of an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, a chain structural unit and an alicyclic group.
In a preferred embodiment, the singlet host material may be selected from compounds comprising at least one of the following groups:
Figure GPA0000264407260000212
wherein R is1Can be selected independently of one another from the following groups: hydrogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl, and heteroaryl; ar (Ar)1Is aryl or heteroaryl with Ar as defined in the HTM above1The meanings are the same; n is an integer from 0 to 20; x1-X8Selected from CH or N; x9And X10Is selected from CR1R2Or NR1。
Some examples of anthracene-based singlet host materials are listed in the following table:
Figure GPA0000264407260000213
3. singlet state luminophor (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 JP2913116B and WO2001021729a1, and indenofluorene and its derivatives disclosed in WO2008/006449 and WO 2007/140847.
In a preferred embodiment, the singlet emitters may be selected from the group consisting of monostyrenamines, distyrenamines, tribenzenes
Figure GPA0000264407260000221
A monostyrene amine is a compound comprising an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine. A distyrene amine refers to a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A tristyrenylamine refers to a compound comprising three unsubstituted or substituted styrene groups and at least one amine, preferably an aromatic amine. A tetrastyrene amine refers to a compound comprising four unsubstituted or substituted styrene groups and at least one amine, preferably an aromatic amine. One preferred styrene is stilbene, which may be further substituted. The corresponding phosphines and ethers are defined analogously to the amines. Arylamine or aromatic amine refers to a compound comprising three unsubstituted or substituted aromatic rings or heterocyclic systems directly linked to nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably a fused ring system and preferably has at least 14 aromatic ring atoms. Among them, preferred examples are aromatic anthracenamines, aromatic anthracenediamines, aromatic pyrenediamines, aromatic chrysenamines and aromatic chrysenediamines. An aromatic anthracylamine refers to a compound in which a diarylamine group is attached directly to the anthracene, preferably at the 9 position. An aromatic anthracenediamine refers to a compound in which two diarylamine groups are attached directly to the anthracene, preferably at the 9, 10 positions. Aromatic pyrene amines, aromatic pyrene diamines, aromatic chrysene amines and aromatic chrysene diamines are similarly defined, wherein the diarylamine groups are preferably attached to the 1 or 1, 6 position of pyrene.
Examples, which are also preferred, of singlet emitters based on vinylamines and arylamines can be found in the following patent documents: WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549, WO 2007/115610, US 7250532B 2, DE 102005058557 a1, CN 1583691 a, JP 08053397 a, US 6251531B 1, US 2006/210830 a, EP 1957606A 1 and US 2008/0113101 a1 the entire contents of the patent documents listed above are hereby incorporated by reference.
An example of singlet emitters based on stilbene and its derivatives is US 5121029.
Further preferred singlet emitters may be selected from indenofluorene-amines and indenofluorene-diamines, as disclosed in WO 2006/122630, benzindenofluorene-amines and benzindenofluorene-diamines, as disclosed in WO2008/006449, dibenzoindenofluorene-amines and dibenzoindenofluorene-diamines, as disclosed in WO 2007/140847.
Other materials which can be used as singlet emitters are polycyclic aromatic compounds, in particular derivatives of the following compounds: anthracenes such as 9, 10-bis (2-naphthoanthracene), naphthalene, tetraphenes, xanthenes, phenanthrenes, pyrenes (e.g. 2, 5, 8, 11-tetra-t-butylperylene), indenopyrenes, phenylenes such as (4, 4 '-bis (9-ethyl-3-carbazolylethenyl) -1, 1' -biphenyl), diindenopyrenes, decacycloalkenes, coronenes, fluorenes, spirobifluorenes, arylpyrenes (e.g. US20060222886), aryleneethylenes (e.g. US5121029, US5130603), cyclopentadienes such as tetraphenylcyclopentadiene, rubrene, coumarin, rhodamine, quinacridones, pyrans such as 4 (dicyanomethylene) -6- (4-p-dimethylaminostyryl-2-methyl) -4H-pyran (DCM), thiopyran, bis (azinyl) imine boron compounds (US 2007/0092753A 1), bis (azinyl) methylene compounds, carbostyryl compounds, oxazinones, benzoxazoles, benzothiazoles, benzimidazoles and pyrrolopyrrolediones. Some singlet emitter materials can be found in the following patent documents: US 20070252517 a1, US 4769292, US 6020078, US 2007/0252517 a1, US 2007/0252517 a 1. The entire contents of the above listed patent documents are hereby incorporated by reference.
Figure GPA0000264407260000231
Figure GPA0000264407260000232
4. Thermally excited delayed fluorescence luminescent material (TADF material)
The traditional organic fluorescent material can only emit light by utilizing 25% singlet excitons formed by electric excitation, and the internal quantum efficiency of the device is low (up to 25%). Although the phosphorescence material enhances the intersystem crossing due to the strong spin-orbit coupling of the heavy atom center, the singlet excitons and the triplet excitons formed by the electric excitation can be effectively used for emitting light, so that the internal quantum efficiency of the device reaches 100 percent. However, the application of the phosphorescent material in the OLED is limited by the problems of high price, poor material stability, serious efficiency roll-off of the device and the like. The thermally activated delayed fluorescence emitting material is a third generation organic emitting material developed after organic fluorescent materials and organic phosphorescent materials. Such materials generally have a small singlet-triplet energy level difference (Δ Est), and triplet excitons may be converted to singlet excitons for emission by intersystem crossing. This can make full use of singlet excitons and triplet excitons formed upon electrical excitation. The quantum efficiency in the device can reach 100%. Meanwhile, the material has controllable structure, stable property, low price and no need of noble metal, and has wide application prospect in the field of OLED.
TADF materials are required to have a small singlet-triplet level difference, preferably Δ Est < 0.3eV, less preferably Δ Est < 0.2eV, and most preferably Δ Est < 0.1 eV. In a preferred embodiment, the TADF material has a relatively small Δ Est, and in another preferred embodiment, the TADF has a good fluorescence quantum efficiency. Some TADF luminescent materials 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.phtt.lett, 98, 2011, 083302, Adachi, et.al.appl.phys.lett.101, 2012, 093306, Adachi, et.al.chem.commu.s.48, 2012, 11392, Adachi, et.al.nature photonia, 6, 2012, 253, Adachi, 492.al.Nature, 234, Adachi j.al.m.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，
Figure GPA0000264407260000241
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, the entire contents of the above listed patents or article documents are hereby incorporated by reference.
Some examples of suitable TADF phosphors are listed in the following table:
Figure GPA0000264407260000242
Figure GPA0000264407260000251
publications in which the above organic functional materials appear 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 evaporative OLED device. For this purpose, the deuterated fused-ring compound or polymer has a molecular weight of 1000mol/kg or less, preferably 900mol/kg or less, very preferably 850mol/kg or less, more preferably 800mol/kg or less, and most preferably 700mol/kg or less.
It is another object of the present invention to provide a material solution for printing OLEDs.
For this purpose, the molecular weight of the deuterated fused-ring compound or polymer is 700mol/kg or more, preferably 900mol/kg or more, very preferably 900mol/kg or more, more preferably 1000mol/kg or more, and most preferably 1100mol/kg or more.
In other preferred embodiments, the deuterated fused-ring compound or polymer has a solubility in toluene of 10mg/ml or more, preferably 15mg/ml or more, and most preferably 20mg/ml or more, at 25 ℃.
Figure GPA0000264407260000261
In some embodiments, the deuterated fused ring compound can serve 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 fluorescence emitting material.
In other preferred embodiments, the composition further comprises a Hole Transport 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 of the embodiment of the present invention may include 0.01 to 20 wt% of deuterated fused ring compound or polymer, preferably 0.1 to 15 wt%, more preferably 0.2 to 10 wt%, and most preferably 0.25 to 5 wt% of deuterated fused ring compound or polymer.
In some preferred embodiments, a composition according to the present invention, wherein said first organic solvent is selected from an inorganic ester compound such as an aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, alicyclic or olefinic compound, or a borate or phosphate, or a mixture of two or more solvents.
In other preferred embodiments, a composition according to the present invention comprises at least 50 wt% of an aromatic or heteroaromatic solvent; preferably at least 80 wt% of an aromatic or heteroaromatic solvent; particularly preferably at least 90% by weight of an aromatic or heteroaromatic solvent.
Examples of first organic solvents based on aromatic or heteroaromatic compounds according to the 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-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, diphenyl ether, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether, N-methyldiphenylamine, 4-isopropylbiphenyl, α -dichlorodiphenylmethane, 4- (3-phenylpropyl) pyridine, benzyl benzoate, 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, 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, particularly 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 alone or as a mixture of two or more organic solvents.
Figure GPA0000264407260000271
Sub, including (but not limited to): methanol, ethanol, 2-methoxy ethanol, dichloromethane, trichloromethane, chlorobenzene,O-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1, 4-dioxane, acetone, methyl ethyl ketone, 1, 2-dichloroethane, 3-phenoxytoluene, 1, 1, 1-trichloroethane, 1, 1, 2, 2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene, decalin, indene and/or mixtures thereof.
In some preferred embodiments, organic solvents particularly suitable for the present invention are those having Hansen (Hansen) solubility parameters within the following ranges:
δd(dispersion force) of 17.0 to 23.2MPa1/2In particular in the range of 18.5 to 21.0MPa1/2A range of (d);
δp(polar force) is 0.2 to 12.5MPa1/2In particular in the range of 2.0 to 6.0MPa1/2A range of (d);
δh(hydrogen bonding force) of 0.9 to 14.2MPa1/2In particular in the range of 2.0 to 6.0MPa1/2The range of (1).
The compositions according to the invention, in which the organic solvent is selected taking into account its boiling point parameter. In the invention, the boiling point of the organic solvent is more than or equal to 150 ℃; preferably equal to or more than 180 ℃; more preferably more than or equal to 200 ℃; more preferably more than or equal to 250 ℃; most preferably more than or equal to 275 ℃ or more than or equal to 300 ℃. Boiling points in these ranges are beneficial for preventing nozzle clogging in inkjet print heads. The organic solvent may be evaporated from the solvent system to form a thin film comprising the functional material.
In some preferred embodiments, the composition:
1) having a viscosity in the range of 1cPs (millipascal seconds) to 100cPs at 25 ℃, and/or
2) The surface tension is in the range of 19dyne/cm (dyne/cm) to 50dyne/cm at 25 ℃.
The composition according to the invention, wherein the organic solvent is selected taking into account its surface tension parameters. Suitable ink surface tension parameters are appropriate for a particular substrate and a particular printing process. For example, for ink jet printing, in a preferred embodiment, the organic solvent has a surface tension in the range of about 19dyne/cm to about 50dyne/cm at 25 ℃; more preferably in the range of 22dyne/cm to 35 dyne/cm; most preferably in the range of 25dyne/cm to 33 dyne/cm.
In a preferred embodiment, the ink according to the invention has a surface tension at 25 ℃ in the range of about 19dyne/cm to about 50 dyne/cm; more preferably in the range of 22dyne/cm to 35 dyne/cm; preferably in the range of 25dyne/cm to 33 dyne/cm.
The composition according to the invention, wherein the organic solvent is selected taking into account the viscosity parameters of the ink. The viscosity can be adjusted by different methods, such as by the selection of a suitable organic solvent and the concentration of the functional material in the ink. In a preferred embodiment, the viscosity of the organic solvent is less than 100 cps; more preferably below 50 cps; most preferably 1.5 to 20 cps. The viscosity here means the viscosity at ambient temperature at the time of printing, and is generally 15 to 30 ℃, preferably 18 to 28 ℃, more preferably 20 to 25 ℃, most preferably 23 to 25 ℃. The compositions so formulated will be particularly suitable for ink jet printing.
In a preferred embodiment, the viscosity of the composition according to the invention ranges from about 1cps to about 100cps at 25 ℃; more preferably in the range of 1cps to 50 cps; preferably in the range of 1.5cps to 20 cps.
Figure GPA0000264407260000281
And a functional material film with composition properties.
The invention also aims to provide application of the deuterated fused ring compound and the polymer in organic electronic devices.
The Organic electronic device can be selected from Organic Light Emitting Diodes (OLEDs), Organic photovoltaic cells (OPVs), Organic light Emitting cells (OLEECs), Organic Field Effect Transistors (OFETs), Organic light Emitting field effect transistors (efets), Organic lasers, Organic spintronic devices, Organic sensors, and Organic Plasmon Emitting diodes (Organic plasma Emitting diodes).
It is another object of the present invention to provide a method for preparing the above organic electronic device,
the method comprises the following steps: forming a functional layer on a substrate by evaporating the deuterated fused ring compound, the high polymer or the mixture; or forming a functional layer on a substrate by combining the deuterated fused ring compound or the high polymer and a second organic functional material by a co-evaporation method; or coating the composition on a substrate by printing or coating to form a functional layer. The Printing or coating method can be selected from, but not limited to, ink jet Printing, jet Printing (Nozzle Printing), letterpress Printing, screen Printing, dip coating, spin coating, doctor blade coating, roll Printing, twist roll Printing, offset Printing, flexographic Printing, rotary Printing, spray coating, brush or pad Printing, slit die coating, and the like.
The invention also relates to the use of said composition as a printing ink for the production of organic electronic devices, particularly preferably by printing or coating.
Suitable printing or coating techniques include, but are not limited to, ink jet printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roll printing, twist roll printing, lithographic printing, flexographic printing, rotary printing, spray coating, brush or pad printing, slot die coating, and the like. Gravure printing, screen printing and ink jet printing are preferred. Gravure printing, ink jet printing, will be used in the examples of the present invention. The solution or suspension may additionally include one or more components such as surface active compounds, lubricants, wetting agents, dispersants, hydrophobing agents, binders, and the like, for adjusting viscosity, film forming properties, enhancing adhesion, and the like. For details on printing techniques and their requirements relating to the solutions, such as solvents and concentrations, viscosities, etc., see the printed media handbook, edited by Helmut Kipphan: techniques and Production Methods (Handbook of Print Media: Technologies and Production Methods), ISBN 3-540 and 67326-1.
According to the preparation method, the thickness of the functional layer is 5nm-1000 nm.
The invention further relates to an organic electronic device comprising the deuterated fused ring compound or the polymer. The organic electronic device may include a functional layer prepared using the composition. In general, the organic electronic device comprises at least a cathode, an anode and a functional layer disposed between the cathode and the anode, wherein the functional layer comprises the deuterated fused ring compound or the polymer as described above.
In a more preferred embodiment, the organic electronic device described above is an electroluminescent device, in particular an OLED, which comprises a substrate 101, an anode 102, at least one light-emitting layer 104, and a cathode 106, as shown in fig. 1.
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,
Figure GPA0000264407260000291
the sheet has a smooth surface. A substrate free of surface defects is a particularly desirable choice. In a preferred embodiment, the substrate is flexible, and may be selected from polymeric films or plastics having a glass transition temperature Tg of 150 deg.C or greater, preferably greater than 200 deg.C, more preferably greater than 250 deg.C, and most preferably greater than 300 deg.C. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).
The anode 102 may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL) or an emission layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light emitting layer or the p-type semiconductor material acting as a HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. Examples of anode materials include, but are not limited to: al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is pattern structured. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.
Cathode 106 may include a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the light emitting layer. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO level or conduction band level of the emitter in the light-emitting layer or of the n-type semiconductor material as Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. In principle, all materials which can be used as cathodes in OLEDs are possible as cathode materials for the device according to the invention. Examples of cathode materials include, but are not limited to: al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2/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 further functional layers, such as a Hole Injection Layer (HIL) or Hole Transport Layer (HTL)103, an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL) or Electron Transport Layer (ETL)105, a Hole Blocking Layer (HBL). Suitable materials for use in these functional layers are described in detail in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of these 3 patent documents being hereby incorporated by reference.
In a preferred embodiment, the light-emitting layer 104 is formed by vacuum evaporation, and the evaporation source thereof includes the deuterated fused ring compound or the polymer.
In another preferred embodiment, the luminescent layer 104 is prepared by printing the composition.
The electroluminescent device according to the invention emits light at a wavelength of between 300 and 1000nm, preferably between 350 and 900nm, more preferably between 400 and 800 nm.
The invention also relates to the use of said organic electronic device in various electronic devices, includingBut is not limited to, a display device,
Figure GPA0000264407260000301
the invention also relates to electronic devices including, but not limited to, display devices, lighting devices, light sources, sensors, etc., comprising the organic electronic device according to the invention.
The present invention will be described in connection with preferred embodiments, but the present invention is not limited to the following embodiments, and it should be understood that the appended claims outline the scope of the present invention and those skilled in the art, guided by the inventive concept, will appreciate that certain changes may be made to the embodiments of the invention, which are intended to be covered by the spirit and scope of the appended claims.
Example 1: synthesis of Compound 1
Figure GPA0000264407260000302
In a 250mL three-necked flask equipped with a condenser under nitrogen flow, 2- (3-bromophenyl-5-d) naphthalene (5.7g, 20mmol), (10- (naphthalen-1-yl) anthracen-9-yl) boronic acid (7.0g, 20mmol), potassium carbonate (8.3g, 60mmol), Pd (PPh)3)4(690mg, 0.6mmol), 100mL of toluene, and 30mL of water, and stirred at 90 ℃ overnight. After the reaction was completed, the organic phase was washed with water, collected and purified by spin dry column chromatography to obtain a white solid product (8.1g, 80%).
Example 2: synthesis of Compound 2
Figure GPA0000264407260000303
In a 250mL three-necked flask equipped with a condenser under nitrogen flow, 2- (3-bromophenyl-5-d) naphthalene (5.1g, 18mmol), (10- (d) was added5-phenyl) anthracen-9-yl) boronic acid (5.5g, 18mmol), potassium carbonate (7.5g, 54mmol), Pd (PPh)3)4(624mg, 0.54mmol), 80mL of toluene, and 20mL of water, and stirred at 90 ℃ overnight. After the reaction is finished, washing the organic phase with water,the organic phase was collected and purified by spin dry column chromatography to give the product as a white solid (7.1g, 85%).
Example 3: synthesis of Compound 3
Figure GPA0000264407260000304
Figure GPA0000264407260000311
mmol), (10- (naphthalen-1-yl-4-d) anthracen-9-yl) boronic acid (8.7g, 25mmol), potassium carbonate (10.4g, 75mmol), Pd (PPh)3)4(870mg, 0.75mmol), 120mL of toluene, and 30mL of water, and stirred at 90 ℃ overnight. After the reaction was completed, the organic phase was washed with water, collected and purified by spin dry column chromatography to obtain a white solid product (9.3g, 73%).
Example 4: synthesis of Compound 4
Figure GPA0000264407260000312
In a 250mL three-necked flask equipped with a condenser under nitrogen flow, 2- (4-bromophenyl) -6-d-naphthalene (5.7g, 20mmol), (10- (4-d-naphthalen-1-yl) anthracen-9-yl) boronic acid (7.0g, 20mmol), potassium carbonate (8.3g, 60mmol), Pd (PPh)3)4(690mg, 0.6mmol), 120mL of toluene, and 30mL of water, and stirred at 90 ℃ overnight. After the reaction was completed, the organic phase was washed with water, collected and purified by spin dry column chromatography to obtain a white solid product (8.4g, 83%).
Example 5: synthesis of Compound 5
Figure GPA0000264407260000313
In a 250mL three-necked flask equipped with a condenser under nitrogen flow, 2- (4-bromo-d) was added4-phenyl) -6-d-naphthalene (4.6g, 16mmol), (10- (4-d-naphthalen-1-yl) anthracen-9-yl) boronic acid (5.6g, 16mmol), potassium carbonate (6.6g, 48mmol), Pd (PPh)3)4(570mg, 0.5mmol), 80mL of tolueneAnd 20mL of water, stirred at 90 ℃ overnight. After the reaction was completed, the organic phase was washed with water, collected and purified by spin dry column chromatography to obtain a white solid product (6.3g, 77%).
Comparative example 1: synthesis of comparative Compound 1
Figure GPA0000264407260000314
In a 250mL three-necked flask equipped with a condenser under a nitrogen stream, 2- (4-bromophenyl) naphthalene (8.5g, 30mmol), (10- (naphthalen-1-yl) anthracen-9-yl) boronic acid (10.4g, 30mmol), potassium carbonate (12.4g, 90mmol), Pd (PPh)3)4(1.0g, 0.9mmol), 150mL of toluene, and 40mL of water, and stirred at 90 ℃ overnight. After the reaction was completed, the organic phase was washed with water, collected and purified by spin dry column chromatography to obtain a white solid product (12.8g, 84%).
Example 6: preparing and characterizing an OLED device:
materials used for the layers of the OLED device:
HIL: a triarylamine derivative;
Figure GPA0000264407260000321
host: compound 1-compound 5, comparative compound.
The volume of the Dopan: a pyrene derivative.
Having an ITO/HIL (50nm)/HTL (35 nm)/Host: the preparation steps of the OLED device with 5% of Dopan (25nm)/ETL (28nm)/LiQ (1nm)/Al (150 nm)/cathode are as follows:
a. cleaning the conductive glass substrate: for the first time, the cleaning agent can be cleaned by various solvents, such as chloroform, ketone and isopropanol, and then ultraviolet ozone plasma treatment is carried out;
b. HIL (50nm), HTL (35nm), EML (25nm), ETL (28 nm): under high vacuum (1X 10)-6Mbar, mbar).
c. Cathode: LiQ/Al (1nm/150nm) in high vacuum (1X 10)-6Millibar) hot evaporation;
d. packaging: the devices were encapsulated with uv curable resin in a nitrogen glove box.
The current-voltage (J-V) characteristics of each OLED device were characterized by a characterization device, while recording important parameters such as efficiency, lifetime, and external quantum efficiency. Through detection, the color coordinates of the blue light device prepared by adopting the compound 1-the compound 5 as the EML layer main body are better than those of the comparative compound 1, for example, the color coordinates of the device prepared by the compound 5 are (0.149, 0.086); in addition, the luminous efficiency of the blue light device prepared by adopting the compound 1-the compound 5 as the EML layer main body is in the range of 6-8cd/A, so that the blue light device has more excellent luminous efficiency; the lifetime of blue devices prepared using compounds 1-5 as the EML layer host is much better than that of comparative compound 1 in terms of device lifetime, e.g., the T95 at 1000nits for devices prepared from compound 5 is greater than 1000 hours.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (8)

1. A deuterated fused ring compound has a structure represented by the general formula (V' -2):
Figure 796394DEST_PATH_IMAGE001
wherein the content of the first and second substances,
R531-R535each independently is D, or deuterated benzene, or deuterated naphthalene;
l represents a linking group selected from a single bond, or a deuterated or non-deuterated benzene, or a deuterated or non-deuterated naphthalene;
Ar3is deuterated or non-deuterated benzene, deuterated or non-deuterated naphthalene;
m is 0.
2. The deuterated fused-ring compound according to claim 1, wherein L is selected from a single bond or benzene.
3. A deuterated fused ring compound having a structure represented by any one of:
Figure 779393DEST_PATH_IMAGE002
。
4. a mixture comprising the deuterated fused ring compound according to any one of claims 1-3 and a second organic functional material, wherein the second organic functional material is at least one of a hole injection material or a hole transport material, a hole blocking material, an electron injection material or an electron transport material, an electron blocking material, an organic matrix material, a singlet emitter, a triplet emitter, a thermal excitation delayed fluorescence material, and an organic dye.
5. A composition comprising the deuterated fused ring compound of any one of claims 1-3 and an organic solvent, or comprising the mixture of claim 4 and an organic solvent.
6. An organic electronic device comprising the deuterated fused ring compound of any one of claims 1-3 or the mixture of claim 4.
7. The organic electronic device according to claim 6, wherein the organic electronic device is 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, or an organic plasmon emitting diode.
8. The organic electronic device according to claim 6, which is an organic electroluminescent device comprising a light-emitting layer comprising the deuterated fused ring compound according to any one of claims 1-3 or the mixture according to claim 4.
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