CN110272441B - Biboroxadibenzo [ A, H ] anthracene derivatives and application thereof - Google Patents
Biboroxadibenzo [ A, H ] anthracene derivatives and application thereof Download PDFInfo
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- 150000001454 anthracenes Chemical class 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 50
- 230000003287 optical effect Effects 0.000 claims abstract description 11
- ZOCHARZZJNPSEU-UHFFFAOYSA-N diboron Chemical compound B#B ZOCHARZZJNPSEU-UHFFFAOYSA-N 0.000 claims abstract description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 230000031700 light absorption Effects 0.000 claims description 4
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 3
- 229910052805 deuterium Inorganic materials 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 230000005693 optoelectronics Effects 0.000 claims 2
- 230000009477 glass transition Effects 0.000 abstract description 5
- 238000002360 preparation method Methods 0.000 abstract description 5
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 5
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 abstract 1
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 24
- 239000000243 solution Substances 0.000 description 20
- 150000001875 compounds Chemical class 0.000 description 19
- 238000000295 emission spectrum Methods 0.000 description 19
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 12
- 229910052757 nitrogen Inorganic materials 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 description 10
- 238000000034 method Methods 0.000 description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 9
- HEDRZPFGACZZDS-MICDWDOJSA-N deuterated chloroform Substances [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 9
- 125000001424 substituent group Chemical group 0.000 description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 8
- 238000002411 thermogravimetry Methods 0.000 description 7
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- ILAHWRKJUDSMFH-UHFFFAOYSA-N boron tribromide Chemical compound BrB(Br)Br ILAHWRKJUDSMFH-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 239000012074 organic phase Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000004809 thin layer chromatography Methods 0.000 description 6
- 230000005284 excitation Effects 0.000 description 5
- 238000000695 excitation spectrum Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 230000005281 excited state Effects 0.000 description 4
- 229910052736 halogen Inorganic materials 0.000 description 4
- 150000002367 halogens Chemical class 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N DMSO-d6 Substances [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 3
- BBZUFTGDSAMCIV-UHFFFAOYSA-M [Br-].CC1=C(C(=C(C=C1)[Mg+])C)C Chemical compound [Br-].CC1=C(C(=C(C=C1)[Mg+])C)C BBZUFTGDSAMCIV-UHFFFAOYSA-M 0.000 description 3
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- VNFWTIYUKDMAOP-UHFFFAOYSA-N sphos Chemical compound COC1=CC=CC(OC)=C1C1=CC=CC=C1P(C1CCCCC1)C1CCCCC1 VNFWTIYUKDMAOP-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CHCLRVOURKGRSW-UHFFFAOYSA-N 1,4-dibromo-2,5-dimethoxybenzene Chemical compound COC1=CC(Br)=C(OC)C=C1Br CHCLRVOURKGRSW-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical group CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000007983 Tris buffer Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- -1 concentration Substances 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 125000002524 organometallic group Chemical group 0.000 description 2
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- 239000010409 thin film Substances 0.000 description 2
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 2
- ROEQGIFOWRQYHD-UHFFFAOYSA-N (2-methoxyphenyl)boronic acid Chemical compound COC1=CC=CC=C1B(O)O ROEQGIFOWRQYHD-UHFFFAOYSA-N 0.000 description 1
- BIWQNIMLAISTBV-UHFFFAOYSA-N (4-methylphenyl)boronic acid Chemical compound CC1=CC=C(B(O)O)C=C1 BIWQNIMLAISTBV-UHFFFAOYSA-N 0.000 description 1
- LFMWZTSOMGDDJU-UHFFFAOYSA-N 1,4-diiodobenzene Chemical compound IC1=CC=C(I)C=C1 LFMWZTSOMGDDJU-UHFFFAOYSA-N 0.000 description 1
- 101100481028 Arabidopsis thaliana TGA2 gene Proteins 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 239000011903 deuterated solvents Substances 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000001072 heteroaryl group Chemical group 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229940078552 o-xylene Drugs 0.000 description 1
- 239000000382 optic material Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000001296 phosphorescence spectrum Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000013558 reference substance Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000001757 thermogravimetry curve Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
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- 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
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
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- 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
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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
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):
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:
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:
it is understood to be equivalent to the following formula:
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:
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:
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)。
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:
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)。
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:
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)。
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.
TABLE 1 photophysical properties and thermogravimetric analysis data of Bisborooxadibenzo [ A, H ] anthracene derivative materials
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
The structure of the blue light material PtON1 is as follows:
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):
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.
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