CN105418679A - Triphenylphosphine oxide unit bridged bipolar host material and application thereof - Google Patents
Triphenylphosphine oxide unit bridged bipolar host material and application thereof Download PDFInfo
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- CN105418679A CN105418679A CN201510725758.6A CN201510725758A CN105418679A CN 105418679 A CN105418679 A CN 105418679A CN 201510725758 A CN201510725758 A CN 201510725758A CN 105418679 A CN105418679 A CN 105418679A
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- host material
- triphenylphosphine oxide
- bipolar host
- oxide unit
- xanthene
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- 239000000463 material Substances 0.000 title claims abstract description 62
- FIQMHBFVRAXMOP-UHFFFAOYSA-N triphenylphosphane oxide Chemical group C=1C=CC=CC=1P(C=1C=CC=CC=1)(=O)C1=CC=CC=C1 FIQMHBFVRAXMOP-UHFFFAOYSA-N 0.000 title claims abstract description 20
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims description 25
- 239000004327 boric acid Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- -1 aromatic ring boric acid ester Chemical class 0.000 claims description 5
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 abstract description 4
- 230000005525 hole transport Effects 0.000 abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 3
- QFUPJXCUNNWZJQ-UHFFFAOYSA-N 2-bromofluoren-1-one Chemical compound C1=CC=C2C3=CC=C(Br)C(=O)C3=CC2=C1 QFUPJXCUNNWZJQ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000006069 Suzuki reaction reaction Methods 0.000 abstract description 2
- 238000007363 ring formation reaction Methods 0.000 abstract description 2
- QQNLHOMPVNTETJ-UHFFFAOYSA-N spiro[fluorene-9,9'-xanthene] Chemical group C12=CC=CC=C2OC2=CC=CC=C2C11C2=CC=CC=C2C2=CC=CC=C21 QQNLHOMPVNTETJ-UHFFFAOYSA-N 0.000 abstract 3
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 abstract 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 24
- 238000010025 steaming Methods 0.000 description 12
- 150000002220 fluorenes Chemical class 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 8
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 238000000605 extraction Methods 0.000 description 6
- 239000011368 organic material Substances 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
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- 239000007924 injection Substances 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- DHNRAGGXWCCERB-UHFFFAOYSA-N [O].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 Chemical group [O].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 DHNRAGGXWCCERB-UHFFFAOYSA-N 0.000 description 3
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 241001597008 Nomeidae Species 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 238000001840 matrix-assisted laser desorption--ionisation time-of-flight mass spectrometry Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- MYTWGZHEZWIILW-UHFFFAOYSA-N 1-bromo-9-ethylcarbazole Chemical compound C1=CC(Br)=C2N(CC)C3=CC=CC=C3C2=C1 MYTWGZHEZWIILW-UHFFFAOYSA-N 0.000 description 1
- YOXUOHDHFCBGHY-UHFFFAOYSA-N 1-bromofluoren-9-one Chemical compound C12=CC=CC=C2C(=O)C2=C1C=CC=C2Br YOXUOHDHFCBGHY-UHFFFAOYSA-N 0.000 description 1
- QRVQUBKLRBKFCG-UHFFFAOYSA-N 1-phenylpyrene Chemical compound C1=CC=CC=C1C1=CC=C(C=C2)C3=C4C2=CC=CC4=CC=C13 QRVQUBKLRBKFCG-UHFFFAOYSA-N 0.000 description 1
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 1
- LTBWKAYPXIIVPC-UHFFFAOYSA-N 3-bromo-9h-carbazole Chemical compound C1=CC=C2C3=CC(Br)=CC=C3NC2=C1 LTBWKAYPXIIVPC-UHFFFAOYSA-N 0.000 description 1
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 description 1
- COVZYZSDYWQREU-UHFFFAOYSA-N Busulfan Chemical compound CS(=O)(=O)OCCCCOS(C)(=O)=O COVZYZSDYWQREU-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- IVDFJHOHABJVEH-UHFFFAOYSA-N HOCMe2CMe2OH Natural products CC(C)(O)C(C)(C)O IVDFJHOHABJVEH-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 150000001454 anthracenes Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- RJCQBQGAPKAMLL-UHFFFAOYSA-N bromotrifluoromethane Chemical compound FC(F)(F)Br RJCQBQGAPKAMLL-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
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- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- XTLNYNMNUCLWEZ-UHFFFAOYSA-N ethanol;propan-2-one Chemical compound CCO.CC(C)=O XTLNYNMNUCLWEZ-UHFFFAOYSA-N 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- MRNHPUHPBOKKQT-UHFFFAOYSA-N indium;tin;hydrate Chemical compound O.[In].[Sn] MRNHPUHPBOKKQT-UHFFFAOYSA-N 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- KYKLWYKWCAYAJY-UHFFFAOYSA-N oxotin;zinc Chemical compound [Zn].[Sn]=O KYKLWYKWCAYAJY-UHFFFAOYSA-N 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- LFGREXWGYUGZLY-UHFFFAOYSA-N phosphoryl Chemical group [P]=O LFGREXWGYUGZLY-UHFFFAOYSA-N 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 229920002098 polyfluorene Polymers 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
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- 238000001953 recrystallisation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000010186 staining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 239000012780 transparent material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/6558—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system
- C07F9/65586—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom containing at least two different or differently substituted hetero rings neither condensed among themselves nor condensed with a common carbocyclic ring or ring system at least one of the hetero rings does not contain nitrogen as ring hetero atom
-
- 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
- H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Electroluminescent Light Sources (AREA)
Abstract
The present invention discloses a triphenylphosphine oxide unit bridged bipolar host material and an application thereof. Firstly, a spiro-[fluorene-9,9'-xanthene] structure is prepared by a cyclization reaction between 2-bromo-fluorenone and phenol, by two steps of Suzuki reaction, carbazole and spiro-[fluorene-9,9'-xanthene] is introduced on a triphenylphosphine oxide structure to obtain a target product SFOPO-Cz. According to the material disclosed by the present invention, the material has the spiro-[fluorene-9,9'-xanthene] group; properties of fluorene of wide energy gap and high luminous efficiency can be fully used; meanwhile, the carbazole group having good hole transporting property is adopted as a hole transport unit; the triphenylphosphine oxide group having strong electron transporting ability is adopted as an electron transport unit; so that implementation of carrier transporting balance is facilitated. A device which is designed and prepared by the material has the advantages of high efficiency, high stability and relatively small efficiency roll-off, and has excellent potential for being a new generation of an electroluminescent phosphor host material.
Description
Technical field
The present invention relates to bipolar host material and the application thereof of triphenylphosphine oxide unit bridging.
Background technology
Organic electroluminescent phenomenon is developed so far the history of existing nearly 50 years.Its plurality of advantages had is expected to as technique of display of future generation.As everyone knows, organic electroluminescence device (OLEDs) further develops and the basis of large-scale commercial and key are luminous organic materials, especially high-performance, the three primary colours luminous organic material of low cost.At present, red, green luminous organic material research has been tending towards ripe, substantially meets commercialization demand.And require wide can system, high stability, high performance blue light material progress unsatisfactory.Because the luminous efficiency of blue light material is low, work-ing life is shorter, the effect of full-color display and the exploitation of commercially produced product are had a strong impact on.
In recent years, the luminescent layer of phosphorescence Organic Light Emitting Diode is owing to passing through host-guest system, on internal quantum efficiency, theory can reach 100%, and can the gathering quencher of effective Fluorophotometry, the photoluminescence efficiency of boost device, purity of color and device lifetime, and become the study hotspot of electroluminescent device.The material of main part of design and synthesis high triplet energy level, wide energy gap, high-performance and high stability also becomes learns one of patient's study hotspot at present.The derivative of anthracene, few fluorenes, few quinoline, tetraphenyl silicomethane, two pyrenyl benzene etc. are reported in succession as OLEDs material of main part.But find one and have high stability, high device efficiency, high color purity, the electroluminescent material of main part of high triplet energy level and wide energy gap still needs to be studied further.Fluorenes and derivative thereof become the star molecule in electroluminescent organic material, mainly due to the feature such as energy gap and high luminous efficiency that fluorenes is wider.But the electron affinity of fluorenes is little, and the solvability of polyfluorene is limited, 9 carbon atoms of fluorenes become carbonyl than being easier to oxidation again, and carbonyl easily forms " trap " to the exciton produced by electron-hole recombination and have certain " quencher " effect, finally can reduce the luminous efficiency of device.In order to the feature of the wide energy gap and high luminous efficiency that make full use of fluorenes, suppress 9 carbon atoms oxidations, by design and synthesis, the structure of spiral shell [anthracene-9,9 '-fluorenes] just effectively can utilize the advantage of fluorenes.And in recent years, the electroluminescent material based on phosphorus oxide structure has attracted the attention of large quantities of scholar, can effectively hinder phenyl ring electron conjugated mainly due to triphenylphosphine oxide derivant structure; Itself can promote the electronic transmission performance of material again to some extent as electron-withdrawing group.And triphenylphosphine oxide derivant structure presents down three-dimensional configuration in space, molecular aggregates when this form can effectively stop solid-state, improves the thermostability of material, and effectively can suppress formation and the quenching of fluorescence of exciton.Based on the material of this structure at blue-fluorescence, material of main part, Subjective and Objective mixes up material of main part, and hybrid agent material and the luminescence of single Subjective and Objective wait application much existing.And the device of a superior performance will be prepared, reach high balanced charge transport, high current efficiency, device architecture is simple, and material of main part is key point.
Summary of the invention
The object of the invention is the bipolar host material providing a kind of triphenylphosphine oxide unit bridging, can be applied to organic electro phosphorescent device.
The present invention is by the following technical solutions:
The bipolar host material of triphenylphosphine oxide unit bridging, the general structure of this bipolar host material is as follows:
Wherein, X, Y and Z are all the one in hydrogen, carbazole or spiral shell [fluorenes-9,9 '-xanthene], and are that monosubstituted, two replacement or three replaces, and X, Y and Z replacement mode on phenyl ring has ortho position to replace and para-orientation.
As preferably, the structural formula of this bipolar host material is as follows:
Above-claimed cpd SFOPO-Cz take triphenylphosphine oxide as structural framework, introduces carbazole and spiral shell [fluorenes-9,9 '-xanthene], has bipolarity feature.First utilize the bromo-Fluorenone of 2-and phenol to be reacted by cyclization and prepare spiral shell-[fluorenes-9,9 '-xanthene] structure, by two step Suzuki reactions, triphenyl phosphorus oxide structure is introduced carbazole and spiral shell-[fluorenes-9,9 '-xanthene] thus obtains target product SFOPO-Cz.This material has spiral shell-[fluorenes-9,9 '-xanthene] group, the feature such as wide energy gap and high luminous efficiency of fluorenes can be made full use of, adopt the carbazole group that hole transport performance is strong as hole transporting unit simultaneously, adopt the strong triphenylphosphine oxygen groups of electron transport ability to be electric transmission unit, thus be of value to and realize balanced charge transport.
As preferably, this material of main part is obtained by the Suzuki linked reaction between the halogen on the phenyl ring different positions of electrophilic triphenylphosphine and aromatic ring boric acid ester.
The guest materials compound that the bipolar host material of described triphenylphosphine oxide unit bridging mates with its triplet is mixed up as the application of luminescent layer in organic electro phosphorescent device.
The application of bipolar host material in high efficiency electroluminous diode of described triphenylphosphine oxide unit bridging.
The invention has the beneficial effects as follows:
1) triphenylphosphine oxygen groups can form space tetrahedral structure, and effectively hinder the conjugation of phenyl ring, intermolecular heap sum crystallization, enhances the rigidity of molecule, add the stability after film forming.The synthesis of triphenylphosphine oxygen groups is simple, and structural modification is strong, has stronger electron transport ability.
2) adopt the carbazole group that hole transport performance is strong as hole transporting unit, contribute to the cavity transmission ability improving material.
3) introduce spiral shell-[fluorenes-9,9 '-xanthene] group, not only overcome some defects that fluorenes itself exists, can also fluorenes be made full use of
The feature such as wide energy gap and high luminous efficiency.
Accompanying drawing explanation
Fig. 1 is the uv-absorbing of compound S FOPO-Cz under methylene dichloride and filminess and fluorescence emission spectrogram.
Fig. 2 is the phosphorescence emission spectra figure of compound S FOPO-Cz under 77K low temperature.
Fig. 3 is compound S FOPO-Cz redox electrochemical profiles figure.
The different I r (ppy) that Fig. 4 is is material of main part with compound S FOPO-Cz
3current density-luminance-voltage the working curve diagram of doping concentration electro phosphorescent device.
The different I r (ppy) that Fig. 5 is is material of main part with compound S FOPO-Cz
3current efficiency-Brightness Duty the graphic representation of doping concentration electro phosphorescent device.
The different I r (ppy) that Fig. 6 is is material of main part with compound S FOPO-Cz
3external quantum efficiency-Brightness Duty the graphic representation of doping concentration electro phosphorescent device.
The different I r (ppy) that Fig. 7 is is material of main part with compound S FOPO-Cz
3the electroluminescent spectrum figure of doping concentration electro phosphorescent device.
The different I r (pq) that Fig. 8 is is material of main part with compound S FOPO-Cz
2(acac) current density-luminance-voltage working curve diagram of doping concentration electro phosphorescent device.
The different I r (pq) that Fig. 9 is is material of main part with compound S FOPO-Cz
2(acac) current efficiency-Brightness Duty graphic representation of doping concentration electro phosphorescent device.
The different I r (pq) that Figure 10 is is material of main part with compound S FOPO-Cz
2(acac) external quantum efficiency-Brightness Duty graphic representation of doping concentration electro phosphorescent device.
The different I r (pq) that Figure 11 is is material of main part with compound S FOPO-Cz
2(acac) the electroluminescent spectrum figure of doping concentration electro phosphorescent device.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail.
The synthesis of embodiment 1:SFOPO-Cz
The synthesis of compound 2-bromine spiral shell [fluorenes-9,9 '-xanthene]
By methanesulfonic (2.14mL, 24.4mmol), the bromo-9-Fluorenone (6g, 24.63mmol) of 2-and phenol (23.15g, 246.3mmol) add in two mouthfuls of flasks.At N after pump drainage 3 times
2in atmosphere, at 150 DEG C of temperature, react 8h.Reaction substrate shrend is gone out, and uses MgSO with after dichloromethane extraction three times
4dry.Pure product 6.1g (60%) is obtained through tlc analysis.
1H-NMR(400MHz),CDCl
3,δ:δ7.78(s,1H),δ7.66(s,1H),δ7.50(s,1H),δ7.38(m,1H),δ7.3-7.15(m,7H),δ6.79(m,2H),δ6.40(s,2H).
The synthesis of two (4-bromobenzene) (phenyl) phosphine oxygen of compound
First at N
2under atmosphere, in twoport flask, Isosorbide-5-Nitrae-dibromobenzene (4.72g, 20mmol) is dissolved in the tetrahydrofuran solvent dewatered of 140ml.At-78 DEG C of temperature, 1.6mol/L n-Butyl Lithium (11.865mL, 19mmol) is dropwise added.After reaction 2h, add 1.26mL (9.3mmol) phenyl dichloro phosphorus, reaction is spent the night.Substrate, with after dichloromethane extraction three times, uses MgSO
4dry.Afterwards solution is removed completely, dissolve with methylene dichloride (60ml) and add H
2o
2(30ml) stirring is spent the night afterwards.Pure product 3.30g (81%) is obtained through tlc analysis after final substrate dichloromethane extraction and drying.1H-NMR(400MHz),CDCl
3,δ:7.68-7.58(m,6H),7.58-7.45(m,7H).
The bromo-9-ethyl carbazole of compound 3-
By 3-bromine carbazole (13g, 40mmol), bromotrifluoromethane (5.24g, 40mmol), potassium hydroxide (6.72g, 120mmol) and 120ml dimethyl sulfoxide (DMSO) join in twoport flask.Pump drainage three times, at N
2in atmosphere, stir 24 hours under 50 DEG C of conditions.Treat that temperature is down to room temperature, add appropriate shrend and go out, and with dichloromethane extraction repeatedly.After the organic solution aqueous hydrochloric acid obtained washs three times, use anhydrous magnesium sulfate drying organic solution.Organic solvent is removed, the solid crude product recrystallization in ethanol of acquisition by Rotary Evaporators.The white pure products 16.03g (89%) of final acquisition.
1hNMR (400MHz), CDCl
3, δ 8.25-8.20 (d, 1H), 8.10-8.00 (d, 1H), 7.60-7.45 (m, 2H), 7.43-7.35 (d, 1H), 7.30-7.20 (m, 2H), 4.35-4.25 (m, 2H), the synthesis of 1.50-1.35 (t, 3H) .3-pinacol boric acid ester 9-ethyl carbazole and the synthetic method of 2-pinacol boric acid ester spiral shell [fluorenes-9,9 '-xanthene] similar.
Compound 2-pinacol boric acid ester spiral shell [fluorenes-9,9 '-xanthene]
2-bromine spiral shell [fluorenes-9 is added in single port bottle, 9 '-xanthene] (6g, 14.63mmol) after strict deoxygenation, be dissolved in 140mL anhydrous tetrahydro furan (existing steaming dewaters) under ice bath (0 DEG C), after dissolving completely, n-Butyl Lithium (the 11.2ml of slow dropping 1.6mol/L, 17.56mmol), stir 30 minutes, after adding Virahol pinacol boric acid ester (6.1ml, 30.4mmol), reactive bath technique temperature is warmed up to room temperature gradually by 0 DEG C, reacts 12 hours.Add water after reaction terminates quencher, with dichloromethane extraction, is that chromatography column crossed by the ethyl acetate of 1:2 and the mixed solvent of sherwood oil, obtains solid, productive rate 50% by volume ratio.
1HNMR(400MHz,CDCl
3,ppm):δ7.90-7.80(m,3H),7.58(s,1H),7.35(m,1H),7.25-7.10(m,6H),6.76(d,2H),6.37(d,2H),1.28(s,12H).MALDI-TOF:458.
The synthesis of compound S FOPO-Cz
By 2-pinacol boric acid ester spiral shell [fluorenes-9,9 '-xanthene] (1g, 2.18mmol), two (4-bromobenzene) (phenyl) phosphine oxygen (0.95g, 2.18mmol), four (triphenyl) phosphine palladium (0), saturated K
2cO
3the aqueous solution, toluene, Tetrabutyl amonium bromide adds in 100ml twoport flask, at N
2in atmosphere, react 2 days at 85 DEG C of temperature.Substrate dichloromethane extraction dissolves, and obtains pure product 0.52g (30.5%) after washing three times through tlc analysis.Above-mentioned product and 3-boric acid ester-9-Ethy-Carbazole (0.23g, 0.73mmol) just can be obtained target compound SFOPO-Cz according to same Suzuki linked reaction step,
1h-NMR (400MHz), CDCl
3, δ: 8.33 (s, 1H), δ: 8.15-8.10 (d, 1H), δ: 7.94-7.34 (m, 22H), δ: 7.3-7.1 (m, 7H), δ: 6.82-6.75 (m, 2H), δ: 6.50-6.40 (d, 2H), δ: 4.45-4.35 (m, 2H), δ: 1.50-1.40 (m, 3H) .MALDI-TOF:803.3
Fig. 1-3 is is the uv-absorbing of compound S FOPO-Cz under methylene dichloride and filminess and fluorescence emission spectrum respectively, phosphorescence emission spectra under 77K low temperature and redox electrochemical profiles.
Material of main part involved in the present invention does not limit to above one, below two what enumerate is all the chemical structural formula of material of main part of the present invention:
Embodiment 2: the electro phosphorescent device taking SFOPO-Cz as material of main part
We use SFOPO-Cz as material of main part, with guest materials Ir (ppy)
3, Ir (pq)
2(acac) electroluminescent ruddiness and green device have been prepared in doping, and device architecture is: ITO/MoO
3/ CBP/EML/TPBi/LiF/Al, prepares the concrete steps of electroluminescent device:
(1) ITO electrode sheet glass is passed through clean-out system supersound process, then rinse in deionized water, then use acetone-ethanol (1:3) mixed solvent to carry out supersound process oil removing, be baked under clean environment and remove moisture completely, irradiate 10 minutes with ultraviolet rays cleaning machine;
(2) on above-mentioned ito glass plate, steaming crosses CBP layer as hole injection layer, and it is 0.1nm/s that speed is crossed in steaming, and it is 45nm that thickness is crossed in steaming;
(3) ito glass of the above-mentioned CBP of being coated with layer is placed in vacuum chamber, vacuumizes.
(4) luminous organic material SFOPO-Cz of the present invention and guest materials are crossed in steaming, and it is 0.1nm/s that speed is crossed in steaming, and it is 15nm that thickness is crossed in steaming;
(5) on luminescent layer, continue steaming and cross one deck TPBI as electron transfer layer, it is 0.1nm/s that speed is crossed in steaming, and it is 65nm that thickness is crossed in steaming;
(6) last, face on the electron transport layer, steams according to this and crosses LiF and Al layer, and as negative electrode, it is 0.1nm/s that speed is crossed in steaming, and steaming is crossed thickness and is respectively 0.7nm and 120nm.
By with triphenylphosphine oxide structure for core builds material frame, by introducing the carbazole group of high hole transport performance, the SFOPO-Cz of spiral shell [fluorenes-9,9 '-xanthene], as the research of the electroluminescent device performance of material of main part, obtains higher electroluminescent efficiency.According to Fig. 4 ~ Figure 11, green device maximum current efficiency reaches 52.8cd/A, and the highest external quantum efficiency reaches 14.1%; Red device maximum current efficiency reaches 18.2cd/A, and the highest external quantum efficiency reaches 11.1%.Compound S FOPO-Cz of the present invention is applied in electroluminescent device, has high brightness, high-luminous-efficiency, the features such as little and Heat stability is good of roll-offing.
Embodiment 3: electroluminescent organic material is preparing the application in electroluminescent device
Compound of the present invention can be used as electroluminescent material and prepare electroluminescent device, especially may be used for the active coating of electroluminescent device.So-called active coating is exactly can be luminous or have the organic thin film layer of electric charge note, transmission performance under certain driving voltage.Active coating can be hole transmission layer, organic luminous layer, electron transfer layer.Electroluminescent device is with one or more active coating.Compound of the present invention, as electroluminescent material, can preferably mix as luminescent layer with other staining agents.
The basic structure of organic electroluminescent is: substrate/anode/hole injection layer/hole transmission layer/hole blocking layer/organic luminous layer/electron transfer layer/electron injecting layer/negative electrode.
Substrate is organic or inorganic transparent material, is preferably glass here.
Anode material generally can adopt the metal oxides such as tin indium oxide (ITO), zinc tin oxide or zinc oxide, or is the metal of gold and silver, the contour merit culvert of copper, and we are preferred ITO and MoO
3as anode.
Hole injection layer and exciton barrier-layer are steam the CBP layer crossed, and thickness is 45nm;
In the present invention, electron injection and transport layer material are preferably TPBI;
Luminescent layer is described SFOPO-Cz doping Ir (ppy) of the present invention
3or Ir (pq)
2(acac) guest materials.
Cathode material generally adopts the low workfunction metal such as aluminium, magnesium, lithium, barium, calcium or they and copper, silver, golden alloy.Thickness of electrode is 10-2000nm.In further preferred embodiment, cathode material is chosen as aluminum metal successively.
Object of the present invention can as the object electroluminescent device preparing host-guest system.Preferred emitting device structure comprises ITO/MoO
3layer, CBP layer, luminescent layer, TPBI layer and LiF/Al layer.
The different I r (ppy) that Fig. 4-7 is is material of main part with compound S FOPO-Cz
3the working curve diagram of doping concentration electro phosphorescent device and spectrogram.
The different I r (pq) that Fig. 8-11 is is material of main part with compound S FOPO-Cz
2(acac) working curve diagram of doping concentration electro phosphorescent device and spectrogram.
The above; be only exemplary embodiment of the present invention; protection scope of the present invention is not limited thereto; anyly be familiar with within technical scope that those skilled in the art disclose in the present invention, obviously can obtain the simple change of technical scheme or equivalence and replace and all fall into protection scope of the present invention.
Claims (5)
1. the bipolar host material of triphenylphosphine oxide unit bridging, is characterized in that, the general structure of such bipolar host material is as follows:
，
Wherein, X, Y and Z are all the one in hydrogen, carbazole or spiral shell [fluorenes-9,9 '-xanthene], and X, Y and Z are monosubstituted, two replacement or three replacements, and X, Y and Z replacement mode on phenyl ring is that ortho position replaces or para-orientation.
2. the bipolar host material of triphenylphosphine oxide unit bridging according to claim 1, it is characterized in that, the structural formula of this bipolar host material is as follows:
。
3. the bipolar host material of triphenylphosphine oxide unit bridging according to claim 1, is characterized in that, this material of main part is obtained by the Suzuki linked reaction between the halogen on the phenyl ring different positions of electrophilic triphenylphosphine and aromatic ring boric acid ester.
4. the guest materials compound that the bipolar host material of triphenylphosphine oxide unit bridging according to claim 1 mates with its triplet is mixed up as the application of luminescent layer in organic electro phosphorescent device.
5. the application of bipolar host material in high efficiency electroluminous diode of triphenylphosphine oxide unit bridging according to claim 1.
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| CN107098931A (en) * | 2017-05-27 | 2017-08-29 | 南京邮电大学 | A kind of multi-functional amphipathic conjugated molecular material and preparation method and application |
| CN109336926A (en) * | 2018-10-23 | 2019-02-15 | 南京邮电大学 | Multi-functional luminous organic material of the one kind based on triphenylphosphine oxide and carbazole derivates |
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| CN107098931A (en) * | 2017-05-27 | 2017-08-29 | 南京邮电大学 | A kind of multi-functional amphipathic conjugated molecular material and preparation method and application |
| CN107098931B (en) * | 2017-05-27 | 2019-02-26 | 南京邮电大学 | Multi-functional amphipathic conjugated molecular material of one kind and the preparation method and application thereof |
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