CN110272441B - Biboroxadibenzo [ A, H ] anthracene derivatives and application thereof - Google Patents

Biboroxadibenzo [ A, H ] anthracene derivatives and application thereof Download PDF

Info

Publication number
CN110272441B
CN110272441B CN201910478956.5A CN201910478956A CN110272441B CN 110272441 B CN110272441 B CN 110272441B CN 201910478956 A CN201910478956 A CN 201910478956A CN 110272441 B CN110272441 B CN 110272441B
Authority
CN
China
Prior art keywords
materials
equiv
room temperature
diboron
derivative
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201910478956.5A
Other languages
Chinese (zh)
Other versions
CN110272441A (en
Inventor
李贵杰
戴健鑫
陈少海
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang University of Technology ZJUT
Original Assignee
Zhejiang University of Technology ZJUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang University of Technology ZJUT filed Critical Zhejiang University of Technology ZJUT
Priority to CN201910478956.5A priority Critical patent/CN110272441B/en
Publication of CN110272441A publication Critical patent/CN110272441A/en
Application granted granted Critical
Publication of CN110272441B publication Critical patent/CN110272441B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
    • C07F5/02—Boron compounds
    • C07F5/025—Boronic and borinic acid compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1003—Carbocyclic compounds
    • C09K2211/1007—Non-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
    • C09K2211/10—Non-macromolecular compounds
    • C09K2211/1018—Heterocyclic compounds
    • C09K2211/1025—Heterocyclic compounds characterised by ligands
    • C09K2211/1096—Heterocyclic compounds characterised by ligands containing other heteroatoms

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention relates to the technical field of optical and photoelectric materials, and discloses a derivative based on diboron xanthene, a preparation method and application thereof. The diboron oxadibenzo [ A, H ] anthracene derivative has the characteristics of high quantum efficiency, high thermal decomposition temperature and glass transition temperature, easily adjustable triplet state energy level and the like, and has huge application prospect in the field of main body materials or luminescent materials.

Description

Biboroxadibenzo [ A, H ] anthracene derivatives and application thereof
Technical Field
The invention relates to the technical field of optical and photoelectric materials, in particular to a functional material based on a diboron-oxadibenzo [ A, H ] anthracene derivative, which can be applied to optical or photoelectric devices.
Background
Compounds capable of absorbing and/or emitting light are desirable materials for a wide variety of optical and electroluminescent devices, and may be used in 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 compounds with excellent photophysical properties such as high triplet energy levels have been reported.
The OLED device is composed of an anode and a cathode, and one or more organic compound layers disposed between the anode and the cathode. Wherein the organic compound layer includes a light emitting layer, an electron and hole injection, transport layer. Therefore, active research into organic materials having charge transport ability such as holes and electrons, 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 there are few related boron-nitrogen-polycyclic aromatic hydrocarbon compound materials suitable as host materials or light-emitting materials for electro-optical devices.
Disclosure of Invention
The invention aims to provide a diboron-oxadibenzo [ A, H ] anthracene derivative and application thereof in optical or photoelectric devices.
The purpose of the invention is realized by the following scheme: a diboron oxadibenzo [ A, H ] anthracene derivative has a structure shown in formulas (I) and (II):
Figure BDA0002082607600000021
wherein R isa、Rb、Rc、RdAnd ReEach 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 4.
Preferably, the diboron oxadibenzo [ a, H ] anthracene derivative is:
Figure BDA0002082607600000031
Figure BDA0002082607600000041
Figure BDA0002082607600000051
Figure BDA0002082607600000061
Figure BDA0002082607600000071
Figure BDA0002082607600000081
preferably, the derivative is electrically neutral.
The application of the derivative is used as a luminescent material or a host material in an optical or photoelectric device.
Further, the optical device or the photovoltaic device includes a solar device, a photosensitive device, an organic light emitting diode light emitting device, and a device capable of compatible light absorption and emission.
The invention provides a diboronoxydibenzo [ A, H ]]The anthracene derivative has the following advantages: first, it has a high luminescence quantum efficiency (PLQY) and a short excited state lifetime. Secondly, the high thermal decomposition temperature and glass transition temperature facilitate its use in hosts or light emitting materials in OLED devices. Tris, diborono-dibenzo [ A, H ]]The anthracene derivative has various structures and is easy to modify, so that the anthracene derivative has an easily-adjusted triplet state energy level (T)1) Can be used as the host material of various luminophors. The invention provides a diboron-oxadibenzo [ A, H ]]In the anthracene derivative, part of the material has a very high triplet energy level (2.78eV), and can be used as a host material of a blue light emitter. Therefore, the invention provides an effective solution for the existing critical blue-light host material, and can greatly promote the development of the field of blue-light host materials.
Drawings
FIG. 1 is an excitation and emission spectrum of a dichloromethane solution of the compound BO1 at room temperature and a 2-methyltetrahydrofuran solution thereof at 77K;
FIG. 2 is an excitation and emission spectrum of a dichloromethane solution of the compound BO77 at room temperature and a 2-methyltetrahydrofuran solution thereof at 77K;
FIG. 3 is an emission spectrum of a dichloromethane solution of the compound BO80 at room temperature and a 2-methyltetrahydrofuran solution thereof at 77K.
Detailed Description
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:
Figure BDA0002082607600000101
it is understood to be equivalent to the following formula:
Figure BDA0002082607600000102
where n is typically an integer. Namely, RnIs understood to mean five individual substituents Rn(a)，Rn(b)，Rn(c)，Rn(d)，Rn (e). By "individual substituents" is meant that each R substituent can be independently defined. For example, if atIn one case Rn(a)Is halogen, then in this case Rn(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.
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 500MHz in solution1H NMR spectrum, recorded at 125MHz13C 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 CDCl3(δ 77.00 ppm) is reported as an internal standard13C NMR spectrum. If DMSO-d6As a solvent, tetramethylsilane (δ ═ 0.00ppm) was used as an internal standard for recording1H 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, m is multiplet, br is broad.
The compounds of the present invention may be prepared by a variety of methods by the relevant person, including, but not limited to, those methods enumerated in the examples provided herein.
General synthetic route
The general synthetic route for the compounds disclosed in the present patent is as follows:
Figure BDA0002082607600000111
Figure BDA0002082607600000121
wherein R isa、Rb、Rc、RdAnd ReEach independently hydrogen, deuterium, alkyl, alkoxy, cycloalkyl, ether, heterocyclyl, phenyl, aryloxy, halogen, cyano, or combinations thereof; m is an integer of 0 to 5; n is an integer of 0 to 4.
Preparation examples
Example 1: compound BO1 can be synthesized as follows:
Figure BDA0002082607600000122
to a dry three-necked flask with a magnetic rotor were added sequentially p-diiodobenzene (6.7327g, 20mmol, 98%, 1.0 equiv.), 2-methoxyphenylboronic acid (6.8245g, 44mmol, 98%, 2.2 equiv.), palladium acetate (0.2245g, 1mmol, 0.05 equiv.) and ligand S-Phos (1.0053g, 2.4mmol, 98%, 0.12 equiv.). Nitrogen was purged three times, followed by addition of an aqueous solution (30mL) of 1, 4-dioxane (90mL) and potassium carbonate (13.8200g, 100mmol, 5.0 equiv.) under nitrogen. The three-necked bottle was then placed in a 105 ℃ 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 (30 mL. times.2). All organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated and the crude product recrystallized from ethyl acetate to give A1 as a pale gray solid 5.1635g, 89% yield.1H NMR(500MHz，DMSO)δ7.50(s，4H)，7.38-7.31(m，4H)，7.13(d，J＝7.7Hz，2H)，7.05(t，J＝7.4Hz，2H)，3.79 (s，6H)。
Figure BDA0002082607600000131
To a dry three-necked flask with a magnetic rotor was added A1(0.8712g, 3mmol, 1.0 equiv.), in that order, o-xylene (40 mL). 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 24 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. The mixture was concentrated, and the crude product was recrystallized from n-hexane/dichloromethane to obtain BO1 as a white solid (1.2917 g, 83% yield).1H NMR(500MHz，CDCl3) δ8.74(s，2H)，8.20(dd，J＝8.1，1.4Hz，2H)，7.55(dd，J＝8.1，1.2Hz，2H)，7.47(t，J＝7.6Hz，2H)， 7.31(t，J＝7.6Hz，2H)，7.01(s，4H)，2.43(s，6H)，2.25(s，12H)。
FIG. 1 shows the excitation and emission spectra of a solution of the compound BO1 in methylene chloride at room temperature and of a solution of it in 2-methyltetrahydrofuran at 77K. The peak value of an emission spectrum at room temperature is 408nm and is in a visible light region; the peak value of the emission spectrum with the highest 77K level is 475nm, so that the triplet state energy level can be calculated to be up to 2.61eV, and the material can be used as a green light host material.
Example 2: compound BO77 can be synthesized as follows:
Figure BDA0002082607600000132
to a dry three-necked flask with a magnetic rotor were added 1, 4-dibromo-2, 5-dimethoxybenzene (4.5773g, 15mmol, 97%, 1.0 equiv.), phenylboronic acid (4.1048g, 33mmol, 98%, 2.2 equiv.), palladium acetate (0.1010g, 0.45mmol, 0.03 equiv.) and ligand S-Phos (0.3770g, 0.9mmol, 98%, 0.06 equiv.) in that order. Nitrogen was purged three times, followed by addition of an aqueous solution (30mL) of 1, 4-dioxane (90mL) and potassium carbonate (10.3650g, 75mmol, 5.0 equiv.) under nitrogen. The three-necked flask was then placed in a 110 ℃ 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 (30 mL. times.2). All organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated and the crude product recrystallized from n-hexane/dichloromethane to give A2 as a white solid 5.1132g, 88% yield.1H NMR(500MHz，DMSO)δ7.56(d，J＝7.8Hz，4H)，7.43(t，J＝7.6Hz，4H)，7.34(t，J＝7.4Hz， 2H)，7.03(s，2H)，3.76(s，6H)。
Figure BDA0002082607600000141
To a dry three-necked flask with a magnetic rotor were added A2(0.8712g, 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,the three-necked bottle was then placed in a 75 ℃ oil bath. After stirring for 24 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. Concentration, recrystallization of the crude product from n-hexane/dichloromethane gave BO77 as a pink solid 1.3079g, 84% yield.1H NMR (500MHz，CDCl3)δ8.44(s，2H)，8.33(d，J＝8.1Hz，2H)，7.82(t，J＝8.6Hz，4H)，7.48(t，J＝7.3 Hz，2H)，7.25(s，1H)，6.96(s，4H)，2.38(s，6H)，2.23(s，12H)。
FIG. 2 shows the excitation and emission spectra of a solution of the compound BO77 in methylene chloride at room temperature and of a solution of it in 2-methyltetrahydrofuran at 77K. The peak value of an emission spectrum at room temperature is 376nm and is positioned in an ultraviolet light region; the peak value of the emission spectrum with the highest 77K level is 478nm, so that the triplet state energy level can be calculated to be up to 2.59eV, and the material can be used as a green light and red light main body material.
Example 3: compound BO80 can be synthesized as follows:
Figure BDA0002082607600000142
to a dry three-necked flask with a magnetic rotor were added 1, 4-dibromo-2, 5-dimethoxybenzene (3.0515g, 10mmol, 97%, 1.0 equiv.), 4-methylbenzeneboronic acid (3.0531g, 22mmol, 98%, 2.2 equiv.), palladium acetate (0.0674g, 0.3 mmol, 0.03 equiv.) and ligand S-Phos (0.2513g, 0.6mmol, 98%, 0.06 equiv.) in that order. Nitrogen was purged three times, followed by addition of an aqueous solution (20mL) of 1, 4-dioxane (60mL) and potassium carbonate (6.9100g, 50mmol, 5.0 equiv.) under nitrogen. The three-necked bottle was then placed in a 100 ℃ oil bath. After stirring for 19 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 (30 mL. times.2). All organic phases were combined, dried over anhydrous sodium sulfate, filtered, concentrated and the crude product recrystallized from n-hexane/dichloromethane to give A3 as a white solid 3.0051g, 94% yield.1H NMR(500MHz，DMSO)δ7.45(d，J＝8.1Hz，4H)，7.23(d，J＝7.9Hz，4H)，6.98(s，2H)， 3.74(s，6H)，2.35(s，6H)。
Figure BDA0002082607600000151
To a dry three-necked flask with a magnetic rotor were added A3(0.9552g, 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 25 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 17 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. The mixture was concentrated, and the crude product was recrystallized from n-hexane/dichloromethane to obtain BO80 as a white solid (1.4098 g, 85% yield).1H NMR(500MHz，CDCl3)δ8.38(s，2H)，8.22(d，J＝8.1Hz，2H)，7.67-7.58(m，4H)，6.97(s， 4H)，2.41(s，6H)，2.39(s，6H)，2.23(s，12H)。
FIG. 3 is an emission spectrum of a dichloromethane solution of the compound BO80 at room temperature and a 2-methyltetrahydrofuran solution thereof at 77K. The peak value of an emission spectrum at room temperature is 364nm and is positioned in an ultraviolet light region; the peak of the emission spectrum with the highest 77K level is 446nm, from which its triplet level can be calculated as up to 2.78eV, as a crash and green host material.
Performance evaluation examples
The bisboroxadibenzo [ a, H ] anthracene derivatives 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 are aerated with nitrogen5 minutes; the triplet state lifetime measurements were all measured at the most intense peak of the sample emission spectrum.
Electrochemical analysis: the test was carried out using cyclic voltammetry 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.
The structures of the diboron oxadibenzo [ A, H ] anthracene derivatives prepared in examples 1-3 above and the control are shown below.
Figure BDA0002082607600000161
TABLE 1 photophysical properties and thermogravimetric analysis data of Bisborooxadibenzo [ A, H ] anthracene derivative materials
Figure BDA0002082607600000162
Note: peak refers to diboronoxydibenzo [ A, H ]]The most intense emission peak of the room temperature emission spectrum of the anthracene derivative material. PLQY refers to absolute luminescence quantum efficiency. Biboroxodibenzo [ A, H ]]The room temperature emission spectrum of the anthracene 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 bisboroxadibenzo [ A, H ] anthracene derivative materials in dichloromethane solution at room temperature, and in 2-methyltetrahydrofuran (2-Me-THF) at 77K, see FIGS. 1-3.
TABLE 2 photophysical property data of thin film devices using diboron-oxapyrene derivatives as blue and deep blue host materials
Figure BDA0002082607600000171
The structure of the blue light material PtON1 is as follows:
Figure BDA0002082607600000172
as can be seen from FIGS. 1-3 and Table 1: first, the diboron-oxadibenzo [ A, H ] provided by the invention]The anthracene derivative materials have high luminescent quantum efficiency (PLQY) which can reach 45.8-62.1% and is 1.8-2.4 times of that of a reference substance; and all show short excited state lifetimes (1.45-4.42ns), all in nanoseconds (ns, 10)-9Seconds) order of magnitude. Secondly, the thermal decomposition temperature and the glass transition temperature are high, for example, the thermal decomposition temperature of BO80 is more than 100 degrees higher than that of the control, and the glass transition temperature is nearly 2 times higher than that of the control. Tris, diborono-dibenzo [ A, H ]]The anthracene derivative has various structures and is easy to modify, so that the anthracene derivative has an easily-adjusted 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 BO1 and BO77 are between 2.59-2.61eV and can be used as host materials for red and green emitters; whereas BO80 has a very high triplet energy level (2.78eV) and can be used as host material for blue emitters. These properties make the derivatives of the present invention useful as light emitting materials or host materials in optical or electro-optical devices, including photosensitive devices, organic light emitting diodes, light emitting devices, and devices capable of compatible light absorption and emission. As shown in Table 2, the absolute quantum efficiencies of the thin film devices using BO80 as the host material are all as high as 78.3%, which shows that the efficient energy transfer from the host to the guest occurs in the excited state, and BO80 is shown as the host for blue lightBulk materials are fully feasible. Provides an effective solution for the current critical blue light host material, thereby greatly promoting the development of the field.
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 (3)

1. A diboron oxadibenzo [ A, H ] anthracene derivative, characterized in that the structural formula of the derivative is shown as (I), (II):
Figure FDA0002803868030000011
wherein R isaIs alkyl, alkoxy, cycloalkyl; rb、Rc、RdAnd ReEach independently hydrogen, deuterium, alkyl, alkoxy, cycloalkyl, phenyl, aryloxy, 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 4.
2. Use of the derivative of claim 1 as a host material in an optical or optoelectronic device.
3. Use according to claim 2, wherein the optical or optoelectronic device comprises a light sensing device, an organic light emitting diode light emitting device and a device compatible with light absorption and emission.
CN201910478956.5A 2019-06-03 2019-06-03 Biboroxadibenzo [ A, H ] anthracene derivatives and application thereof Active CN110272441B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910478956.5A CN110272441B (en) 2019-06-03 2019-06-03 Biboroxadibenzo [ A, H ] anthracene derivatives and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910478956.5A CN110272441B (en) 2019-06-03 2019-06-03 Biboroxadibenzo [ A, H ] anthracene derivatives and application thereof

Publications (2)

Publication Number Publication Date
CN110272441A CN110272441A (en) 2019-09-24
CN110272441B true CN110272441B (en) 2021-01-29

Family

ID=67961922

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910478956.5A Active CN110272441B (en) 2019-06-03 2019-06-03 Biboroxadibenzo [ A, H ] anthracene derivatives and application thereof

Country Status (1)

Country Link
CN (1) CN110272441B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112225752B (en) * 2020-11-11 2023-01-06 浙江虹舞科技有限公司 Centrosymmetric type double-boron oxapolycyclic aromatic compound luminescent material and application thereof
CN112442057B (en) * 2020-11-19 2022-07-08 浙江工业大学 Deep blue light luminescent material containing plane-symmetric type bisboroxapolycyclic aromatic compound

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3417123A (en) * 1965-10-22 1968-12-17 Mobil Oil Corp Heteroaromatic boron compounds and their preparation
US3389123A (en) * 1965-10-22 1968-06-18 Mobil Oil Corp Compositions stabilized with cyclic boron compounds
US3532626A (en) * 1966-07-29 1970-10-06 Mobil Oil Corp Lubricant compositions
KR20090008736A (en) * 2007-07-18 2009-01-22 제일모직주식회사 Aza-/oxa-boraphenanthrene derivatives for organic electroluminescent device thereby

Also Published As

Publication number Publication date
CN110272441A (en) 2019-09-24

Similar Documents

Publication Publication Date Title
CN107089990B (en) It is a kind of using fluorenes as the organic compound of core and its application on organic electroluminescence device
KR20090073928A (en) Organic electroluminescent compounds and organic light emitting diode using the same
CN110183475B (en) Biboroxapyrene compound based on donor-acceptor and application thereof
CN107602542A (en) A kind of organic compound containing dibenzo hexatomic ring and its application
CN109824684A (en) A kind of Spirofluorene derivative species organic compound and its application on organic electroluminescence device
CN110272441B (en) Biboroxadibenzo [ A, H ] anthracene derivatives and application thereof
CN106883218A (en) A kind of organic compound with equal benzene as core and its application on organic electroluminescence device
US11515488B2 (en) Thermally activated delayed fluorescence material having red, green, or blue color, synthesis method thereof, and application thereof
CN110305063B (en) Heat-activated delayed fluorescence blue light material, and synthesis method and application thereof
CN114249759B (en) Boron-doped Z-acene derivative and preparation method and application thereof
CN110183476B (en) Biboroxadibenzo [ A, J ] anthracene derivatives and application thereof
CN107602397A (en) A kind of compound and its application using dibenzocycloheptene as core
CN111454279A (en) Organic electroluminescent compound and preparation method and application thereof
JP2022513608A (en) Organic electroluminescence material and its preparation method and organic electroluminescence device
CN113149864B (en) Synthesis and application of thermal activity delay fluorescent material based on indeno [2,1-a ] indene condensed ring unit
CN108218853A (en) It is a kind of using the nitrogenous hexa-member heterocycle of dibenzo as the compound of core and its application on organic electroluminescence device
CN113201026B (en) Four-tooth ring metal platinum (II) or palladium (II) complex luminescent material based on donor-acceptor structure and application thereof
CN111808097B (en) Solvent yellow 184 derivative and preparation method and application thereof
CN112174959B (en) Organic luminescent material based on 1,6-naphthyridine receptor structural unit and application thereof
CN116120350A (en) Boron-nitrogen compound and preparation method and application thereof
CN116120349A (en) Boron-nitrogen compound and preparation method and application thereof
CN107868037A (en) A kind of organic compound containing fluorenes and its application
CN111675709B (en) Fluorescent material and synthetic method thereof
CN113897193B (en) Blue luminescent material based on dibenzofuran derivatives
CN116947905A (en) Boron-nitrogen compound and preparation method and application thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant