CN109575058B

CN109575058B - 4, 10-dioxo-5, 9-diboropyrene derivative, preparation method and application

Info

Publication number: CN109575058B
Application number: CN201811558306.3A
Authority: CN
Inventors: 李贵杰; 戴健鑫; 冯琦; 陈少海; 佘远斌
Original assignee: Zhejiang University of Technology ZJUT; AAC Optoelectronic Changzhou Co Ltd
Current assignee: Zhejiang University of Technology ZJUT; AAC Optoelectronic Changzhou Co Ltd
Priority date: 2018-12-19
Filing date: 2018-12-19
Publication date: 2021-03-09
Anticipated expiration: 2038-12-19
Also published as: CN109575058A

Abstract

The invention relates to the technical field of optical and electro-optic materials, and discloses a derivative based on 4, 10-dioxo-5, 9-diboropyrene, a preparation method and application thereof. The diboron oxapyrene derivative can be a delayed fluorescence and/or phosphorescence emitter, has the characteristics of high thermal decomposition temperature, easily adjustable triplet state energy level, high quantum effect and the like, and has great application prospect in the fields of main body materials, blue light emitting materials or charge transmission/barrier materials.

Description

4, 10-dioxo-5, 9-diboropyrene derivative, preparation method and application

Technical Field

The invention relates to the technical field of optical and electro-optic materials, in particular to a functional material based on a4, 10-dioxo-5, 9-diboropyrene derivative, which can be used in the fields of OLED display and illumination.

Background

Compounds capable of absorbing and/or emitting light are ideally suited for use in a wide variety of optical and electroluminescent devices, including light absorbing devices such as solar sensitive and photosensitive devices, Organic Light Emitting Diodes (OLEDs), light emitting devices, or devices capable of both light absorption and light emission, and as markers (markers) for biological applications. Much research has been devoted to the discovery and optimization of organic and organometallic materials for use in optical and electroluminescent devices. In general, research in this field is aimed at achieving a number of goals, including improvements in absorption and emission efficiencies, and improvements in processing capabilities.

Despite significant advances in the research of chemical and electro-optic materials, such as red-green phosphorescent organometallic materials, which have been commercialized and applied to OLEDs, illumination devices, and advanced displays, there are many disadvantages of currently available materials, including poor machinability, inefficient emission or absorption, and less than ideal stability.

In addition, good blue light emitting materials are rare, and a great challenge is that blue light devices are not good enough in stability, and meanwhile, the selection of the host material has an important influence on the stability and efficiency of the devices. Compared with a red-green phosphorescent material, the lowest triplet state energy level of the blue phosphorescent material is higher, which means that the triplet state energy level of a host material in a blue light device needs to be higher. Therefore, the limitation of host materials in blue devices is an important issue for their development. Few reports of compounds with excellent photophysical properties such as high triplet state energy level exist, and particularly, materials capable of meeting the requirements of deep blue light phosphorescence device preparation are more limited.

An OLED device is composed of a pair of electrodes including an anode and a cathode, and one or more functional layers including an organic compound disposed between the pair of electrodes. Wherein the organic compound layer includes a light emitting layer, an electron and hole injection layer, and an electron and hole transport layer. Accordingly, active research into organic materials having charge transport capabilities, which may be semiconductors, has been conducted to promote the development of this field.

In addition, polycyclic aromatic hydrocarbons have been receiving much attention in recent years as materials for organic electronics, pigments, sensors, and liquid-layer displays, and a few examples of synthesis of boron-nitrogen-polycyclic aromatic hydrocarbon compounds have been reported, but related boron-nitrogen-polycyclic aromatic hydrocarbon compound materials suitable as host materials or light-emitting materials for electro-optical devices are more rare.

Disclosure of Invention

The invention aims to provide a functional material of a4, 10-dioxo-5, 9-diboropyrene derivative and application thereof as a host material, a luminescent material or a charge transmission/blocking material in the field of OLED.

The structure of the 4, 10-dioxo-5, 9-diboropyrene derivative provided by the embodiment of the invention is shown as the formula (I):

wherein R is^a、R^bAnd R^cEach independently hydrogen, deuterium, alkyl, alkoxy, cycloalkyl, ether, heterocyclyl, phenyl, aryloxy, halogen, cyano, or combinations thereof; ar is six-membered aryl, heteroaryl, fused aryl and aza-fused aryl;

m is an integer of 0 to 5;

n is an integer of 0 to 3;

and the whole molecule has a symmetrical structure with 5 and 9 positions containing two boron atoms.

Preferably, the 4, 10-dioxo-5, 9-diboropyrene derivative provided by the embodiment of the invention is characterized in that in the structural formula (I), Ar is phenyl, naphthyl, triphenylene, indolyl, carbazolyl, pyridyl, pyrazinyl, quinolyl and isoquinolyl.

Preferably, the 4, 10-dioxo-5, 9-diboropyrene derivative provided by the embodiment of the invention has a structure selected from one of BO1-BO 592:

embodiments of the present invention also provide an optical or electro-optical device comprising one or more of the above 4, 10-dioxo-5, 9-diboropyrene derivatives.

Preferably, the optical or electro-optical device provided by the embodiment of the present invention includes a light absorption device (such as a solar device or a photo-sensitive device), an Organic Light Emitting Diode (OLED), a light emitting device, or a device capable of both light absorption and emission.

Embodiments of the present invention also provide an OLED device in which the light emitting material or host material comprises one or more of the above 4, 10-dioxo-5, 9-diboropyrene derivatives. The 4, 10-dioxo-5, 9-diboropyrene derivative provided by the embodiment of the invention can be used as a host material of an OLED device, such as a full-color display and the like; it is also applicable to light-emitting materials of OLED devices, such as light-emitting devices and displays.

Compared with the prior art, the embodiment of the invention provides a series of luminescent materials based on 4, 10-dioxo-5, 9-diboropyrene derivatives, and the materials can be fluorescent, delayed fluorescence and/or phosphorescence emitters. The compound provided by the embodiment of the invention has the following characteristics: firstly, the boron oxapyrene derivative materials have high luminescence quantum efficiency (PLQY), short excited state life and high thermal decomposition temperature which is higher than the thermal evaporation temperature of the materials during the manufacturing of devices (the thermal evaporation temperature of the materials during the manufacturing of the devices is generally not higher than 280 ℃), and the properties are favorable for the boron oxapyrene derivative to be used for luminescent materials and further commercialized application. Secondly, the boron oxapyrene derivative has various structures and is easy to modify, so that the boron oxapyrene derivative has easily-adjusted triplet state energy level (T)₁) Can be used as the host material of various luminophors. In the 4, 10-dioxo-5, 9-diboropyrene derivative provided by the invention, part of materials have very high triplet state energy levels (2.97-3.06eV), and can be used as a main body material of a blue light, especially a deep blue light emitter. Therefore, the invention provides an effective solution for the current critical deep blue light host material, and can greatly promote the development of the blue light and deep blue light host material field.

The thin film data and device data provided by the embodiment of the invention by using the 4, 10-dioxo-5, 9-diboropyrene derivative as the host material also fully show that the boron oxapyrene derivative can be used as a good host material, and particularly has better feasibility and superiority when being used as a host material of a blue light and deep blue light luminous body which is in short supply at present.

Drawings

FIG. 1 is an emission spectrum of a dichloromethane solution of the compound BO3 at room temperature and a 2-methyltetrahydrofuran solution thereof at 77K;

FIG. 2 is a thermogravimetric analysis (TGA) curve raw spectrum of compound BO 3; the thermal decomposition temperature is close to 300 ℃.

FIG. 3 is an excitation and emission spectrum of a dichloromethane solution of the compound BO80 at room temperature and a 2-methyltetrahydrofuran solution thereof at 77K;

FIG. 4 is an excitation and emission spectrum of a dichloromethane solution of the compound BO312 at room temperature and a 2-methyltetrahydrofuran solution thereof at 77K;

FIG. 5 is an emission spectrum of a dichloromethane solution of the compound BO466 at room temperature and a 2-methyltetrahydrofuran solution thereof at 77K;

FIG. 6 is an emission spectrum of a dichloromethane solution of a compound BO543 at room temperature and a 2-methyltetrahydrofuran solution thereof at 77K;

FIG. 7 is an excitation and emission spectrum of a dichloromethane solution of the compound BO555 at room temperature and a 2-methyltetrahydrofuran solution thereof at 77K;

FIG. 8 is a graph of luminance vs. power efficiency for a device with compound BO80 as the host material;

FIG. 9 is a graph of luminance versus external quantum efficiency for a device with compound BO80 as the host material;

FIG. 10 is a voltage-luminance curve of a device with compound BO80 as the host material;

FIG. 11 is a graph showing the electroluminescence spectrum of a device using the compound BO80 as a host material at a luminance of 1000 nits.

Detailed Description

The disclosure may be understood more readily by reference to the following detailed description and the examples included therein. Before the present compounds, devices, and/or methods are disclosed and described, it is to be understood that they are not limited to the particular synthetic methods (otherwise specified), or to the particular reagents (otherwise specified), as such can, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. Although any methods and materials similar or equivalent to those described herein can be used in the practice or testing, the exemplary methods and materials are described below.

As used in the specification and the appended claims, the singular forms "a", "an", and "the" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "a component" includes mixtures of two or more components.

The term "optional" or "optionally" as used herein means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances where it does not.

Components useful in preparing the compositions of the present invention are disclosed, as well as the compositions themselves to be used in the methods disclosed herein. These and other materials are disclosed herein, and it is understood that when combinations, subsets, interactions, groups, etc. of these materials are disclosed that while specific reference of each various individual and collective combinations and permutation of these compounds may not be specifically disclosed, each is specifically contemplated and described herein. For example, if a particular compound is disclosed and discussed, and a number of modifications that can be made to a number of molecules comprising the compound are discussed, then various and each combination and permutation of the compound are specifically contemplated and may be made, otherwise specifically indicated to the contrary. Thus, if a class of molecules A, B, and C are disclosed as well as a class of molecules D, E, and F, and an example of a combination molecule A-D is disclosed, then even if each is not individually recited, it is contemplated that each individually and collectively contemplated combination of meanings, A-E, A-F, B-D, B-E, B-F, C-D, C-E, and C-F, will be disclosed. Likewise, any subset or combination of these is also disclosed. Thus, for example, it is contemplated that subgroups A-E, B-F, and C-E are disclosed. These concepts are applicable to all aspects of the invention, including but not limited to the steps of the methods of making and using the compositions. Thus, if there are a variety of additional steps that can be performed it is understood that each of these additional steps can be performed with a specific embodiment or combination of embodiments of the method.

The linking atom used in the present invention can link two groups, for example, N and C groups. The linking atom can optionally (if valency permits) have other chemical moieties attached. For example, in one aspect, oxygen does not have any other chemical group attached because once bonded to two atoms (e.g., N or C) valences have been satisfied. Conversely, when carbon is a linking atom, two additional chemical moieties can be attached to the carbon atom. Suitable chemical moieties include, but are not limited to, hydrogen, hydroxyl, alkyl, alkoxy, ═ O, halogen, nitro, amine, amide, thiol, aryl, heteroaryl, cycloalkyl, and heterocyclyl.

The term "cyclic structure" or similar terms as used herein refers to any cyclic chemical structure including, but not limited to, aryl, heteroaryl, cycloalkyl, cycloalkenyl, heterocyclyl, carbene, and N-heterocyclic carbene.

The term "substituted" as used herein is intended to encompass all permissible substituents of organic compounds. In a broad aspect, permissible substituents include acyclic and cyclic, branched and unbranched, carbocyclic and heterocyclic, and aromatic and nonaromatic substituents of organic compounds. Illustrative substituents include, for example, those described below. The permissible substituents can be one or more, identical or different for suitable organic compounds. For the purposes of the present invention, a heteroatom (e.g. nitrogen) can have a hydrogen substituent and/or any permissible substituents of organic compounds described herein which satisfy the valences of the heteroatom. The present disclosure is not intended to be limited in any way by the permissible substituents of organic compounds. Likewise, the term "substituted" or "substituted with" includes the implicit proviso that such substitution is consistent with the atom being substituted and the allowed valence of the substituent, and that the substitution results in a stable compound (e.g., a compound that does not spontaneously undergo transformation (e.g., by rearrangement, cyclization, elimination, etc.)). It is also contemplated that, in certain aspects, individual substituents can be further optionally substituted (i.e., further substituted or unsubstituted), unless explicitly stated to the contrary.

In defining the terms, "R¹”、“R²”、“R³"and" R⁴"in the bookThe general symbols used in the present invention represent various specific substituents. These symbols can be any substituent, are not limited to those disclosed herein, and when they are defined as certain substituents in one instance, they can be defined as some other substituents in other instances.

The term "alkyl" as used herein is a branched or unbranched saturated hydrocarbon group of 1 to 24 carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neopentyl, hexyl, heptyl, half-yl, nonyl, decyl, dodecyl, tetradecyl, hexadecyl, eicosyl, tetracosyl and the like. The alkyl group may be cyclic or acyclic. The alkyl group may be branched or unbranched. The alkyl group may also be substituted or unsubstituted. For example, the alkyl group may be substituted with one or more groups including, but not limited to, optionally substituted alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxy, nitro, silyl, Sulfo-OXO (Sulfo-OXO), or thiol as described herein. A "lower alkyl" group is an alkyl group containing 1 to 6 (e.g., 1 to 4) carbon atoms.

Throughout the specification, "alkyl" is generally used to refer to both unsubstituted alkyl and substituted alkyl; however, substituted alkyl groups are also specifically mentioned in the present invention by identifying specific substituents on the alkyl group. For example, the term "halogenated alkyl" or "haloalkyl" specifically refers to an alkyl substituted with one or more halogens (e.g., fluorine, chlorine, bromine, or iodine). The term "alkoxyalkyl" specifically refers to an alkyl group substituted with one or more alkoxy groups, as described below. The term "alkylamino" particularly refers to an alkyl group substituted with one or more amino groups. As described below, when "alkyl" is used in one instance and a specific term such as "alkyl alcohol" is used in another instance, it is not meant to imply that the term "alkyl" does not refer to the specific term such as "alkyl alcohol" or the like at the same time.

Embodiments of the present invention are also useful in other groups described herein. That is, when a term such as "cycloalkyl" refers to both unsubstituted and substituted cycloalkyl moieties, the substituted moiety may be otherwise specifically identified in the present invention; for example, a specifically substituted cycloalkyl group can be referred to as, for example, "alkylcycloalkyl". Similarly, a substituted alkoxy group may be specifically referred to as, for example, "halogenated alkoxy", and a specific substituted alkenyl group may be, for example, "enol" and the like. Likewise, practice of using general terms such as "cycloalkyl" and specific terms such as "alkylcycloalkyl" is not intended to imply that the general terms do not also encompass the specific terms.

The term "cycloalkyl" as used herein is a non-aromatic carbon-based ring made up of at least three carbon atoms. Examples of cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclononyl, and the like. The term "heterocycloalkyl" is a class of cycloalkyl groups as defined above and is included within the meaning of the term "cycloalkyl" in which at least one ring carbon atom is substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. The cycloalkyl and heterocycloalkyl groups can be substituted or unsubstituted. The cycloalkyl and heterocycloalkyl groups may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, amino, ether, halogen, hydroxy, nitro, silyl, sulfo-oxo, or thiol groups as described herein.

The terms "alkoxy" and "alkoxy group," as used herein, refer to an alkyl or cycloalkyl group bonded through an ether linkage; that is, "alkoxy" may be defined as-OR¹Wherein R is¹Is alkyl or cycloalkyl as defined above. "alkoxy" also includes polymers of the alkoxy groups just described; that is, the alkoxy group may be a polyether such as-OR¹—OR²OR-OR¹—(OR²)_a—OR³Wherein "a" is an integer of 1 to 200, and R¹,R²And R³Each independently is an alkyl group, a cycloalkyl group, or a combination thereof.

The term "alkenyl" as used herein is a hydrocarbon group of 2 to 24 carbon atoms, the structural formula of which contains at least one carbon-carbon double bond. Asymmetric structures such as (R)¹R²)C＝C(R³R⁴) Intended to encompass E and Z isomerismAnd (3) a body. This can be presumed in the structural formula of the present invention in which an asymmetric olefin is present, or it can be explicitly represented by the bond symbol C ═ C. The alkenyl group may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxy, ketone, azido, nitro, silyl, thio-oxo (sulfo-oxo), or thiol as described herein.

The term "cycloalkenyl" as used herein is a non-aromatic, carbon-based ring, consisting of at least 3 carbon atoms and containing at least one carbon-carbon double bond, i.e., C ═ C. Examples of cycloalkenyl groups include, but are not limited to, cyclopropenyl, cyclobutenyl, cyclopentenyl, cyclopentadienyl, cyclohexenyl, cyclohexadienyl, norbornenyl, and the like. The term "heterocycloalkenyl" is a type of cycloalkenyl group as defined above, and is included within the meaning of the term "cycloalkenyl", where at least one carbon atom of the ring is substituted with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. Cycloalkenyl and heterocycloalkenyl groups can be substituted or unsubstituted. The cycloalkenyl and heterocycloalkenyl groups may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxy, ketone, azido, nitro, silyl, thio-oxo (sulfo-oxo), or thiol groups as described herein.

The term "alkynyl" as used herein is a hydrocarbon group having 2 to 24 carbon atoms and having a structural formula containing at least one carbon-carbon triple bond. Alkynyl groups can be unsubstituted or substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxy, ketone, azido, nitro, silyl, thio-oxo (sulfo-oxo), or thiol groups as described herein.

The term "cycloalkynyl" as used herein is a non-aromatic, carbon-based ring containing at least seven carbon atoms and containing at least one carbon-carbon triple bond. Examples of cycloalkynyl include, but are not limited to, cycloheptynyl, cyclooctynyl, cyclononynyl, and the like. The term "heterocycloalkynyl" is a type of cycloalkenyl group as defined above and is included within the meaning of the term "cycloalkynyl" wherein at least one of the carbon atoms of the ring is replaced with a heteroatom such as, but not limited to, nitrogen, oxygen, sulfur, or phosphorus. Cycloalkynyl and heterocycloalkynyl can be substituted or unsubstituted. Cycloalkynyl and heterocycloalkynyl may be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde, amino, carboxylic acid, ester, ether, halogen, hydroxy, ketone, azido, nitro, silyl, thio-oxo (sulfo-oxo), or thiol as described herein.

The term "aryl" as used herein is a group containing any carbon-based aromatic group including, but not limited to, benzene, naphthalene, phenyl, biphenyl, phenoxybenzene, and the like. The term "aryl" also includes "heteroaryl," which is defined as a group containing an aromatic group having at least one heteroatom incorporated into the ring of the aromatic group. Examples of heteroatoms include, but are not limited to, nitrogen, oxygen, sulfur, and phosphorus. Likewise, the term "non-heteroaryl" (which is also included in the term "aryl") defines a group that contains an aromatic group, which does not contain heteroatoms. The aryl group may be substituted or unsubstituted. The aryl group can be substituted with one or more groups including, but not limited to, alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, heteroaryl, aldehyde groups, amino, carboxylic acid groups, ester groups, ether groups, halogens, hydroxyl, ketone groups, azido, nitro, silyl, thio-oxo groups, or mercapto groups as described herein. The term "biaryl" is a specific type of aryl group and is included in the definition of "aryl". Biaryl refers to two aryl groups joined together via a fused ring structure, as in naphthalene, or two aryl groups connected via one or more carbon-carbon bonds, as in biphenyl.

The term "amine" or "amino" as used herein is defined by the formula-NR¹R²Is represented by the formula (I) in which R¹And R²Can be independently selected from hydrogen, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl.

The term "alkylamino" as used herein is represented by the formula-NH (-alkyl), wherein alkyl is as described herein. Representative examples include, but are not limited to, methylamino, ethylamino, propylamino, isopropylamino, butylamino, isobutylamino, (sec-butyl) amino, (tert-butyl) amino, pentylamino, isopentylamino, (tert-pentyl) amino, hexylamino, and the like.

The term "dialkylamino" as used herein, is defined by the formula-N (_ alkyl)₂Wherein alkyl is as described herein. Representative examples include, but are not limited to, dimethylamino, diethylamino, dipropylamino, diisopropylamino, dibutylamino, diisobutylamino, di (sec-butyl) amino, di (tert-butyl) amino, dipentylamino, diisopentylamino, di (tert-pentyl) amino, dihexylamino, N-ethyl-N-methylamino, N-methyl-N-propylamino, N-ethyl-N-propylamino, and the like.

The term "ether" as used herein is defined by the formula R¹OR²Is represented by, wherein R is¹And R²May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. The term "polyether" as used herein is of the formula (R) — (R)¹O-R²O)_a-represents wherein R¹And R²May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group described herein and "a" is an integer from 1 to 500. Examples of polyether groups include polyethylene oxide, polypropylene oxide, and polybutylene oxide.

The term "halogen" as used herein refers to the halogens fluorine, chlorine, bromine, and iodine.

The term "heterocyclyl" as used herein refers to monocyclic and polycyclic non-aromatic ring systems, and "heteroaryl" as used herein refers to monocyclic and polycyclic aromatic ring systems: wherein at least one of the ring members is not carbon. The term includes azetidinyl, dioxanyl, furanyl, imidazolyl, isothiazolyl, isoxazolyl, morpholinyl, oxazolyl including 1,2, 3-oxadiazolyl, 1,2, 5-oxadiazolyl and 1,3, 4-oxadiazolyl, piperazinyl, piperidinyl, pyrazinyl, pyrazolyl, pyridazinyl, pyridinyl, pyrimidinyl, pyrrolyl, pyrrolidinyl, tetrahydrofuryl, tetrahydropyranyl, tetrazinyl including 1,2,4, 5-tetrazinyl, tetrazolyl including 1,2,3, 4-tetrazolyl and 1,2,4, 5-tetrazolyl, thiadiazolyl including 1,2, 3-thiadiazolyl, 1,2, 5-thiadiazolyl and 1,3, 4-thiadiazolyl, thiazolyl, thienyl, thiadiazolyl including 1,3, 5-triazinyl and 1, triazinyl groups of 2, 4-triazinyl groups, triazolyl groups including 1,2, 3-triazolyl groups and 1,3, 4-triazolyl groups, and the like.

The term "hydroxy" as used herein is represented by the formula-OH.

The term "ketone" as used herein is defined by the formula R¹C(O)R²Is represented by the formula (I) in which R¹And R²May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.

The term "azido" as used herein is of the formula-N₃And (4) showing.

The term "nitro" as used herein refers to the formula-NO₂And (4) showing.

The term "nitrile" as used herein is represented by the formula — CN.

The term "silyl" as used herein, is defined by the formula-SiR¹R²R³Is represented by the formula (I) in which R¹,R²And R³And may independently be hydrogen or an alkyl, cycloalkyl, alkoxy, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.

The term "thio-oxo" as used herein is defined by the formula-S (O) R¹,—S(O)₂R¹,—OS(O)₂R¹or-OS (O)₂OR¹Is represented by the formula (I) in which R¹May be hydrogen orThe alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl groups described herein. Throughout the specification, "S (O)" is a shorthand form of S ═ O. The term "sulfonyl", as used herein, refers to a compound of the formula-S (O)₂R¹A thio-oxo group of the formula, wherein R¹Can be alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl. The term "mock" as used herein is defined by the formula R¹S(O)₂R²Table in which R¹And R²May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein. The term "sulfoxide" as used herein is defined by the formula R¹S(O)R²Is represented by, wherein R is¹And R²May independently be an alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, cycloalkynyl, aryl, or heteroaryl group as described herein.

The term "mercapto" as used herein is represented by the formula-SH

"R" used in the present invention¹,”“R²,”“R³,”“Rⁿ"(wherein n is an integer) may independently have one or more of the groups listed above. For example, if R¹Being a straight chain alkyl, then one hydrogen atom of the alkyl group may be optionally substituted with hydroxyl, alkoxy, alkyl, halogen, and the like. Depending on the group selected, the first group may be incorporated within the second group, or alternatively, the first group may be pendent (i.e., attached) to the second group. For example, for the phrase "alkyl group comprising an amino group," the amino group can be incorporated within the backbone of the alkyl group. Alternatively, the amino group may be attached to the backbone of the alkyl group. The nature of the selected group will determine whether the first group is intercalated or attached to the second group.

The compounds of the present invention may contain "optionally substituted" moieties. Generally, the term "substituted" (whether or not the term "optionally" is present above) means that one or more hydrogens of the indicated moiety are replaced with a suitable substituent. Unless otherwise specified, an "optionally substituted" group may have suitable substituents at each substitutable position of the group, and when more than one position may be substituted with more than one substituent selected from a specified group in any given structure, the substituents at each position may be the same or different. The combinations of substituents contemplated by the present invention are preferably those that form stable or chemically feasible compounds. In certain aspects, it is also contemplated that each substituent may be further optionally substituted (i.e., further substituted or unsubstituted), unless clearly indicated to the contrary.

The structure of the compound can be represented by the following formula:

it is understood to be equivalent to the following formula:

where n is typically an integer. Namely, RⁿIs understood to mean five individual substituents R^n(a),R^n(b),R^n(c),R^n(d),Rⁿ ^(e). By "individual substituents" is meant that each R substituent can be independently defined. For example, if in one instance R^n(a)Is halogen, then in this case R^n(b)Not necessarily halogen.

R is referred to several times in the chemical structures and parts disclosed and described in this specification¹,R²,R³,R⁴,R⁵,R⁶And the like. In the specification, R¹,R²,R³,R⁴,R⁵,R⁶Etc. are each applicable to the citation of R¹,R²,R³,R⁴,R⁵,R⁶Etc., unless otherwise specified.

1. Compound (I)

The structure of the derivative containing 4, 10-dioxo-5, 9-diboropyrene provided by the embodiment of the invention is shown as the formula (I):

m is an integer of 0 to 5;

n is an integer of 0 to 3;

The invention also provides an OLED device which comprises one or more of the 4, 10-dioxo-5, 9-diboropyrene derivatives provided by the invention.

In some embodiments of the invention, the 4, 10-dioxo-5, 9-diboropyrene-containing derivative has a structure selected from one of:

in some embodiments of the invention, the 4, 10-dioxo-5, 9-diboropyrene derivative is electrically neutral.

In some embodiments of the invention, there is also provided an optical or electro-optical device comprising one or more of the 4, 10-dioxo-5, 9-diboropyrene derivatives described above.

In some embodiments of the invention, optical or electro-optical devices are provided that include light absorbing devices (e.g., solar devices or photosensitive devices), Organic Light Emitting Diodes (OLEDs), light emitting devices, or devices capable of both light absorption and emission.

In some embodiments of the present invention, there is also provided an OLED device in which the light emitting material or host material comprises one or more of the above 4, 10-dioxo-5, 9-diboropyrene derivatives. The compound provided by the embodiment of the invention can be used as a host material of an OLED device, such as a full-color display and the like; it is also applicable to light-emitting materials of OLED devices, such as light-emitting devices and displays.

Preparation and evaluation of Properties examples

The following examples are put forth so as to provide those of ordinary skill in the art with a complete disclosure and description of how the compounds, compositions, articles, devices, and/or methods described herein are made and evaluated, and are intended to be merely exemplary of the disclosure and are not intended to limit the scope thereof. Although efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.), some errors and deviations should be accounted for. Unless otherwise indicated, parts are parts by weight, temperature is in degrees celsius or at ambient temperature, and pressure is at or near atmospheric pressure.

Various methods for the preparation of the disclosed compounds described herein are set forth in the examples. These methods are provided to illustrate various methods of preparation, but the disclosure is not intended to be limited to any one of the methods recited herein. Thus, one of skill in the art to which this disclosure pertains may readily modify the methods described or utilize different methods for preparing one or more of the disclosed compounds. The following aspects are merely exemplary and are not intended to limit the scope of the present disclosure. The temperature, catalyst, concentration, reactant composition, and other process conditions may be varied, and appropriate reactants and conditions for the desired complex may be readily selected by one skilled in the art to which the present disclosure pertains.

CDCl on a Varian Liquid State NMR instrument₃Or DMS0-d₆Recording at 400MHz in solution¹H spectrum, recorded at 100MHz¹³C NMR spectrum, chemical shift referenced to residual deuterated solvent. If CDCl₃As a solvent, tetramethylsilane (δ ═ 0.00ppm) was used as an internal standard for recording¹H NMR spectrum; using DMSO-d₆(δ 77.00ppm) is reported as an internal standard¹³C NMR spectrum. If it is to be H₂When O (delta. 3.33ppm) is used as solvent, residual H is used₂O (δ ═ 3.33ppm) was recorded as an internal standard¹H NMR spectrum; using DMSO-d₆(delta. 39.52ppm) is recorded as internal standard¹³C NMR spectrum. The following abbreviations (or combinations thereof) are used for explanation¹Multiplicity of H NMR: s is singleplex, d is doublet, t is triplet, q is quartet, P is quintuple, m is multiplet, br is wide.

General synthetic route

The general synthetic route for the compounds disclosed in the present patent is as follows:

wherein the content of the first and second substances,

R^a、R^band R^cEach independently hydrogen, deuterium, alkyl, alkoxy, cycloalkyl, ether, heterocyclyl, phenyl, aryloxy, halogen, cyano, or combinations thereof; ar is six-membered aryl, heteroaryl, fused aryl and aza-fused aryl;

m is an integer of 0 to 5;

n is an integer of 0 to 3.

Preparation examples

Example 1: compound BO3 can be synthesized as follows:

to a dry three-necked flask with a magnetic rotor was added 2, 6-dimethoxyphenylboronic acid (3.7143g,20mmol, 98%, 1.0 equiv.), palladium acetate (0.1123g,0.5mmol,0.025 equiv.) and ligand S-Phos (0.5027g,1.2mmol, 98%, 0.06 equiv.) in that order. The nitrogen is pumped and exchanged for three timesThen, an aqueous solution (20mL) of 1, 4-dioxane (60mL), iodobenzene (4.5796g,22mmol, 98%, 1.1 equiv.) and potassium carbonate (8.2920g,60mmol,3.0 equiv.) was added under nitrogen. The three-necked bottle was then placed in a 105 ℃ oil bath. After stirring for 12 hours, the reaction was monitored by thin layer chromatography for completion. After cooling to room temperature, the organic phase was separated off and the aqueous phase was extracted with ethyl acetate (10 mL. times.2). All organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated and the crude product purified by flash column chromatography on silica gel (eluent: petroleum ether/ethyl acetate 50/1) to give a1 as a white solid 3.7215g with 87% yield.¹H NMR(400MHz,CDCl₃):δ7.37-7.49(m,5H),7.34(t,J＝8.4Hz,1H),6.71(d,J＝8.4Hz,2H),3.78(s,6H)。

To a dry three-necked flask with a magnetic rotor were added A1(0.6429g,3mmol,1.0 equiv.), toluene (20mL) and n-hexane (20mL) in that order. Boron tribromide (0.72mL, d 2.6g/mL,7.5mmol,2.5 eq) was then added dropwise under nitrogen. After stirring at room temperature for 19.5 hours, aluminum trichloride (0.0160g,0.12mmol,0.04 eq.) was added quickly and the three-necked flask was placed in a 75 ℃ oil bath. After stirring for 6 hours, cool to room temperature and add dropwise trimethylphenylmagnesium bromide (12mL,1M solution in tetrahydrofuran, 12mmol,4.0 equiv.) under nitrogen. Stirring was continued for 1 hour and the reaction was monitored by thin layer chromatography for completion. Concentrating, and separating and purifying the crude product by flash silica gel column chromatography (eluent: petroleum ether-petroleum ether/dichloromethane: 100/1) to obtain BO3 as white solid 1.2459g with yield of 94%.¹H NMR(500MHz,DMSO-d₆)δ8.08(d,J＝7.4Hz,2H),7.77(t,J＝7.3Hz,2H),7.57(d,J＝8.2Hz,2H),6.95(s,4H),2.33(s,6H),2.15(s,12H)。

Example 2: compound BO80 can be synthesized as follows:

to a dry three-necked flask with a magnetic rotor were added 2, 6-dimethoxyphenylboronic acid (3.7143g,20mmol, 98%, 1.0 equiv.), 4-iodotoluene (4.8939g,22mmol, 98%, 1.1 equiv.), palladium acetate (0.0898g,0.4mmol,0.02 equiv.) and ligand S-Phos (0.3351g,0.8mmol, 98%, 0.04 equiv.) in that order. Nitrogen was purged three times, followed by the addition of an aqueous solution (20mL) of 1, 4-dioxane (60mL) and potassium carbonate (8.2920g,60mmol,3.0 equiv.) under nitrogen. The three-necked bottle was then placed in a 100 ℃ oil bath. After stirring for 16 hours, the reaction was monitored by thin layer chromatography for completion. After cooling to room temperature, the organic phase was separated off and the aqueous phase was extracted with ethyl acetate (10 mL. times.2). All organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated and the crude product purified by flash column chromatography on silica gel (eluent: petroleum ether/ethyl acetate 50/1) to give a2 as a white solid 4.1399g in 91% yield.¹H NMR(500MHz,DMSO-d₆)δ7.27(t,J＝8.4Hz,1H),7.14(d,J＝7.8Hz,2H),7.10-7.03(m,2H),6.72(d,J＝8.4Hz,2H),3.64(s,6H),2.32(s,3H)。

To a dry three-necked flask with a magnetic rotor were added A2(0.6849g,3mmol,1.0 equiv.), toluene (20mL) and n-hexane (20mL) in that order. Boron tribromide (0.72mL, d 2.6g/mL,7.5mmol,2.5 eq) was then added dropwise under nitrogen. After stirring at room temperature for 41 hours, aluminum trichloride (0.0160g,0.12mmol,0.04 eq.) was added quickly and the three-necked flask was placed in a 75 ℃ oil bath. After stirring for 8 hours, cool to room temperature and add dropwise trimethylphenylmagnesium bromide (12mL,1M solution in tetrahydrofuran, 12mmol,4.0 equiv.) under nitrogen. Stirring was continued for 1 hour and the reaction was monitored by thin layer chromatography for completion. Concentrating, separating and purifying the crude product by flash silica gel column chromatography (eluent: petroleum ether-petroleum ether/dichloromethane: 100/1) to obtain BO80 as white solid1.2218g, 89% yield.¹H NMR(500MHz,DMSO-d₆)δ7.88(s,2H),7.73(t,J＝8.3Hz,1H),7.55(d,J＝8.2Hz,2H),6.95(s,4H),2.44(s,3H),2.33(s,6H),2.15(s,12H)。

FIG. 3 shows the excitation and emission spectra of a solution of the compound BO80 in dichloromethane at room temperature and a solution of it in 2-methyltetrahydrofuran at 77K.

Example 3: compound BO312 can be synthesized as follows:

to a dry three-necked flask with a magnetic rotor were added 2, 6-dimethoxyphenylboronic acid (4.0857g,22mmol, 98%, 1.2 equiv.), 4-iodo-1, 1' -biphenyl (5.7753g,20mmol, 97%, 1.0 equiv.), palladium acetate (0.0898g,0.4mmol,0.02 equiv.) and ligand S-Phos (0.3351g,0.8mmol, 98%, 0.04 equiv.) in that order. Nitrogen was purged three times, followed by the addition of an aqueous solution (20mL) of 1, 4-dioxane (60mL) and potassium carbonate (8.2920g,60mmol,3.0 equiv.) under nitrogen. The three-necked bottle was then placed in a 100 ℃ oil bath. After stirring for 17 hours, the reaction was monitored by thin layer chromatography for completion. After cooling to room temperature, the organic phase was separated off and the aqueous phase was extracted with ethyl acetate (10 mL. times.2). All organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated and the crude product purified by flash column chromatography on silica gel (eluent: petroleum ether/ethyl acetate 50/1) to give A3 as a white solid 5.2177g in 90% yield.¹H NMR(500MHz,DMSO-d₆)δ7.70(d,J＝7.1Hz,2H),7.64(d,J＝8.3Hz,2H),7.48(t,J＝7.7Hz,2H),7.37(t,J＝7.4Hz,1H),7.34-7.26(m,3H),6.76(d,J＝8.4Hz,2H),3.68(s,6H)。

To a dry three-necked flask with a magnetic rotor was added A3(0.8712g,3mmol,1.0 equiv.), o-xylene (30mL) and n-hexane (10mL) in that order. Boron tribromide (0.72mL, d 2.6g/mL,7.5mmol,2.5 eq) was then added dropwise under nitrogen. Stirring at room temperature for 24 hoursAfter this time, aluminum trichloride (0.0160g,0.12mmol,0.04 eq.) was added quickly and the three-necked flask was then placed in a 75 ℃ oil bath. After stirring for 8 h, cool to room temperature and add dropwise trimethylphenylmagnesium bromide (15mL,1M in ether, 15mmol,5.0 equiv.) under nitrogen. Stirring was continued for 1 hour and the reaction was monitored by thin layer chromatography for completion. Concentrating, and separating and purifying the obtained crude product by flash silica gel column chromatography (eluent: petroleum ether-petroleum ether/dichloromethane: 100/1) to obtain BO312 as white solid 1.3911g, yield 89%.¹H NMR(500MHz,DMSO-d₆)δ8.20(s,2H),7.78(t,J＝8.3Hz,1H),7.59(d,J＝8.2Hz,2H),7.52(d,J＝7.2Hz,2H),7.46(t,J＝7.6Hz,2H),7.38(t,J＝7.3Hz,1H),6.96(s,4H),2.33(s,6H),2.20(s,12H)。

FIG. 4 shows excitation and emission spectra of a dichloromethane solution of the compound BO312 at room temperature and a 2-methyltetrahydrofuran solution thereof at 77K.

Example 4: the compound BO543 can be synthesized by the following route:

to a dry three-necked flask with a magnetic rotor were added 2, 6-dimethoxyphenylboronic acid (4.0857g,22mmol, 98%, 1.1 equiv.), 1-bromo-4-tert-butylbenzene (4.3490g,20mmol, 98%, 1.0 equiv.), palladium acetate (0.0898g,0.4mmol,0.02 equiv.) and ligand S-Phos (0.3351g,0.8mmol, 98%, 0.04 equiv.) in that order. Nitrogen was purged three times, followed by the addition of an aqueous solution (20mL) of 1, 4-dioxane (60mL) and potassium carbonate (8.2920g,60mmol,3.0 equiv.) under nitrogen. The three-necked bottle was then placed in a 100 ℃ oil bath. After stirring for 24 hours, the reaction was monitored by thin layer chromatography for completion. After cooling to room temperature, the organic phase was separated off and the aqueous phase was extracted with ethyl acetate (10 mL. times.2). All organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated and the crude product purified by flash column chromatography on silica gel (eluent: petroleum ether/ethyl acetate 50/1) to give a5 as a white solid 4.6955g with 87% yield.¹H NMR(500MHz,DMSO-d₆)δ7.41(d,J＝8.4Hz,2H),7.29(d,J＝8.4Hz,2H),7.25(d,J＝8.5Hz,1H),6.65(d,J＝8.4Hz,2H),3.74(s,6H),1.36(s,9H)。

To a dry three-necked flask with a magnetic rotor were added A5(0.8112g,3mmol,1.0 equiv.), toluene (20mL) and n-hexane (20mL) in that order. Boron tribromide (0.72mL, d 2.6g/mL,7.5mmol,2.5 eq) was then added dropwise under nitrogen. After stirring at room temperature for 21 hours, aluminum trichloride (0.0160g,0.12mmol,0.04 eq.) was added quickly and the three-necked flask was placed in a 75 ℃ oil bath. After stirring for 15 h, cool to room temperature and add dropwise trimethylphenylmagnesium bromide (15mL,1M solution in tetrahydrofuran, 15mmol,5.0 equiv.) under nitrogen. Stirring was continued for 1 hour and the reaction was monitored by thin layer chromatography for completion. Concentrating, and separating and purifying the crude product by flash silica gel column chromatography (eluent: petroleum ether-petroleum ether/dichloromethane: 100/1) to obtain BO543 as white solid 1.2641g, yield 85%.¹H NMR(500MHz,CDCl₃)δ8.23(s,2H),7.60(t,J＝8.0Hz,1H),7.46(d,J＝8.1Hz,2H),6.96(s,4H),2.39(s,6H),2.26(s,12H),1.30(s,9H)。

FIG. 6 is an emission spectrum of a dichloromethane solution of the compound BO543 at room temperature and a 2-methyltetrahydrofuran solution thereof at 77K.

Example 5: the compound BO555 can be synthesized by the following route:

to a dry three-necked flask with a magnetic rotor were added 2, 6-dimethoxyphenylboronic acid (4.0857g,22mmol, 98%, 1.2 equiv.), 1-iodo-3, 5-dimethylbenzene (4.8863g,20mmol, 95%, 1.0 equiv.), palladium acetate (0.0898g,0.4mol,0.02 equiv.) and ligand S-Phos (0.3351g,0.8mmol, 98%, 0.04 equiv.) in that order. Nitrogen was purged three times, followed by the addition of an aqueous solution (20mL) of 1, 4-dioxane (60mL) and potassium carbonate (8.2920g,60mmol,3.0 equiv.) under nitrogen. The three-necked bottle was then placed in a 100 ℃ oil bath. After stirring for 18 hours, the reaction was monitored by thin layer chromatography for completion. Cooling to room temperature, and separatingThe organic phase was removed and the aqueous phase was extracted with ethyl acetate (10 mL. times.2). All organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated and the crude product purified by flash column chromatography on silica gel (eluent: petroleum ether/ethyl acetate 50/1) to give a4 as a white solid 4.2587g in 88% yield.¹H NMR(500MHz,DMSO-d₆)δ7.27(t,J＝8.4Hz,1H),6.88(s,1H),6.75(s,2H),6.70(d,J＝8.4Hz,2H),3.63(s,6H),2.26(s,6H)。

To a dry three-necked flask with a magnetic rotor were added A4(0.7299g,3mmol,1.0 equiv.), toluene (20mL) and n-hexane (20mL) in that order. Boron tribromide (0.72mL, d 2.6g/mL,7.5mmol,2.5 eq) was then added dropwise under nitrogen. After stirring at room temperature for 41 hours, aluminum trichloride (0.0160g,0.12mmol,0.04 eq.) was added quickly and the three-necked flask was placed in a 75 ℃ oil bath. After stirring for 8 h, cool to room temperature and add dropwise trimethylphenylmagnesium bromide (15mL,1M in ether, 15mmol,5.0 equiv.) under nitrogen. Stirring was continued for 1 hour and the reaction was monitored by thin layer chromatography for completion. Concentrating, and separating and purifying the obtained crude product by flash silica gel column chromatography (eluent: petroleum ether-petroleum ether/dichloromethane: 100/1) to obtain BO555 as white solid 1.2017g with yield of 85%.¹H NMR(500MHz,CDCl₃)δ7.57(t,J＝8.3Hz,1H),7.41(d,J＝8.1Hz,2H),7.25(s,1H),6.93(s,4H),2.35(s,6H),2.28(s,6H),2.21(s,12H)。

FIG. 7 shows the excitation and emission spectra of a solution of compound BO555 in dichloromethane at room temperature and of a solution of it in 2-methyltetrahydrofuran at 77K.

Example 6: the compound BO466 can be synthesized by the following route:

to a clean three-necked flask with a rotor was added 3, 5-dimethyl-4-bromoaniline (232mg, 1.00mmol, 1.00 eq.), tetrakistriphenylphosphinePalladium (58mg, 0.05mmol, 0.05 equiv.), anhydrous potassium carbonate (276mg, 2.00mmol, 2.00 equiv.). Nitrogen was purged and added three times to 1, 4-dioxane/water (15mL/7mL) and the mixture was bubbled for 20 minutes and reacted at 100 ℃ for 24 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, water (50mL) was added thereto, and the mixture was extracted with ethyl acetate (50mL × 2), and the organic layers were combined, dried over anhydrous sodium sulfate, separated and concentrated, and separated with a silica gel column (petroleum ether: ethyl acetate ═ 3: 1) to obtain 228mg of a white solid with a yield of 99%.¹H NMR(500MHz,DMSO-d₆):δ3.56(s,6H),5.23(s,2H),5.96(s,2H),7.14-7.18(m,3H),7.26-7.29(m,2H).

To a clean three-necked flask with a rotor was added aniline derivative (228mg, 1.00mmol, 1.00 equiv), concentrated hydrochloric acid (0.4ml, 10M/L in water), purified water (20ml) and cooled to 0 deg.C, and an aqueous solution of sodium nitrite (76mg, 1.10mmol, 1.10 equiv) was added dropwise. After completion of the dropwise addition, the reaction mixture was reacted at 0 ℃ for 30 minutes, and then an aqueous solution of potassium iodide (199mg, 1.20mmol, 1.20 equiv.) was added to the reaction mixture, and the reaction mixture was slowly raised to 25 ℃ for 15 hours. After completion of the reaction, an aqueous sodium thiosulfate solution (1M/L in water 50mL) was added, and the mixture was sufficiently stirred and extracted with ethyl acetate (50 mL). The organic layer was dried over anhydrous sodium sulfate, separated and concentrated, and separated with a silica gel column (petroleum ether: ethyl acetate: 20: 1) to obtain 220mg of a white solid with a yield of 65%.¹H NMR(500MHz,DMSO-d₆):δ3.67(s,6H),7.08(s,2H),7.17-7.19(m,2H),7.26-7.29(m,1H),7.34-7.37(m,2H).

To a clean three-necked flask with a rotor was added iodobenzene derivative (220mg, 0.65mmol, 1.00 equiv.), phenylboronic acid (95mg, 0.78mmol, 1.20 equiv.), palladium tetrakistriphenylphosphine (38mg, 0.03mmol, 0.05 equiv.), potassium carbonate (180mg, 1.30mmol, 2.00 equiv.). Nitrogen was purged three times and 1, 4-dioxane/water (15mL/7mL) was added. After bubbling for 20 minutes, the reaction was carried out at 100 ℃ for 24 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, water (50mL) was added and extracted with ethyl acetate (50 mL. times.2), the organic layers were combined, dried over anhydrous sodium sulfate, separated and concentrated, and separated with a silica gel column (petroleum ether: ethyl acetate)1) gave a white solid a 6187 mg in 99% yield.¹H NMR(500MHz,DMSO-d₆):δ3.76(s,6H),6.98(s,2H),7.24-7.30(m,3H),7.36-7.42(m,3H),7.49-7.52(m,2H),7.77-7.79(m,2H).

To a clean three-necked flask with a rotor was added terphenyl derivative A6(618mg, 2.13mmol, 1.00 eq.) and nitrogen was purged three times. Hexane (50ml), a 1M/L hexane solution of boron tribromide (5.3ml, 2.5 equiv) was added to the mixture, and the mixture was reacted at 25 ℃ for 18 hours. Then, anhydrous aluminum trichloride (10mg, 0.08mmol, 0.04 eq.) was added and the temperature was raised to 75 ℃ for reaction for 18 hours. After the reaction was completed, 2-mesitylene magnesium bromide 1M/L diethyl ether solution (6.4ml, 3.00 equiv.) was added thereto and reacted at 25 ℃ for 18 hours. After the reaction was completed, the reaction mixture was distilled to dryness under reduced pressure, and separated with a silica gel column (50: 1 petroleum ether/dichloromethane) to obtain BO466 as a white solid in a yield of 76% in the range of 840 mg.¹H NMR(500MHz,CDCl₃):δ2.28(s,12H),2.40(s,6H),6.99(s,4H),7.41-7.45(m,1H),7.51-7.54(m,2H),7.62(t,J＝7.4Hz,1H),7.71-7.79(m,4H),8.20(d,J＝7.3Hz,2H).

FIG. 5 shows the emission spectra of a dichloromethane solution of the compound BO466 at room temperature and a 2-methyltetrahydrofuran solution thereof at 77K.

Performance evaluation examples

The 4, 10-dioxo-5, 9-diboropyrene derivatives (hereinafter also referred to as boroxapyrene derivative materials) prepared in the above examples of the present invention were subjected to photophysical, electrochemical and thermogravimetric analyses as follows:

and (3) photophysical analysis: the phosphorescence emission spectrum, the fluorescence emission spectrum, the triplet state lifetime and the excited state lifetime are tested and finished on a HORIBA FL3-11 spectrometer. And (3) testing conditions are as follows: in the room temperature emission spectrum, all samples were dichloromethane (chromatographic grade) dilute solutions (10)^-5-10^-6M), and the samples are prepared in a glove box, and nitrogen is introduced for 5 minutes; the triplet state lifetime measurements were all measured at the most intense peak of the sample emission spectrum.

Electrochemical analysis: by means of circulating voltsThe Ann method is carried out on an electrochemical workstation of the type CH 670E. With 0.1M tetra-n-butylammonium hexafluorophosphate (b)ⁿBu₄NPF₆) The N, N-dimethyl acetamide (DMF) solution is an electrolyte solution; the metal platinum electrode is a positive electrode; graphite is used as a negative electrode; the metal silver is used as a reference electrode; ferrocene is the reference internal standard and its redox potential is set to zero.

Thermogravimetric analysis: the thermogravimetric analysis curves were all completed on the TGA2(SF) thermogravimetric analysis. The thermogravimetric analysis test conditions were: the testing temperature is 50-700 ℃; the heating rate is 20K/min; the crucible is made of aluminum oxide; and testing is completed under nitrogen atmosphere; the sample mass is generally 2-5 mg.

TABLE 1 photophysical properties and thermogravimetric analysis data of boroxapyrene derivative materials

Note: peak refers to the strongest emission Peak of the room temperature emission spectrum of the boron oxapyrene derivative material. PLQY refers to absolute luminescence quantum efficiency. The room temperature emission spectrum of the boroxapyrene derivative material was measured in a dichloromethane solution, and the 77K emission spectrum was measured in 2-methyltetrahydrofuran (2-Me-THF). Triplet energy level (T)₁) Calculated from its phosphorescence spectrum at 77K. Thermal decomposition temperature (T)_d) From thermogravimetric analysis (TGA) curves. Glass transition temperature (T)_g) And melting point (m.p.) from Differential Scanning Calorimetry (DSC) curves.

Excitation and emission spectra of boroxapyrene derivative materials in methylene chloride solution at room temperature, excitation and emission spectra in 2-methyltetrahydrofuran (2-Me-THF) at 77K, and thermogravimetric analysis (TGA) curves of a portion of the materials are shown in FIGS. 1-7.

From table 1, it can be seen that: firstly, the boron-oxapyrene derivative materials provided by the invention have very high luminescent quantum efficiency (PLQY) which can reach 21.49-45.77%; and all exhibit short excited state lifetimes of 2.39-5.84 ns; in addition, the thermal decomposition temperature is high, and the properties are favorable for the application of the boron-oxapyrene derivative in luminescent materials. Di, boroxapyrene derivatives thereofThe biological structure is various and is easy to modify, so that the biological structure has easily-regulated triplet state energy level (T)₁) Can be used as the host material of various luminophors. As shown in table 1, the triplet energy levels of BO312, BO555 and BO466 are between 2.61-2.63eV and can be used as host materials for red and green emitters; BO3, BO80 and BO543 have very high triplet energy levels (3.00-3.06eV), and are useful as host materials for blue, especially deep blue, light emitters. Provides an effective solution for the current critical deep blue light main body material, thereby greatly promoting the development of the field.

The film photophysical property data of the boron-oxapyrene derivative provided by the invention as a blue light and deep blue light main body material are shown in the following table.

TABLE 2 thin film photophysical property data of boroxapyrene derivatives as host materials for blue and deep blue light

The structures of the blue and deep blue materials PtON1, PtLA5t and host material 26mCPy are as follows:

from table 2, it can be seen that: first, the boron oxapyrene derivative material can be well used as the host material of the blue light material PtON1 and the deep blue light material PtLA5t, so that the absolute quantum efficiency of the doped film is respectively as high as 74.88% and 73.12% (the 2 nd row and the 1 st row). First, comparing the data in table 2 and 3, it can be seen that BO80 is superior to the currently widely used 26mCPy as the host material of the blue emitter PtON 1. This is mainly due to the fact that BO80 has a very high triplet level (3.00eV), which is about 0.2eV higher than PtON1 and PtLA5t, and can promote the efficient transfer of energy from the host material to the emitter, thereby increasing the absolute quantum efficiency of the thin film. The data result further shows the advantages of the boron-oxapyrene derivative as the host material, so that the boron-oxapyrene derivative has wide use space in the field of OLED, and especially promotes the development of blue light and deep blue light host materials.

Device examples

All materials are subjected to a high vacuum (10) prior to use^-5-10^-6Torr) to carry out gradient heating sublimation purification. Indium Tin Oxide (ITO) substrates used by the devices were sequentially sonicated in deionized water, acetone, and isopropanol. The device passes through the vacuum degree of less than 10^-7And vacuum thermal evaporation is carried out under the pressure of Torr. The anode electrode has a thickness of

Indium Tin Oxide (ITO), the cathode is made of a material having a thickness of

LiF and

al of (1). After all devices are prepared, the glass cover and the epoxy resin are packaged in a nitrogen glove box, and a moisture absorbent is added into the package.

The device structure is as follows:

Device 1:ITO/HATCN(10nm)/HTL(70nm)/EBL(5nm)/BO80:PtON1(25nm,8％)/DPEPO(10nm)/TmPyPb(30nm)/LiF(1nm)/Al.

Device 2:ITO/HATCN(10nm)/HTL(70nm)/EBL(5nm)/BO80:PtLA5t(25nm,8％)/DPEPO(10nm)/TmPyPb(30nm)/LiF(1nm)/Al.

the molecular structure of the materials used in the above devices is as follows:

FIG. 8 is a graph of luminance vs. power efficiency for a device with compound BO80 as the host material.

FIG. 9 is a graph of luminance versus external quantum efficiency for a device with compound BO80 as the host material.

FIG. 10 is a voltage-luminance curve of a device with compound BO80 as the host material.

The device performance data using the boroxapyrene derivative BO80 as the host material are shown in table 3 below.

TABLE 3 device Performance Using Boroxapyrene derivative BO80 as host Material

Note: peak refers to the strongest emission Peak of the device emission spectrum at room temperature; FWHM refers to the half-peak width of the emission spectrum of the device at room temperature; v refers to the turn-on voltage of the device; CE refers to the current efficiency of the device; PE refers to the power efficiency of the device; EQE refers to the external quantum efficiency of the device; CE_maxRefers to the maximum current efficiency of the device; PE (polyethylene)_maxRefers to the maximum power efficiency of the device; EQE_maxRefers to the maximum external quantum efficiency of the device.

As can be seen from table 3: first, the device 1 using the boron oxapyrene derivative BO80 as a host material and PtON1 as a light emitter has an external quantum efficiency of 12.0% at a luminance of 1000 nits, CIE coordinates (0.151,0.189), and is a blue light emitting device, and has a maximum external quantum efficiency of 14.0%, further indicating that the boron oxapyrene derivative BO80 is a good host material. Secondly, the CIE coordinates of the device 2 using the boron-oxapyrene derivative BO80 as the host material and the PtLA5t as the light emitter at 1000 nits are (0.145,0.106), which is a deep blue device, the external quantum efficiency of the device 2 can reach 9.0%, and the maximum external quantum efficiency of the device 2 can reach 13.3%. The half-peak width of the emission spectrum of the device 2 is 33.7nm, which is obviously smaller than that of the device 1, so that the light emission of the device is further blue-shifted to 450nm, and the deep blue light emission is realized.

The above device data fully indicate that the boron oxapyrene derivative is feasible as a host material, especially the feasibility and superiority of the boron oxapyrene derivative as a host material of a blue light and deep blue light luminous body which is in urgent need at present.

It will be understood by those of ordinary skill in the art that the foregoing embodiments are specific examples for carrying out the invention, and that various changes in form and details may be made therein without departing from the spirit and scope of the invention in practice. For example, many of the materials and structures described herein may be substituted with other materials and structures without departing from the spirit of the invention.

Claims

1. A4, 10-dioxo-5, 9-diboropyrene derivative is characterized in that the structure of the derivative is shown as the formula (I):

wherein the content of the first and second substances,

R^a、R^band R^cEach independently hydrogen, deuterium, alkyl, alkoxy, cycloalkyl, phenyl, aryloxy, cyano, or a combination thereof; ar is a six-membered aryl group;

m is an integer of 0 to 5;

n is an integer of 0 to 3;

2. The 4, 10-dioxo-5, 9-diboropyrene derivative of claim 1, wherein Ar in formula (I) is phenyl.

3. An optical or electro-optical device, characterized by: the device comprises one or more of the 4, 10-dioxo-5, 9-diboropyrene derivatives of any of claims 1-2.

4. An optical or electro-optical device as claimed in claim 3, wherein the device comprises a light absorbing device, an organic light emitting diode, a light emitting device or a device capable of both light absorption and emission.

5. An OLED device, characterized by: the host material in the OLED device comprises one or more of the 4, 10-dioxo-5, 9-diboropyrene derivatives of any of claims 1-2.