CN107200752A - The aryl fluorenes steric hindrance type luminescent material of N diphenyl phosphorus oxygens carbazole 9 and preparation method - Google Patents
The aryl fluorenes steric hindrance type luminescent material of N diphenyl phosphorus oxygens carbazole 9 and preparation method Download PDFInfo
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- CN107200752A CN107200752A CN201710536845.6A CN201710536845A CN107200752A CN 107200752 A CN107200752 A CN 107200752A CN 201710536845 A CN201710536845 A CN 201710536845A CN 107200752 A CN107200752 A CN 107200752A
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- carbazole
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- 239000000463 material Substances 0.000 title claims abstract description 32
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- -1 aryl fluorenes Chemical class 0.000 title claims abstract description 7
- JPJGNZQDELRZGE-UHFFFAOYSA-N (phenyl-$l^{2}-phosphanyl)benzene Chemical compound C=1C=CC=CC=1[P]C1=CC=CC=C1 JPJGNZQDELRZGE-UHFFFAOYSA-N 0.000 title abstract 2
- 239000011368 organic material Substances 0.000 claims abstract description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 50
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 11
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 9
- 238000004440 column chromatography Methods 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 239000012074 organic phase Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000003599 detergent Substances 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000003208 petroleum Substances 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000012043 crude product Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- 230000004044 response Effects 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 5
- 125000000524 functional group Chemical group 0.000 claims description 5
- 239000012265 solid product Substances 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000007306 functionalization reaction Methods 0.000 claims description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 235000011089 carbon dioxide Nutrition 0.000 claims description 2
- 230000006837 decompression Effects 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 239000000047 product Substances 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims 4
- 239000007864 aqueous solution Substances 0.000 claims 1
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 claims 1
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims 1
- 235000011121 sodium hydroxide Nutrition 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 9
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 230000003335 steric effect Effects 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000004020 luminiscence type Methods 0.000 abstract description 3
- 239000000539 dimer Substances 0.000 abstract description 2
- 239000012769 display material Substances 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- ZJQCOVBALALRCC-UHFFFAOYSA-N 9-phenyl-9h-fluorene Chemical class C1=CC=CC=C1C1C2=CC=CC=C2C2=CC=CC=C21 ZJQCOVBALALRCC-UHFFFAOYSA-N 0.000 description 10
- 150000002220 fluorenes Chemical class 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000010791 quenching Methods 0.000 description 4
- 230000000171 quenching effect Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical class ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- PUFWGUZSDHANBX-UHFFFAOYSA-N 1-phenyl-9h-fluorene Chemical class C=12CC3=CC=CC=C3C2=CC=CC=1C1=CC=CC=C1 PUFWGUZSDHANBX-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000004455 differential thermal analysis Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000002411 thermogravimetry Methods 0.000 description 2
- YMTQRYMSWUKLIN-UHFFFAOYSA-N C1=CC=NC=C1.C1=CC=C2CC3=CC=CC=C3C2=C1 Chemical class C1=CC=NC=C1.C1=CC=C2CC3=CC=CC=C3C2=C1 YMTQRYMSWUKLIN-UHFFFAOYSA-N 0.000 description 1
- 208000033962 Fontaine progeroid syndrome Diseases 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- DBWGAXVWWNKFNI-UHFFFAOYSA-N [O].C1(=CC=CC=C1)[P]C1=CC=CC=C1 Chemical compound [O].C1(=CC=CC=C1)[P]C1=CC=CC=C1 DBWGAXVWWNKFNI-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical class C* 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000005669 field effect Effects 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 150000003413 spiro compounds Chemical class 0.000 description 1
- 238000004832 voltammetry Methods 0.000 description 1
Classifications
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- 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
- C07F9/553—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having one nitrogen atom as the only ring hetero atom
- C07F9/572—Five-membered rings
- C07F9/5728—Five-membered rings condensed with carbocyclic rings or carbocyclic ring systems
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- 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
- C07F9/65583—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 each of the hetero rings containing nitrogen as ring hetero atom
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- 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
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Abstract
The synthesis and its application of the luminous organic material of the aryl fluorenes steric hindrance type of N diphenyl phosphorus oxygens carbazole 9 are related to third generation luminescence display material and technology, the present invention is a kind of luminous organic material of the aryl fluorenes steric hindrance type of N diphenyl phosphorus oxygen carbazole/9, and specific design structure is as follows：Specifically related to preparation method, the application in organic light emitting diode device.The material has：(1) high triplet；(2) excellent luminous efficiency, high heat endurance and stable amorphous state；(3) three-dimensional large volume space steric effect can effectively suppress to be quenched and dimer is luminous；(4) synthetic method is simple and easy to apply.Blue organic electroluminescent device is prepared for using its preliminary structure as material of main part.Show that this kind of compound has broad application prospects and potential commercial value as material of main part in terms of phosphorescence Organic Light Emitting Diode.
Description
Technical field
Present invention relates particularly to based on by 9 hydroxyls of 9- hydroxyl -9- aryl fluorenes with N- diphenyl phosphorus oxygens carbazole substitute make
The preparation method of its functionalization, belongs to the technical field of luminous organic material preparation.
Background technology
In past many decades, phosphorescence Organic Light Emitting Diode (phosphorescent organic light-
Emitting devices, PhOLEDs) correlative study have been achieved for breakthrough progress.Phosphorescence Organic Light Emitting Diode
It is by Thompson and Forrest discoveries earliest.It can be swashed due to there is heavy metal spin-orbit cou-pling using singlet and triplet state
Son, makes its internal quantum efficiency to reach 100% in theory.With the conventional fluorescent organic light emission that internal quantum efficiency is 25%
Diode is compared, and phosphorescence Organic Light Emitting Diode (PhOLEDs) possesses bigger commercial application value, so be considered as most
Potential full-color display and solid state lighting technology.However, phosphorescent devices are because guest materials high concentration is quenched, triplet state is buried in oblivion
Lighted with dimer hinders it to develop always.In order to solve these problems, using host-guest system mechanism, make the organic hair of phosphorescence
Optical diode High Efficiency Luminescence.Therefore, design, to synthesize good material of main part most important to prepare high performance electrophosphorescenoleds device
's.Generally, in order that Energy Efficient is shifted between subject and object, the triplet of material of main part is higher than guest materials
Triplet, makes its effective recombination luminescence so as to which triplet excitons are limited in luminescent layer.In addition, for making
The material of main part of high-performance luminescent device must have high heat endurance and stable appearance.Although convention body material C BP
It is widely used for red-green glow phosphorescent devices, but its low glass transition temperature (Tg, 62 DEG C) and triplet
(2.56eV) causes device performance unstable.In order to solve the above problems, the material of main part mCP after improvement has high ET
(2.90eV) and be used to manufacture blue-light device.But still because of its relatively low glass transition temperature (Tg, 67 DEG C) and cause device
Performance is unstable.
Although the material of main part and its low concentration doping of many high triplet energy levels, heat endurance and stable appearance are efficient
The existing many reports of phosphorescent devices, but because the intrinsic concentration aggregation of phosphor material is quenched, high-concentration dopant, the phosphorus of excellent performance
Optical device and be rarely reported.High concentration aggregation quenching can effectively be suppressed using mechanism of doping effect, but its manufacture craft is more numerous
It is trivial, time-consuming.In addition, device performance further still increases element manufacturing difficulty, reduction device can because its concentration changes and changes
Repeatability, while improving producing cost.Obviously, spiro-compound conduct of the design synthesis with large volume space steric effect
Material of main part is one of effective ways for solving the above problems.In red-green-blue phosphorescent devices, blue phosphorescent device exists
Full-color display and the application of lighting field are vital.Therefore, synthesis has high triplet, heat endurance, shape
The material of main part of looks stability and large volume space steric effect is expected to prepare the phosphorescent devices of stability and high efficiency.It is hot steady in order to synthesize
The qualitative and higher material of main part of stable appearance makes device efficient light, and loop coil aromatic hydrocarbon is introduced into material of main part, not only may be used
High heat endurance and stable appearance is made it have with the interaction for controlling intermolecular π-π, and due to the three of its uniqueness
The conjugation blocking-up structure of dimension large volume steric hindrance makes it have high triplet.
N- diphenyl phosphorus oxygen carbazole/9- aryl fluorenes class luminescent materials have because with larger three dimensions steric effect
Stable amorphous state and high heat endurance, can effectively suppress concentration quenching of the object phosphor material under filminess and
Triplet state is buried in oblivion.In addition, fluorenes has higher triplet (2.95eV), by that can make it both to its 9- modification
There is appropriate triplet because of non-conjugated connection again with good photoelectric properties.The excellent suction of last diphenyl phosphorus oxygen
Characteristic electron causes N- diphenyl phosphorus oxygen carbazoles to have excellent electron injection/transmission characteristic, by with 9- sp of fluorenes3Hydridization carbon
Atom is connected so that each Guan Nengtuan had not only kept high triplet but also do not influenceed respective carrier transmission characteristics, by N- bis-
Phenyl phosphorus oxygen carbazole is connected with 9- aryl fluorenes so that the compound possesses bipolarity feature, so as to simplify device architecture, drop
Low cost.Based on this thought, the present invention with 9- hydroxyls -9- aryl fluorenes and N- diphenyl phosphorus oxygen carbazoles by friedel-crafts reaction, and
It is concisely and efficiently by hydrogen peroxide oxidation and is prepared for a series of sending out N- diphenyl phosphorus oxygen carbazole/9- aryl fluorenes steric hindrance types bipolarity
Luminescent material.
In a word, the present invention is on the premise of being fully understanded to current electroluminescent organic material, to track organic electronic device
Part forward position dynamic, the preparation of synthesis, El element around electroluminescent organic material and its dependent interaction mechanism are deployed.
The content of the invention
Technical problem：It is an object of the invention to provide a kind of N- diphenyl phosphorus oxygen carbazole -9- aryl fluorenes class luminescent material and its
Preparation method, design synthesis is based on a kind of pyridine fluorenes class luminescent material, and effective material of main part is stablized in preparation, and it is in electroluminescent hair
There is extensive use in terms of light, memory device.
Technical scheme：Present invention relates particularly to a kind of N- diphenyl phosphorus oxygen carbazole -9- aryl fluorenes class luminescent material and its system
Preparation Method, the material is to replace 9 aryl of fluorenes in 9- aryl fluorenes classes with different aromatic functional groups to make its functionalization, and it has
There is following structure：
In formula I, X1, X2For 9- aryl fluorenes or hydrogen atom, wherein at least one is 9- aryl fluorenes functional group, R be with
The functional group of aromatic ring structure.
Described R is specially such as having structure：
The compound fluorenes of aryl containing 9- and N- diphenyl phosphorus oxygen carbazoles, the work(of all introducings representated by described formula I
Energy property functional group A r is both connected to 9 of fluorenes.
The preparation method of N- diphenyl phosphorus oxygen carbazole -9- aryl fluorenes steric hindrance type luminous organic materials of the present invention is：
A. carbazole and tetrahydrofuran are added to reactor, low temperature is stirred under the protection of dry ice, acetone and nitrogen, takes positive fourth
Base lithium is slowly added in reactor, and low-temp reaction takes chloride 2-phenyl-phosphine to be added drop-wise to dropwise in reactor, and low-temp reaction 1-5 is small
When, then normal-temperature reaction；PH is adjusted to be about neutrality with water process, and with acetic acid, reactant mixture is extracted with dichloromethane, is associated with
Machine phase is simultaneously dried with anhydrous magnesium sulfate, and concentration, column chromatography obtain product N- diphenylphosphine carbazoles；
B. take 9- hydroxyl -9- aryl fluorenes, N- diphenylphosphines carbazole, acetic acid to add heating stirring in reactor to dissolve, then
The concentrated sulfuric acid is added, back flow reaction is heated to, question response is cooled to room temperature, cold water stirring is added, sodium hydroxide is then added water-soluble
Liquid is extracted to solution alkaline with dichloromethane, is merged organic phase and is dried with anhydrous magnesium sulfate；Then two are used decompression suction filtration and
Chloromethanes washs drier, and gained filtrate is concentrated under reduced pressure with Rotary Evaporators and removes most of solvent, the thick production concentrated
Thing；Then column chromatography, using ethyl acetate and petroleum ether as detergent, obtains white solid product after purification；
C.N- diphenylphosphine carbazole -9- aryl fluorenes stirring and dissolving in the solvent of ethanol and chloroform, is then slowly added into double
Oxygen water, is stirred at room temperature reaction 5-72 hour, and question response is extracted after stopping with dichloromethane, merging organic phase and with anhydrous
Magnesium sulfate is dried；After drying, depressurize suction filtration and wash drier with dichloromethane, gained filtrate is depressurized with Rotary Evaporators dense
Contracting removes most of solvent, the crude product concentrated；Then column chromatography, using ethyl acetate and petroleum ether as detergent, is purified
White solid product N- diphenyl phosphorus oxygen carbazole -9- aryl fluorenes steric hindrance type luminous organic materials are obtained afterwards.
Wherein,
Low-temp reaction described in step a, its reaction time is 0.5-5 hours.
Back flow reaction is heated to described in step b, its reaction time is 2-48 hours.
Described is extracted with dichloromethane, and the number of times of extraction is 1 time -10 times.
The present invention combines N- diphenyl phosphorus oxygen carbazole/9- aryl fluorenes steric hindrance types, and there is 3-D solid structure can effectively suppress dense
Degree is quenched, and is combined with that 9 of fluorenes introduce different feature luminous energy group's timely adjustment spectrum and its energy level, so as to reach conjunction
Into being concisely and efficiently material of main part.In addition, its bipolarity electric transmission feature allows it to simplify device architecture, cost is reduced,
The final commercialization for realizing large scale Organic Light Emitting Diode.
Beneficial effect：By infrared spectrum (FTIR), elementary analysis, nuclear magnetic resonance (NMR), chromaticness online (GCMS), solidifying
Glue chromatogram (GPC) characterizes complicated N- diphenyl phosphorus oxygen carbazole/9- aryl fluorene material structures, passes through thermogravimetric analysis and differential thermal analysis
The heat endurance of material is tested, their light, electrochemistry are characterized by Ultraluminescence spectrum and cyclic voltammetric method
Matter.This kind of material shows good heat endurance, ultraviolet, fluorescence and electrochemical analysis table in thermogravimetric analysis and differential thermal analysis
Bright its has good photoelectric properties.Therefore, this kind of material can be widely applied to Organic Light Emitting Diode, organic laser, have
Electromechanical memory devices, organic field-effect tube etc..
Main advantages of the present invention are：
1. synthesis step is simple, mild condition；
2. maintain high thermal stability and glass transition temperature.
3. with appropriate triplet
4. with suitable HOMO and lumo energy
5. with big space steric effect
Brief description of the drawings
Fig. 1 is the mass spectrogram of 3- (9- phenyl fluorenes)-N- diphenylphosphine carbazoles, and 591.1924 be molecular ion peak；
Fig. 2 is the mass spectrogram of 3,6- bis- (9- phenyl fluorenes)-N- diphenylphosphine carbazoles, and 832.3693 be molecule M+1 ions
Peak；
Fig. 3 is the mass spectrogram of 3,6- bis- (9- phenyl fluorenes)-N- diphenyl phosphorus oxygen carbazoles, and 848.3061 be M+1 peaks；
902.3425 for M+MeOH+Na peaks.
Embodiment
Technical scheme is further described with reference to embodiment, but these embodiments not limit the present invention
Embodiment.The present invention has a variety of different embodiments, is not only limited in content described in this specification.This area
Technical staff is in the case of without prejudice to the present application spirit, and the scheme completed should be within the scope of the invention.
Embodiment 1：The synthesis of 3- (9- phenyl fluorenes)-N- diphenylphosphine carbazoles：
The phenyl fluorenes (0.5160g, 2mmol) of 9- hydroxyls -9, N- diphenylphosphines carbazole (0.7020g, 2 mmol), two are taken successively
Chloromethanes 100mL stirring and dissolvings at room temperature, then add BFEE 0.25mL reactions 24h.Question response is cooled to room temperature,
The stirring quenching reaction of about 50mL cold water is added, it is multiple with dichloromethane extraction, merge organic phase and dried with anhydrous magnesium sulfate.Dry
Afterwards, suction filtration is depressurized, and drier is washed with dichloromethane, gained filtrate is concentrated under reduced pressure with Rotary Evaporators, and it is most of molten to remove
Agent, the crude product concentrated.Then column chromatography, white solid production is obtained using ethyl acetate and petroleum ether as detergent, after purification
Thing 3- (9- phenyl fluorenes)-N- diphenylphosphine carbazole (yields:60%), [M of LC-MS (EI) m/z 590.1928+]。
Embodiment 2：The synthesis of 3,6- bis- (9- phenyl fluorenes)-N- diphenylphosphine carbazoles：
The phenyl fluorenes (0.5160g, 2mmol) of 9- hydroxyls -9, N- diphenylphosphines carbazole (0.3510g, 1 mmol), two are taken successively
Chloromethanes 100mL stirring and dissolvings at room temperature, then add BFEE 0.25mL reactions 24h.Question response is cooled to room temperature,
The stirring quenching reaction of about 50mL cold water is added, it is multiple with dichloromethane extraction, merge organic phase and dried with anhydrous magnesium sulfate.Dry
Afterwards, suction filtration is depressurized, and drier is washed with dichloromethane, gained filtrate is concentrated under reduced pressure with Rotary Evaporators, and it is most of molten to remove
Agent, the crude product concentrated.Then column chromatography, white solid production is obtained using ethyl acetate and petroleum ether as detergent, after purification
Thing 3,6- bis- (9- phenyl fluorenes)-N- diphenylphosphine carbazole (yields:54%), [M of LC-MS (EI) m/z 832.3693+]。
Embodiment 3：The synthesis of 3,6- bis- (9- phenyl fluorenes)-N- diphenyl phosphorus oxygen carbazoles：
3,6- bis- (9- phenyl fluorenes)-N- diphenylphosphines carbazole (0.8320g, 1mmol) is molten in the solvent of ethanol and chloroform
Solve and stir, be then slowly added into 30% hydrogen peroxide 1.2mL, reaction 5-72 hours is stirred at room temperature, is extracted with dichloromethane
Repeatedly, merge organic phase to be dried with anhydrous magnesium sulfate；After drying, depressurize suction filtration and wash drier with dichloromethane, by gained
Filtrate is concentrated under reduced pressure with Rotary Evaporators removes most of solvent, the crude product concentrated；Then column chromatography, with ethyl acetate
It is detergent with petroleum ether, white solid product 3,6- bis- (9- phenyl fluorenes)-N- diphenyl phosphorus oxygen carbazoles is obtained after purification.(yield:
43%).LC-MS(EI)m/z 848.3061 [M+]。
Claims (7)
1. a kind of N- diphenyl phosphorus oxygen carbazole -9- aryl fluorenes steric hindrance type luminous organic materials, it is characterised in that the material is by 9-
9 aryl of fluorenes make its functionalization with different aromatic functional group substitutions in aryl fluorenes class, and it has following structure：
In formula I, X1, X2For 9- aryl fluorenes or hydrogen atom, wherein at least one is 9- aryl fluorenes functional group, and R is with aromatic ring knot
The functional group of structure.
2. N- diphenyl phosphorus oxygen carbazole -9- aryl fluorenes steric hindrance type luminous organic materials according to claim 1, its feature exists
In described R specially such as having structure：
3. N- diphenyl phosphorus oxygen carbazole -9- aryl fluorenes steric hindrance type luminous organic materials according to claim 1, its feature exists
In the fluorenes of aryl containing 9- of the compound representated by described formula I and N- diphenyl phosphorus oxygen carbazoles, the feature official of all introducings
9 that Ar is both connected to fluorenes can be rolled into a ball.
4. a kind of preparation of N- diphenyl phosphorus oxygen carbazole -9- aryl fluorenes steric hindrance type luminous organic materials as claimed in claim 1
Method, it is characterised in that the preparation method is:
A. carbazole and tetrahydrofuran are added to reactor, low temperature is stirred under the protection of dry ice, acetone and nitrogen, takes n-BuLi
It is slowly added in reactor, low-temp reaction takes chloride 2-phenyl-phosphine to be added drop-wise to dropwise in reactor, low-temp reaction 1-5 hours, so
Normal-temperature reaction afterwards；PH is adjusted to be about neutrality with water process, and with acetic acid, reactant mixture is extracted with dichloromethane, merges organic phase
And dried with anhydrous magnesium sulfate, concentration, column chromatography obtain product N- diphenylphosphine carbazoles；
B. take 9- hydroxyl -9- aryl fluorenes, N- diphenylphosphines carbazole, acetic acid to add heating stirring in reactor to dissolve, then add
The concentrated sulfuric acid, is heated to back flow reaction, and question response is cooled to room temperature, adds cold water stirring, then adds sodium hydrate aqueous solution extremely
Solution alkaline, is extracted with dichloromethane, is merged organic phase and is dried with anhydrous magnesium sulfate；Then depressurize suction filtration and use dichloromethane
Alkane washs drier, and gained filtrate is concentrated under reduced pressure with Rotary Evaporators and removes most of solvent, the crude product concentrated；So
Column chromatography, using ethyl acetate and petroleum ether as detergent, obtains white solid product afterwards after purification；
C.N- diphenylphosphine carbazole -9- aryl fluorenes stirring and dissolving in the solvent of ethanol and chloroform, is then slowly added into hydrogen peroxide,
Reaction 5-72 hours is stirred at room temperature, question response is extracted after stopping with dichloromethane, merges organic phase and use anhydrous magnesium sulfate
Dry；After drying, decompression suction filtration simultaneously washs drier with dichloromethane, and gained filtrate is concentrated under reduced pressure removing with Rotary Evaporators
Most of solvent, the crude product concentrated；Then column chromatography, using ethyl acetate and petroleum ether as detergent, is obtained in vain after purification
Color solid product N- diphenyl phosphorus oxygen carbazole -9- aryl fluorenes steric hindrance type luminous organic materials.
5. the preparation side of N- diphenyl phosphorus oxygen carbazole -9- aryl fluorenes steric hindrance type luminous organic materials according to claim 4
Method, it is characterised in that the low-temp reaction described in step a, its reaction time is 0.5-5 hours.
6. the preparation side of N- diphenyl phosphorus oxygen carbazole -9- aryl fluorenes steric hindrance type luminous organic materials according to claim 4
Method, it is characterised in that be heated to back flow reaction described in step b, its reaction time is 2-48 hours.
7. the preparation side of N- diphenyl phosphorus oxygen carbazole -9- aryl fluorenes steric hindrance type luminous organic materials according to claim 4
Method, it is characterised in that described to be extracted with dichloromethane, the number of times of extraction is 1 time -10 times.
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