CN113980054A - Phosphine-oxygen-containing compound and preparation and application thereof - Google Patents
Phosphine-oxygen-containing compound and preparation and application thereof Download PDFInfo
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- CN113980054A CN113980054A CN202111370425.8A CN202111370425A CN113980054A CN 113980054 A CN113980054 A CN 113980054A CN 202111370425 A CN202111370425 A CN 202111370425A CN 113980054 A CN113980054 A CN 113980054A
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- phosphine
- oxygen
- containing compound
- organic solvent
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 56
- 239000001301 oxygen Substances 0.000 title claims abstract description 50
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 32
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000073 phosphorus hydride Inorganic materials 0.000 claims abstract description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 42
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 42
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 30
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 claims description 28
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 20
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 18
- MFRIHAYPQRLWNB-UHFFFAOYSA-N sodium tert-butoxide Chemical compound [Na+].CC(C)(C)[O-] MFRIHAYPQRLWNB-UHFFFAOYSA-N 0.000 claims description 18
- 239000003960 organic solvent Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- IMDXZWRLUZPMDH-UHFFFAOYSA-N dichlorophenylphosphine Chemical compound ClP(Cl)C1=CC=CC=C1 IMDXZWRLUZPMDH-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 12
- WNSNPGHNIJOOPM-UHFFFAOYSA-N 1,4-dibromo-2-fluorobenzene Chemical compound FC1=CC(Br)=CC=C1Br WNSNPGHNIJOOPM-UHFFFAOYSA-N 0.000 claims description 9
- JENANTGGBLOTIB-UHFFFAOYSA-N 1,5-diphenylpentan-3-one Chemical compound C=1C=CC=CC=1CCC(=O)CCC1=CC=CC=C1 JENANTGGBLOTIB-UHFFFAOYSA-N 0.000 claims description 9
- 239000007983 Tris buffer Substances 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 9
- -1 tri-tert-butylphosphine tetrafluoroborate Chemical compound 0.000 claims description 9
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 8
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011261 inert gas Substances 0.000 claims description 8
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 7
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 6
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 6
- OYFFSPILVQLRQA-UHFFFAOYSA-N 3,6-ditert-butyl-9h-carbazole Chemical compound C1=C(C(C)(C)C)C=C2C3=CC(C(C)(C)C)=CC=C3NC2=C1 OYFFSPILVQLRQA-UHFFFAOYSA-N 0.000 claims description 5
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 5
- KBGPFZUZKTUOII-UHFFFAOYSA-N 1,3,6,8-tetramethyl-9h-carbazole Chemical compound C1=C(C)C=C2C3=CC(C)=CC(C)=C3NC2=C1C KBGPFZUZKTUOII-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 150000002927 oxygen compounds Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 235000005811 Viola adunca Nutrition 0.000 abstract description 15
- 240000009038 Viola odorata Species 0.000 abstract description 15
- 235000013487 Viola odorata Nutrition 0.000 abstract description 15
- 235000002254 Viola papilionacea Nutrition 0.000 abstract description 15
- 238000006862 quantum yield reaction Methods 0.000 abstract description 9
- 238000012546 transfer Methods 0.000 abstract description 6
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 abstract description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 45
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 33
- 239000000047 product Substances 0.000 description 32
- 239000003208 petroleum Substances 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000001035 drying Methods 0.000 description 13
- 239000003480 eluent Substances 0.000 description 13
- 238000002189 fluorescence spectrum Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 13
- 238000004440 column chromatography Methods 0.000 description 12
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 10
- 239000012044 organic layer Substances 0.000 description 10
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- 238000001228 spectrum Methods 0.000 description 10
- 150000002500 ions Chemical class 0.000 description 9
- 238000000862 absorption spectrum Methods 0.000 description 7
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000010898 silica gel chromatography Methods 0.000 description 6
- 230000008859 change Effects 0.000 description 5
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000005481 NMR spectroscopy Methods 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- CDTHXJORUCZHMD-UHFFFAOYSA-N 1,4-dibromo-2-(2,5-dibromophenoxy)benzene Chemical compound BrC1=CC=C(Br)C(OC=2C(=CC=C(Br)C=2)Br)=C1 CDTHXJORUCZHMD-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- 229940126062 Compound A Drugs 0.000 description 3
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000012267 brine Substances 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
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- 238000001914 filtration Methods 0.000 description 3
- 238000001819 mass spectrum Methods 0.000 description 3
- 229910052763 palladium Inorganic materials 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 230000001052 transient effect Effects 0.000 description 3
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
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- 230000005540 biological transmission Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 230000021615 conjugation Effects 0.000 description 2
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- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 2
- 238000010884 ion-beam technique Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
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- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
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- 238000010992 reflux Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- ATTVYRDSOVWELU-UHFFFAOYSA-N 1-diphenylphosphoryl-2-(2-diphenylphosphorylphenoxy)benzene Chemical compound C=1C=CC=CC=1P(C=1C(=CC=CC=1)OC=1C(=CC=CC=1)P(=O)(C=1C=CC=CC=1)C=1C=CC=CC=1)(=O)C1=CC=CC=C1 ATTVYRDSOVWELU-UHFFFAOYSA-N 0.000 description 1
- GZPPANJXLZUWHT-UHFFFAOYSA-N 1h-naphtho[2,1-e]benzimidazole Chemical class C1=CC2=CC=CC=C2C2=C1C(N=CN1)=C1C=C2 GZPPANJXLZUWHT-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- SCHRRICRQNJJKN-UHFFFAOYSA-N P.[O] Chemical group P.[O] SCHRRICRQNJJKN-UHFFFAOYSA-N 0.000 description 1
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical compound [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 1
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- 125000003118 aryl group Chemical group 0.000 description 1
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- 239000000969 carrier Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
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- 239000007791 liquid phase Substances 0.000 description 1
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- 239000012452 mother liquor Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical compound [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
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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
- C07F9/6564—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms
- C07F9/6571—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms
- C07F9/657163—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having phosphorus atoms, with or without nitrogen, oxygen, sulfur, selenium or tellurium atoms, as ring hetero atoms having phosphorus and oxygen atoms as the only ring hetero atoms the ring phosphorus atom being bound to at least one carbon atom
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- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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Abstract
The invention provides a phosphine-oxygen-containing compound and preparation and application thereof. The compound takes phosphine oxide as an electron acceptor, and a specific electron donor group is introduced into the phosphine oxide to construct a charge transfer state compound with a donor-acceptor structure, and the phosphine-containing oxide compound has better luminous intensity, color purity, thermal stability and fluorescence quantum yield, provides a new choice for blue-violet light or deep blue light materials, and is suitable for preparing luminescent materials and photoelectric luminescent devices.
Description
Technical Field
The invention belongs to the technical field of luminescent materials. More particularly, it relates to a phosphine-oxygen containing compound and its preparation and application.
Background
The organic electroluminescent device (OLED) has the characteristics of high brightness, low power consumption, fast response, wide viewing angle, good flexibility, high luminous efficiency and the like, is regarded as a new generation of display products with great development prospect in the diversified flat panel display market, is known as a 'dream display', and is widely applied to high-tech fields such as smart phones, notebook computers, intelligent wearable equipment and the like.
The light emitting materials in the OLED can be divided into red, green and blue materials according to the emitted light color, but the blue device as one of the three primary colors (blue, green and red) has a certain difference in performance from the other two light colors, and especially the development of the deep blue or blue-violet device which can be used for high-quality display has not been a substantial breakthrough all the time, and is not satisfactory in terms of device efficiency and light color. At present, the deep blue light or blue-violet light material has the following problems: (1) due to the influence of the energy gap theorem, most blue light materials in the prior art belong to the category of sky blue light, and the red shift of the spectrum often causes the color purity to be too low, so that the high blue light color purity of the luminescent material is difficult to meet; (2) the variety of deep blue light or blue-violet light materials is scarce; (3) the current commercial blue light material is the first generation of traditional compound, and the efficiency is generally low.
The prior researches find that the phosphine-oxygen-containing compound shows better potential when being used as a deep blue light or blue-violet light material, such as a phosphinyloxy boron complex deep blue light thermal excitation delayed fluorescent material and an electroluminescent material of 9-position functionalized fluorenyl aromatic monophosphine oxide, which all show that the phosphine-oxygen-containing compound can be used for preparing the deep blue light or blue-violet light material, but the types of the phosphine-oxygen-containing compound are few in general, so that more novel phosphine-oxygen-containing compounds which can be used for preparing the deep blue light or blue-violet light material are needed to be developed.
Disclosure of Invention
The invention aims to provide a phosphine-oxygen-containing compound and preparation and application thereof. The phosphine-oxygen-containing compound has better luminous intensity, color purity, thermal stability and fluorescence quantum yield, and provides a new choice for blue-violet light or deep blue light materials.
The first object of the present invention is to provide a phosphine-oxygen containing compound.
The second object of the present invention is to provide a process for producing the above phosphine-oxygen containing compound.
The third purpose of the invention is to provide the application of the phosphine-oxygen-containing compound in preparing luminescent materials or photoelectric luminescent devices.
It is a fourth object of the present invention to provide a luminescent material.
It is a fifth object of the present invention to provide a photovoltaic light emitting device.
The above purpose of the invention is realized by the following technical scheme:
the invention provides a phosphine-oxygen-containing compound, which has a chemical structure shown as the following formula (A1) or formula (A2):
the invention also provides a preparation method of the phosphine-oxygen-containing compound, which comprises the following steps:
s1, heating 1, 4-dibromo-2-fluorobenzene, potassium hydroxide and potassium carbonate in an organic solvent and inert gas to react to obtain an intermediate 1;
s2, sequentially adding n-butyl lithium and phenyl phosphorus dichloride into the intermediate 1 obtained in the step S1 at the temperature of-80 to-70 ℃ in an organic solvent for reaction, stirring for 12-16 h, and adding hydrogen peroxide for reaction to obtain an intermediate 2;
s3, heating and reacting the intermediate 2 obtained in the step S2, a donor group, tris (dibenzylacetone) dipalladium, tri-tert-butylphosphine tetrafluoroborate and sodium tert-butoxide in an organic solvent and an inert gas to obtain the phosphine-containing oxygen compound;
wherein the donor group is 3, 6-di-tert-butyl-9H-carbazole or 1,3,6, 8-tetramethyl-9H-carbazole.
The phosphine-oxygen group has an SP3 hybridized electronic structure, so that the conjugation of molecules can be broken, the red shift of a spectrum and the reduction of color purity caused by strong charge transfer in the molecules are inhibited, and the phosphine-oxygen group has better electronic transmission capability, can balance the transmission of carriers, and improves the luminous efficiency and inhibits the efficiency roll-off. Therefore, the charge transfer state compound with the donor-acceptor structure, which is constructed by taking phosphine oxide as an electron acceptor and introducing a specific electron donor group into the electron acceptor, has unique intramolecular twisted charge transfer characteristics, higher luminous intensity, deep blue light or blue-violet light emission and fluorescence delay effects, and can be widely applied to the fields of color display and solid-state lighting, such as preparation of an excellent luminous layer in a blue light OLED.
Preferably, the molar ratio of the 1, 4-dibromo-2-fluorobenzene, the potassium hydroxide and the potassium carbonate in the step S1 is 1: 0.5-0.7: 1 to 2.
Most preferably, the molar ratio of the 1, 4-dibromo-2-fluorobenzene to the potassium hydroxide to the potassium carbonate is 1: 0.6: 1.1, see example 1.
Preferably, in step S2, the molar ratio of the intermediate 1, n-butyl lithium, phenyl phosphorus dichloride and hydrogen peroxide is 1: 2-2.3: 1-2: 3 to 4.
Most preferably, the molar ratio of the intermediate 1, n-butyllithium, phenylphosphorus dichloride and hydrogen peroxide is 1: 2.2: 1.5: 3.5, see example 1.
Preferably, the molar ratio of the intermediate 2, the donor group, the tris (dibenzylacetone) dipalladium, the tri-tert-butylphosphine tetrafluoroborate and the sodium tert-butoxide in step S3 is 1: 2-3: 0.02-0.04: 0.08-0.1: 3 to 5.
Most preferably, the molar ratio of intermediate 2, donor group, tris (dibenzylacetone) dipalladium, tri-tert-butylphosphine tetrafluoroborate, sodium tert-butoxide is 1: 2.5: 0.03: 0.09: see example 1.
Preferably, the organic solvent of step S1 is triglyme, tetraglyme, or glyme. Most preferred is triglyme, see example 1.
Preferably, the organic solvent in step S2 is diethyl ether or tetrahydrofuran.
Preferably, the organic solvent in step S3 is toluene, chlorobenzene or o-dichlorobenzene. Most preferred is toluene, see example 1.
Preferably, the heating temperature in the step S1 is 180-190 ℃, and the time is 72-96 h.
Most preferably, the heating is carried out at 180 ℃ for 96h, see example 1.
Preferably, step S2 is specifically: and (4) dropwise adding n-butyllithium into the intermediate 1 obtained in the step S1 at the temperature of-80 to-70 ℃ in an organic solvent for reaction for 1-1.5 h, adding phenylphosphorus dichloride for reaction for 20-30 min, stirring for 12-16 h at the temperature of 20-30 ℃, and finally adding hydrogen peroxide and stirring for 2-4 h to obtain an intermediate 2.
Most preferably, step S2 is specifically: and (3) dropwise adding n-butyllithium into the intermediate 1 obtained in the step (S1) at the temperature of-78 ℃ in ether or tetrahydrofuran for reacting for 1h, then adding phenylphosphorus dichloride for reacting for 20min, stirring for 12h at the temperature of 25 ℃, and finally adding hydrogen peroxide and stirring for 2h to obtain an intermediate 2.
Preferably, the heating temperature in the step S3 is 100-120 ℃, and the time is 4-6 h.
Most preferably, the heating is carried out at a temperature of 110 ℃ for a period of 5h, see example 1.
Preferably, the inert gas of step S1 includes helium, nitrogen, or argon.
Preferably, the inert gas of step S3 includes helium, nitrogen, or argon.
Preferably, the intermediate 1 in step S1 further needs to be post-processed, specifically: cooling, extracting with dichloromethane, removing solvent, and purifying by column chromatography, wherein the eluent used in the column chromatography is petroleum ether.
Preferably, the intermediate 2 in step S2 needs to be further post-processed, specifically: extracting with ethyl acetate, drying an organic layer by using anhydrous sodium sulfate, distilling under reduced pressure, purifying by using column chromatography, and drying in vacuum, wherein an eluant used in the column chromatography is ethyl acetate: petroleum ether is 1: 1 (v/v).
Preferably, the phosphine-oxygen containing compound in step S3 further needs to be post-treated, specifically: cooling, extracting with dichloromethane, drying an organic layer with anhydrous sodium sulfate, filtering and evaporating, purifying by column chromatography, and drying in vacuum, wherein an eluant used in the column chromatography is ethyl acetate: petroleum ether is 1: 1 (v/v).
As a preferred possible embodiment, the method for producing the phosphine-oxygen compound comprises the steps of:
s1, mixing 1, 4-dibromo-2-fluorobenzene, potassium hydroxide and potassium carbonate according to a proportion of 1: 0.5-0.7: 1-2, heating and reacting in an organic solvent (triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether or ethylene glycol dimethyl ether) and inert gas at 180-190 ℃ for 72-96 h, cooling, extracting with dichloromethane, removing the solvent, and purifying by column chromatography (eluent is petroleum ether) to obtain a middle 1;
s2, dropwise adding n-butyllithium into the intermediate 1 obtained in the step S1 in an organic solvent (diethyl ether or tetrahydrofuran) at a temperature of between 80 and 70 ℃ below zero for reacting for 1 to 1.5 hours, then adding phenylphosphorus dichloride for reacting for 20 to 30 minutes, stirring for 12 to 16 hours at a temperature of between 20 and 30 ℃, finally adding hydrogen peroxide and stirring for 2 to 4 hours, extracting with ethyl acetate, drying an organic layer with anhydrous sodium sulfate, carrying out reduced pressure distillation, purifying by column chromatography (an eluent is ethyl acetate: petroleum ether: 1(v/v)), and carrying out vacuum drying to obtain an intermediate 2;
s3, mixing the intermediate 2 obtained in the step S2, a donor group, tris (dibenzylacetone) dipalladium, tri-tert-butylphosphine tetrafluoroborate and sodium tert-butoxide according to the weight ratio of 1: 2-3: 0.02-0.04: 0.08-0.1: heating and reacting in an organic solvent (toluene, chlorobenzene or o-dichlorobenzene) at a molar ratio of 3-5 in an inert gas at 100-120 ℃ for 4-6 h, cooling, extracting with dichloromethane, drying an organic layer with anhydrous sodium sulfate, filtering, evaporating, purifying by column chromatography (an eluent is ethyl acetate: petroleum ether ═ 1: 1(v/v)), and drying in vacuum to obtain the phosphine-containing oxide compound;
wherein, the molar ratio of the intermediate 1, n-butyllithium, phenylphosphorus dichloride and hydrogen peroxide in the step S2 is 1: 2-2.3: 1-2: 3-4; the donor group is 3, 6-di-tert-butyl-9H-carbazole or 1,3,6, 8-tetramethyl-9H-carbazole.
The phosphine-oxygen-containing compound has better luminous intensity, color purity, thermal stability and fluorescence quantum yield, can be used as an excellent blue-violet light or deep blue light material, and is suitable for preparing a luminescent material and a photoelectric luminescent device. Therefore, the application of the phosphine-oxygen-containing compound in preparing a luminescent material or a photoelectric luminescent device, and the luminescent material and/or the photoelectric luminescent device comprising or prepared from the phosphine-oxygen-containing compound also belong to the protection scope of the invention.
The invention has the following beneficial effects:
1. the compound of the present invention is a charge-transfer state phosphine-oxygen-containing compound (A1, A2) having a donor-acceptor structure constructed by introducing a specific electron donor group to phosphine oxygen as an electron acceptor, and has a preferable luminous intensity (luminous intensities of 2.01X 10, respectively)5、1.05×106) The color purity (full half-peak width is respectively 38nm and 65nm), the thermal stability (thermal decomposition temperature is respectively 440 ℃ and 420 ℃) and the fluorescence quantum yield (yield is respectively 74.01 percent and 85.89 percent), so the material can be used as an excellent blue-violet light or deep blue light material source and is suitable for preparing luminescent materials and photoelectric luminescent devices.
2. The invention realizes the controllable preparation of the phosphine-oxygen-containing compound, has low preparation cost and wide raw material source, and can realize large-scale production.
Drawings
FIG. 1 shows the NMR spectrum of A1 obtained in example 1.
FIG. 2 is a NMR spectrum of product A2 obtained in example 2.
FIG. 3 is a mass spectrum of product A1 obtained in example 1.
FIG. 4 is a mass spectrum of product A2 obtained in example 2.
FIG. 5 is a graph showing an ultraviolet-visible absorption spectrum and a fluorescence emission spectrum of the product A1 obtained in example 1 in a toluene solution.
FIG. 6 is a graph showing an ultraviolet-visible absorption spectrum and a fluorescence emission spectrum of the product A2 obtained in example 2 in a toluene solution.
FIG. 7 is a non-normalized spectrum of product A1 obtained in example 1.
FIG. 8 is a non-normalized spectrum of product A2 obtained in example 2.
FIG. 9 is a graph showing the change in the fluorescence lifetime of product A1 obtained in example 1.
FIG. 10 is a graph showing the change in the fluorescence lifetime of product A2 obtained in example 2.
FIG. 11 is a fluorescence spectrum showing the change in fluorescence intensity of product A1 obtained in example 1.
FIG. 12 is a fluorescence spectrum showing the change in fluorescence intensity of A2 which is a product obtained in example 2.
FIG. 13 shows fluorescence emission spectra of thin films obtained in examples 1 to 2.
FIG. 14 is a thermogravimetric analysis chart of the product obtained in examples 1-2.
Detailed Description
The invention is further described with reference to the drawings and the following detailed description, which are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
EXAMPLE 1 preparation of a phosphine-oxygen containing Compound-A Compound of formula (A1)
S1, preparing an intermediate 1, namely 2,2' -oxybis (1, 4-dibromobenzene):
1, 4-dibromo-2-fluorobenzene (25.00g, 98.46mmol), potassium hydroxide, and potassium carbonate were mixed in the following ratio of 1: 0.6: 1.1 to 10mL of triglyme, heated and stirred at 180 ℃ under nitrogen for 96 hours under reflux, cooled and extracted with dichloromethane to obtain a brown solid, which was then purified by column chromatography using petroleum ether as eluent to obtain 3.50g of intermediate 1 as a white solid (14.80% yield). The reaction equation is as follows:
s2, preparing an intermediate 2, namely 3, 7-dibromo-10-phenylphenoxy phosphine 10-oxide:
dropwise adding the intermediate 1(0.97g, 2.00mmol) obtained in the step S1 into 47mL of anhydrous tetrahydrofuran at-78 ℃ for reaction for 1h, then adding phenylphosphorus dichloride for reaction for 20min, stirring at 25 ℃ for 12h, then dropwise adding hydrogen peroxide for stirring for 2h, extracting with ethyl acetate, washing the obtained organic layers with water, drying with anhydrous sodium sulfate, purifying the product after reduced pressure distillation by silica gel column chromatography (eluent is ethyl acetate: petroleum ether ═ 1: 1(v/v)), and drying in vacuum to obtain 0.20g of white solid intermediate 2 (yield is 22.20%); wherein, the molar ratio of the intermediate 1, n-butyllithium, phenylphosphorus dichloride and hydrogen peroxide in the step S2 is 1: 2.2: 1.5: 3.5. the reaction equation is as follows:
s3. preparation of the compound of formula (A1):
reacting intermediate 2(131.87mg, 0.29mmol) obtained in step S2, 3, 6-di-tert-butyl-9H-carbazole, tris (dibenzylacetone) palladium, tri-tert-butylphosphine tetrafluoroborate, sodium tert-butoxide in a molar ratio of 1: 2.5: 0.03: 0.09: 4 in a 25mL round bottom flask containing 5mL of anhydrous toluene, heated and stirred at 110 ℃ for 5h under nitrogen, cooled and extracted with dichloromethane, the combined organic layers washed with brine, dried over anhydrous sodium sulfate, filtered, evaporated and purified by silica gel column chromatography (eluent ethyl acetate: petroleum ether ═ 1: 1(v/v)), dried under vacuum to give 159mg of a white solid (yield 54.46%). The reaction equation is as follows:
EXAMPLE 2 preparation of a phosphine-oxygen containing Compound-A Compound of formula (A2)
S1, preparing an intermediate 1, namely 2,2' -oxybis (1, 4-dibromobenzene):
1, 4-dibromo-2-fluorobenzene (25.00g, 98.46mmol), potassium hydroxide, and potassium carbonate were mixed in the following ratio of 1: 0.5: 2 to a molar ratio, heating and stirring the mixture at 190 ℃ for reflux reaction for 72 h under a helium atmosphere in a 50mL round-bottom flask containing 10mL ethylene glycol dimethyl ether, cooling the reaction mixture, extracting the reaction product with dichloromethane, removing the solvent to obtain a brown solid, and purifying the brown solid by column chromatography using petroleum ether as an eluent to obtain 3.0g of intermediate 1 (yield 12.68%) as a white solid. The reaction equation is as follows:
s2, preparing an intermediate 2, namely 3, 7-dibromo-10-phenylphenoxy phosphine 10-oxide:
reacting intermediate 1(0.97g, 2.00mmol) obtained in step S1 with 47mL of anhydrous ether at-80 ℃ by dropwise addition of n-butyllithium for 1 hour, further adding phenylphosphorus dichloride for 20min, then stirring at 20 ℃ for 16 hours, then adding hydrogen peroxide by dropwise, stirring for 2 hours, extracting with ethyl acetate, washing the combined organic layers with water, drying with anhydrous sodium sulfate, purifying the product after vacuum distillation by silica gel column chromatography (eluent is ethyl acetate: petroleum ether ═ 1: 1(v/v)), and drying under vacuum to obtain 0.17g of intermediate 2 as a white solid (yield is 18.87%); wherein, the molar ratio of the intermediate 1, n-butyllithium, phenylphosphorus dichloride and hydrogen peroxide in the step S2 is 1: 2.3: 1: 3.
the reaction equation is as follows:
s3. preparation of the compound of formula (A1):
reacting intermediate 2(131.87mg, 0.29mmol) obtained in step S2, 1,3,6, 8-tetramethyl-9H-carbazole, tris (dibenzylacetone) palladium, tri-tert-butylphosphine tetrafluoroborate, and sodium tert-butoxide in a molar ratio of 1: 3: 0.02: 0.08: 3 in a 25mL round bottom flask containing 5mL of anhydrous chlorobenzene, heated and stirred at 120 ℃ for 4h under an atmosphere of helium, cooled, extracted with dichloromethane, washed with brine, combined organic layers dried over anhydrous sodium sulfate, filtered, evaporated, purified by silica gel column chromatography (eluent ethyl acetate: petroleum ether ═ 1: 1(v/v)), and dried under vacuum to give 97mg of a white solid (yield 47.16%). The reaction equation is as follows:
EXAMPLE 3 preparation of a phosphine-oxygen containing Compound-A Compound of formula (A1)
S1, preparing an intermediate 1, namely 2,2' -oxybis (1, 4-dibromobenzene):
1, 4-dibromo-2-fluorobenzene (25.00g, 98.46mmol), potassium hydroxide, and potassium carbonate were mixed in the following ratio of 1: 0.7: 1 to a 50mL round bottom flask containing 10mL of tetraglyme, heated under stirring at 180 ℃ under argon atmosphere and refluxed for 96h, cooled, extracted with dichloromethane to obtain a brown solid, and purified by column chromatography using petroleum ether as eluent to obtain 3.3g of intermediate 1 as a white solid (yield 13.95%). The reaction equation is the same as in example 1.
S2, preparing an intermediate 2, namely 3, 7-dibromo-10-phenylphenoxy phosphine 10-oxide:
dropwise adding n-butyllithium to the intermediate 1(0.97g, 2.00mmol) obtained in the step S1 at 47mL of anhydrous tetrahydrofuran and-70 ℃ for reaction for 1.5h, then adding phenylphosphorus dichloride for reaction for 30min, stirring at 30 ℃ for 12h, then dropwise adding hydrogen peroxide, stirring for 4h, extracting with ethyl acetate, washing the combined organic layers with water, drying with anhydrous sodium sulfate, purifying the product after reduced pressure distillation by silica gel column chromatography (eluent is ethyl acetate: petroleum ether ═ 1: 1(v/v)), and drying in vacuum to obtain 0.18g of intermediate 2 as a white solid (yield is 19.98%); wherein, the molar ratio of the intermediate 1, n-butyllithium, phenylphosphorus dichloride and hydrogen peroxide in the step S2 is 1: 2: 2: 4. the reaction equation is the same as in example 1.
S3. preparation of the compound of formula (A1):
reacting intermediate 2(131.87mg, 0.29mmol) obtained in step S2, 3, 6-di-tert-butyl-9H-carbazole, tris (dibenzylacetone) palladium, tri-tert-butylphosphine tetrafluoroborate, sodium tert-butoxide in a molar ratio of 1: 2: 0.04: 0.1: 5 molar ratio in a 25mL round bottom flask with 5mL o-dichlorobenzene, heated and stirred at 100 ℃ under argon atmosphere for 6h, cooled and extracted with dichloromethane, the combined organic layers washed with brine, dried over anhydrous sodium sulfate, filtered, evaporated and purified by silica gel column chromatography (eluent ethyl acetate: petroleum ether ═ 1: 1(v/v)), dried under vacuum to give 145mg white solid (yield 49.66%). The reaction equation is the same as in example 1.
Example 4 structural characterization and Performance testing
(1) Hydrogen nuclear magnetic resonance spectroscopy:
respectively carrying out nuclear magnetic resonance scanning on the products obtained in the examples 1-2 by adopting a Brooks 400MHz superconducting nuclear magnetic resonance instrument to obtain the products shown in the figures 1-21HMNR graph.
As can be seen from the figure 1 of the drawings,1H NMR(400MHz,CDCl3) δ 8.14(d, J ═ 1.0,4H),7.96(dd, J ═ 12.7,8.3,2H),7.87(dd, J ═ 12.8,7.2,2H),7.65(d, J ═ 3.4,2H), 7.60-7.47 (m,13H),1.47(s,36H), molecular hydrogen spectrum peaks can correspond one-to-one with the target product a1 of example 1, and the amount is reasonable;
as can be seen from the figure 2 of the drawings,1H NMR(400MHz,CDCl3) δ 7.87(dd, J12.8, 8.1,2H),7.70(d, J12.0, 6H),7.53(dt, J13.3, 7.4,3H),7.43(dd, J11.0, 6.5,4H),6.90(s,4H),2.46(s,12H),1.92(s,12H), molecular hydrogen spectrum peaks can correspond one-to-one with the target product a2 of example 2, in reasonable amounts.
(2) Mass spectrum:
5mg of the fluorene-containing phenanthroimidazole derivative was dissolved in dichloromethane and acetonitrile was added dropwise to 5mL, followed by filtration through a 0.22 μm filter to remove particles exceeding 0.22 μm and minimize detection interference. Then putting the products obtained in the embodiments 1-2 into a liquid phase mass spectrometer, ionizing all components in a sample to generate ions with different charge-mass ratios, forming ion beams under the action of an accelerating electric field, entering a mass analyzer, and causing opposite velocity dispersion by using an electric field and a magnetic field, wherein ions with slower velocity in the ion beams are deflected greatly after passing through the electric field, and the deflection with high velocity is small; ions are deflected in a magnetic field with opposite angular velocity vectors, namely the ions with low speed are still deflected greatly, and the ions with high speed are deflected slightly; when the deflection effects of the two fields compensate each other, their tracks intersect at a point. Meanwhile, mass separation can also occur in the magnetic field, so that ions with the same mass-to-charge ratio and different speeds are focused on the same point, ions with different mass-to-charge ratios are focused on different points, and the ions are respectively focused to obtain mass spectrograms of figures 3-4, so that the mass of the ions is determined.
As can be seen from FIG. 3, the relative molecular mass of the product obtained in example 1 was 847.225, which is consistent with the relative molecular mass of the phosphine-oxygen containing compound (A1) synthesized;
as can be seen from fig. 4, the relative molecular mass of the product obtained in example 2 was 735.32, which is consistent with the relative molecular mass of the phosphine-oxygen-containing compound (a2) synthesized.
Therefore, based on the results of nuclear magnetic resonance and mass spectrometry, it can be determined that the structural formulas of the compounds prepared in examples 1-2 are respectively shown as the following formulas (A1) and (A2):
(3) ultraviolet-visible absorption spectrum and fluorescence spectrum:
ultraviolet visible absorption spectrum: the products obtained in examples 1-2 were dissolved in toluene solution to prepare 1X 10- 3The mol/L mother liquor is respectively diluted to 1 × 10 when being tested by an Shimadzu ultraviolet visible spectrophotometer UV-2700- 5And the ultraviolet-visible absorption spectrums of A1 and A2 in the toluene solution are obtained through testing. Setting parameters; the scanning range is set to be 250-700 nm.
Fluorescence spectrum: the products obtained in examples 1-2 were tested by Edinburgh FL980 transient steady state fluorescence phosphorescence spectrometer to obtain fluorescence emission spectrograms of A1 and A2. Setting parameters: setting excitation wavelength to be 345nm, setting slit width to enable the longitudinal coordinate value to be close to one million, and carrying out spectrum test to obtain a spectrogram.
FIG. 5 is a chart showing an ultraviolet-visible absorption spectrum and a fluorescence emission spectrum of the product A1 obtained in example 1 in a toluene solution, and FIG. 6 is a chart showing an ultraviolet-visible absorption spectrum and a fluorescence emission spectrum of the product A2 obtained in example 2 in a toluene solution. As can be seen from FIGS. 5-6, the main absorption peak positions of A1 and A2 are both located at about 345nm, the fluorescence emission peak position of A1 is 381nm, blue-violet light is emitted, and the fluorescence emission peak position of A2 is 418nm, and deep blue light is emitted.
(4) Non-normalized spectra:
the products (A1, A2) obtained in examples 1-2 were tested using a multifunctional fluorometer to obtain the non-normalized spectra shown in FIGS. 7-8. As can be seen from FIGS. 7 to 8, the emission intensities of A1 and A2 were 2.01X 10 respectively5And 1.05X 106Full half-peak widths of 38nm and 65nm, respectively, indicate that A1 and A2 have better luminous intensity and color purity, wherein the luminous intensity and color purity of A1 are optimal.
(5) And (3) testing the fluorescence lifetime of the solution:
the products obtained in examples 1-2 were tested separately using Edinburgh FL980 transient steady state fluorescence phosphorescence spectrophotometers. In the experiment, an excimer laser is used for generating ultraviolet light to excite a sample, the excited fluorescence of the sample enters a photomultiplier through a telescope system, a signal led out by the photomultiplier enters a signal integrator and then enters a computer for data acquisition and processing, and the determination conditions are as follows: the excitation pulse repetition frequency was 10Hz, the pulse width was 10ns, and the center wavelength was 314 nm.
FIGS. 9 to 10 are graphs showing the change in fluorescence lifetime before and after (oxygen removal by blowing nitrogen gas) the products (A1, A2) obtained in examples 1 to 2 were removed in a toluene solution. As can be seen from fig. 9 to 10, a1 and a2 have longer fluorescence lifetimes after removal of oxygen compared to oxygen atmosphere, which indicates that oxygen quenches the triplet fluorescence of the phosphine-oxygen-containing compound (a1 and a2) and reduces the fluorescence lifetime, indicating that the phosphine-oxygen-containing compound (a1 and a2) can utilize excitons from the triplet state, thereby increasing the utilization rate of excitons and thus increasing the fluorescence quantum yield thereof.
FIGS. 11 to 12 are fluorescence spectra showing changes in fluorescence intensity of the products (A1, A2) obtained in examples 1 to 2 after bubbling nitrogen gas and oxygen gas, respectively, into a toluene solution at 25 ℃. From fig. 11 to 12, a1 and a2 show higher fluorescence emission intensity in a nitrogen atmosphere than in an oxygen atmosphere, which indicates that oxygen quenches the triplet fluorescence of the phosphine-oxygen-containing compounds (a1 and a2) to reduce the fluorescence emission intensity, indicating that the phosphine-oxygen-containing compounds (a1 and a2) can utilize excitons from the triplet state to achieve higher fluorescence quantum yield.
The products (A1 and A2) obtained in examples 1-2 were dissolved in toluene solution, nitrogen was bubbled, and then a fluorometer was used to test, which respectively obtained 74.01% and 85.89% absolute fluorescence quantum yield, indicating that A1 and A2 have better fluorescence quantum yield.
(6) Fluorescence spectrum of the film:
the phosphorus-oxygen-containing compounds (a1 and a2) were doped into a commercial host material DPEPO by a spin coating method to prepare thin films, and then tested by an einberg FL980 transient steady state fluorophosphorescence spectrometer to obtain the fluorescence emission spectra of fig. 13.
As can be seen from FIG. 13, the fluorescence emission peak position of the phosphine-oxygen containing compound (A1) after being formed into a thin film is 389nm, which is blue-violet light; after the phosphine-oxygen containing compound (A2) is prepared into a film, the fluorescence emission peak position is 423nm, and the film belongs to deep blue light. The result is consistent with the fluorescence spectrum results of A1 and A2 alone, and shows that the phosphine-oxygen-containing compounds (A1 and A2) interrupt intramolecular conjugation due to the electronic structure hybridized by SP3 in phosphine-oxygen groups, inhibit spectrum red shift caused by intense charge transfer in molecules, and are suitable for preparing blue-violet light or deep blue light materials.
(7) Thermogravimetric analysis:
thermogravimetric analysis was performed on the phosphine-oxygen-containing compounds (a1 and a2) with a high-temperature simultaneous thermal analyzer, respectively, to obtain the thermogravimetric analysis chart of fig. 14. The measurement conditions were as follows: under the protection of nitrogen, the heating rate is 10 ℃/min, and the measurement temperature range is 30-800 ℃.
As can be seen from FIG. 14, the phosphine-oxygen containing compounds (A1 and A2) exhibited thermal decomposition temperatures (T) as high as 440 and 420 ℃ respectivelyd) The method has the advantages of high stability at high temperature, high thermal stability and capability of providing necessary conditions for manufacturing devices by a vacuum evaporation process.
In conclusion, the phosphine-oxygen-containing compound prepared by the invention has better luminous intensity, color purity, thermal stability and fluorescence quantum yield, can be used as an excellent blue-violet light or deep blue light material, and is suitable for preparing a luminescent material and a photoelectric luminescent device.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A phosphine-oxygen containing compound, wherein the phosphine-oxygen containing compound has a chemical structure represented by the following formula (a1) or formula (a 2):
2. the method for producing a phosphine-oxygen-containing compound according to claim 1, comprising the steps of:
s1, heating and reacting 1, 4-dibromo-2-fluorobenzene, potassium hydroxide and potassium carbonate in an organic solvent and an inert gas to obtain a middle 1;
s2, sequentially adding n-butyl lithium and phenyl phosphorus dichloride into the intermediate 1 obtained in the step S1 at the temperature of-80 to-70 ℃ in an organic solvent for reaction, stirring for 12-16 h, and adding hydrogen peroxide for reaction to obtain an intermediate 2;
s3, heating and reacting the intermediate 2 obtained in the step S2, a donor group, tris (dibenzylacetone) dipalladium, tri-tert-butylphosphine tetrafluoroborate and sodium tert-butoxide in an organic solvent and an inert gas to obtain the phosphine-containing oxygen compound;
wherein the donor group is 3, 6-di-tert-butyl-9H-carbazole or 1,3,6, 8-tetramethyl-9H-carbazole.
3. The method according to claim 2, wherein the molar ratio of 1, 4-dibromo-2-fluorobenzene, potassium hydroxide and potassium carbonate in step S1 is 1: 0.5-0.7: 1 to 2.
4. The preparation method according to claim 2, wherein the molar ratio of the intermediate 1, n-butyllithium, phenylphosphorus dichloride and hydrogen peroxide in step S2 is 1: 2-2.3: 1-2: 3 to 4.
5. The method according to claim 2, wherein the molar ratio of the intermediate 2, the donor group, the tris (dibenzylacetone) dipalladium, the tri-tert-butylphosphine tetrafluoroborate and the sodium tert-butoxide in step S3 is 1: 2-3: 0.02-0.04: 0.08-0.1: 3 to 5.
6. The method according to claim 2, wherein the organic solvent in step S1 is triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether or ethylene glycol dimethyl ether; step S2, the organic solvent is diethyl ether or tetrahydrofuran; the organic solvent in the step S3 is toluene, chlorobenzene or o-dichlorobenzene.
7. The method according to claim 2, wherein the heating in step S1 is carried out at 180-190 ℃ for 72-96 h; and S3, heating at 100-120 ℃ for 4-6 h.
8. Use of the phosphine-oxygen-containing compound according to claim 1 for the preparation of a luminescent material or a photovoltaic light-emitting device.
9. A luminescent material comprising the phosphine-oxygen-containing compound according to claim 1 or produced from the phosphine-oxygen-containing compound according to claim 1.
10. A photovoltaic light-emitting device comprising the phosphine-oxygen-containing compound according to claim 1 or produced from the phosphine-oxygen-containing compound according to claim 1.
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|---|---|---|---|---|
| CN114716479A (en) * | 2022-05-05 | 2022-07-08 | 广州青苗新材料科技有限公司 | Phosphine oxide compound with thermal activation delayed fluorescence property and preparation and application thereof |
| CN114716479B (en) * | 2022-05-05 | 2024-01-05 | 广州青苗新材料科技有限公司 | Phosphine oxide compound with thermal activation delayed fluorescence property and preparation and application thereof |
| CN114835752A (en) * | 2022-05-24 | 2022-08-02 | 广东工业大学 | Phosphoryloxybenzonitrile compound and preparation method and application thereof |
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| CN113980054B (en) | 2023-12-15 |
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