CN110498816A - Organic phosphorus luminescent material and preparation method thereof and organic electroluminescence device - Google Patents
Organic phosphorus luminescent material and preparation method thereof and organic electroluminescence device Download PDFInfo
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- CN110498816A CN110498816A CN201910619070.8A CN201910619070A CN110498816A CN 110498816 A CN110498816 A CN 110498816A CN 201910619070 A CN201910619070 A CN 201910619070A CN 110498816 A CN110498816 A CN 110498816A
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- luminescent material
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- substituent group
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- 239000000463 material Substances 0.000 title claims abstract description 52
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 35
- 239000011574 phosphorus Substances 0.000 title claims abstract description 35
- 238000005401 electroluminescence Methods 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 125000001424 substituent group Chemical group 0.000 claims abstract description 31
- 239000003446 ligand Substances 0.000 claims abstract description 17
- 125000003118 aryl group Chemical group 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 14
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims abstract description 13
- 229910052805 deuterium Inorganic materials 0.000 claims abstract description 13
- 229910052736 halogen Inorganic materials 0.000 claims abstract description 13
- 150000002367 halogens Chemical class 0.000 claims abstract description 13
- 125000004093 cyano group Chemical group *C#N 0.000 claims abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 7
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 52
- 229910052757 nitrogen Inorganic materials 0.000 claims description 26
- 125000000217 alkyl group Chemical group 0.000 claims description 9
- WCGIGOVLOFXAMG-UHFFFAOYSA-N silver;trifluoromethanesulfonic acid Chemical compound [Ag].OS(=O)(=O)C(F)(F)F WCGIGOVLOFXAMG-UHFFFAOYSA-N 0.000 claims description 8
- 238000006467 substitution reaction Methods 0.000 claims description 8
- 239000002019 doping agent Substances 0.000 claims description 7
- -1 cyano, hydroxyl Chemical group 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 5
- 125000001931 aliphatic group Chemical group 0.000 claims description 4
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 2
- 239000005864 Sulphur Substances 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 125000005842 heteroatom Chemical group 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 230000017260 vegetative to reproductive phase transition of meristem Effects 0.000 claims description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 2
- 150000001875 compounds Chemical class 0.000 abstract description 22
- 125000000623 heterocyclic group Chemical group 0.000 abstract description 5
- 150000002902 organometallic compounds Chemical class 0.000 abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 36
- 239000010410 layer Substances 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- 238000001556 precipitation Methods 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- 239000007787 solid Substances 0.000 description 13
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 12
- 229960000935 dehydrated alcohol Drugs 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000000706 filtrate Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 7
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000004128 high performance liquid chromatography Methods 0.000 description 6
- 238000001819 mass spectrum Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000003208 petroleum Substances 0.000 description 6
- 230000001376 precipitating effect Effects 0.000 description 6
- 238000010898 silica gel chromatography Methods 0.000 description 6
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical compound C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 238000007740 vapor deposition Methods 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000002347 injection Methods 0.000 description 3
- 239000007924 injection Substances 0.000 description 3
- 229910052741 iridium Inorganic materials 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- UFVXQDWNSAGPHN-UHFFFAOYSA-K bis[(2-methylquinolin-8-yl)oxy]-(4-phenylphenoxy)alumane Chemical compound [Al+3].C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC=C([O-])C2=NC(C)=CC=C21.C1=CC([O-])=CC=C1C1=CC=CC=C1 UFVXQDWNSAGPHN-UHFFFAOYSA-K 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000013086 organic photovoltaic Methods 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 238000005424 photoluminescence Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0033—Iridium compounds
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
- H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/341—Transition metal complexes, e.g. Ru(II)polypyridine complexes
- H10K85/342—Transition metal complexes, e.g. Ru(II)polypyridine complexes comprising iridium
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/185—Metal complexes of the platinum group, i.e. Os, Ir, Pt, Ru, Rh or Pd
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
Abstract
The present invention relates to a kind of organic phosphorus luminescent material and preparation method thereof and organic electroluminescence device, the organic phosphorus luminescent material structure formula as described in chemical formula 1:Wherein: R1、R2、R3、R4And R5It is each independently selected from the condensed ring radical of hydrogen, deuterium, halogen, cyano, substituted or non-substituted C1-C6 alkyl, substituted or non-substituted C6-C18 aryl, substituted or non-substituted C4-C12 aromatic heterocyclic radical, substituted or non-substituted C8~C16；R1、R2The quantity of substituent group is 0~4, R3The quantity of substituent group is 0~2, R4、R5The quantity of substituent group is 0~3；X is O or S.New structural organic phosphorus luminescent material provided by the invention, by selecting the ligand binding of specific heterocycle, the wavelength of modulating compound, obtained organo-metallic compound is after for organic electroluminescence device, so that the luminous efficiency of device improves, and long service life.The preparation method of organic phosphorus luminescent material provided by the invention, simple and easy, product purity is high.
Description
Technical field
The present invention relates to organic photoelectrical material fields, and in particular to a kind of organic phosphorus luminescent material and preparation method thereof and
Organic electroluminescence device.
Background technique
Organic electroluminescent technology is latest generation flat panel display, can be used for flat-panel monitor and lighting source, mesh
The flat-panel monitor of preceding commercialization has put goods on the market.Lighting source is since the absolute predominance of its own is also quickly by industrialization.Electricity
Electroluminescence device has structure of whole solid state, and electroluminescent organic material is core and the basis for constituting the device.New material is opened
Hair is the driving source for pushing electroluminescent technology to be constantly progressive.It is also present Organic Electricity to the preparation of original material and device optimization
The research hotspot of photoluminescence industry.
And phosphorescence luminescence phenomenon is since discovery, is constantly subjected to that everybody chase after is high, because of the luminous efficiency of phosphor material
It is apparently higher than fluorescence radiation efficiency, can theoretically reach 100% luminous efficiency, so many scientific research institutions are all increasing
The R&D intensity of phosphate material, it is intended to which industrialized development is accelerated by phosphor material.But since phosphor material synthesizes price ratio
Higher, synthesis technology requirement is relatively high, and is easy pollution environment in the synthesis process, and purification requires relatively high, the service life
It is short, low efficiency.
Summary of the invention
The invention solves in the prior art the technical issues of, provide a kind of organic phosphorus luminescent material and preparation method thereof with
And organic electroluminescence device.New structural organic phosphorus luminescent material provided by the invention, by selecting specific heterocycle
Ligand binding, the wavelength of modulating compound, obtained organo-metallic compound for after organic electroluminescence device so that
The luminous efficiency of device improves, and long service life.
In order to solve the above-mentioned technical problem, technical solution of the present invention is specific as follows:
The present invention provides a kind of organic phosphorus luminescent material, structural formula as described in chemical formula 1:
Wherein:
R1、R2、R3、R4And R5Be each independently selected from hydrogen, deuterium, halogen, cyano, substituted or non-substituted C1-C6 alkyl,
Substituted or non-substituted C6-C18 aryl, substituted or non-substituted C4-C12 aromatic heterocyclic radical, substituted or non-substituted C8~C16
Condensed ring radical；
R1、R2、R3、R4、R5The position of substitution is any position of place ring；R1、R2The quantity of substituent group is 0~4, R3It takes
The quantity of Dai Ji is 0~2, R4、R5The quantity of substituent group is 0~3；
X is O or S.
In the above-mentioned technical solutions, the alkyl is straight chained alkyl, branched alkyl, naphthenic base, the substitution of at least one substituent group
Direct-connected alkyl, at least one substituent group replace branched alkyl or at least one substituent group replace naphthenic base；Wherein, described
Substituent group is independent selected from one or more of halogen, deuterium, cyano, hydroxyl and sulfydryl.
In the above-mentioned technical solutions, the aryl is preferably the aryl that unsubstituted aryl or at least one substituent group replace；
Wherein, the substituent group is independent is selected from halogen, deuterium, amino, cyano, nitro, hydroxyl or sulfydryl.
In the above-mentioned technical solutions, the aromatic heterocyclic radical is preferably that unsubstituted heteroaryl or at least one substituent group take
The aromatic heterocyclic radical in generation；Wherein, the hetero atom in heteroaryl is nitrogen, sulphur or oxygen；The substituent group it is independent selected from halogen, deuterium,
Amino, cyano, nitro, hydroxyl or sulfydryl.
In the above-mentioned technical solutions, R1、R2、R3、R4、R5Independent mutually form with other substituent groups on the ring of place takes
Generation or non-substituted C3~C30 aliphatic ring, substituted or non-substituted C6~C60 aromatic ring, substituted or non-substituted C2~C60 virtue
Heterocycle, substituted or non-substituted C6~C60 condensed ring or substituted or non-substituted C5~C60 loop coil；In foregoing substituents group
Substituent group is at least selected from hydrogen, deuterium, halogen, cyano, substituted or non-substituted C1-C6 alkyl, substituted or non-substituted C6-C18 virtue
Base, substituted or non-substituted C4-C12 aromatic heterocyclic radical, substituted or non-substituted C8~C16 condensed ring radical, substituted or non-substituted
One of C5~C60 loop coil.
In the above-mentioned technical solutions, R1、R2、R3、R4Between mutually form substituted or non-substituted C3~C30 aliphatic ring,
Substituted or non-substituted C6~C60 aromatic ring, substituted or non-substituted C2~C60 heteroaromatic, substituted or non-substituted C6~C60
Condensed ring or substituted or non-substituted C5~C60 loop coil；Substituent group in foregoing substituents group is at least selected from hydrogen, deuterium, halogen, cyanogen
Base, substituted or non-substituted C1-C6 alkyl, substituted or non-substituted C6-C18 aryl, substituted or non-substituted C4-C12 aromatics
One of heterocycle, the condensed ring radical of substituted or non-substituted C8~C16, substituted or non-substituted C5~C60 loop coil.
In the above-mentioned technical solutions, the most preferably described organic phosphorus luminescent material is selected from any one in flowering structure:
Some specific structure types are only listed above, but this series compound does not limit to above-mentioned molecular structure, it is all
It is that the simple transformation of these groups and its these substituted groups and the position of substitution can be obtained by other specific molecule knots
Structure, this is no longer going to repeat them.
The present invention also provides a kind of preparation methods of organic phosphorus luminescent material, comprising the following steps:
Step 1 sufficiently reacts raw material A with iridous chloride, and bridge ligand intermediate B is made；
Step 2 sufficiently reacts intermediate B with trifluoro-methane sulfonic acid silver, and intermediate C is made；
Step 3 sufficiently reacts intermediate C with intermediate D, and organic phosphorus luminescent material described in chemical formula 1 is made；
Its synthetic route is as follows:
Wherein, R1、R2、R3、R4、R5And the restriction of respective substituent group number and X are consistent with the restriction in chemical formula 1,
Which is not described herein again.
The present invention also provides a kind of organic electroluminescences comprising organic phosphorus luminescent material shown in chemical formula 1 of the present invention
Part.
The organic electroluminescence device includes:
First electrode, second electrode and the organic matter layer being placed between two electrode, wherein wrapped in the organic matter layer
Contain organic phosphorus luminescent material shown in chemical formula 1 of the present invention；Organic phosphorus luminescent material shown in chemical formula 1 of the present invention can be with
It is single form or is mixed in organic matter layer with other materials.
The organic matter layer includes at least hole injection layer, hole transmission layer, had both had hole injection but also with hole biography
Defeated technical ability layer, electronic barrier layer, luminescent layer, hole blocking layer, electron transfer layer, electron injecting layer and both has electron-transport
But also with one or more of electron injection technical ability layer.
The organic electroluminescence device includes that at least one layer of functional layer contains organic phosphorus hair shown in chemical formula 1 of the present invention
Luminescent material.
The organic electroluminescence device includes luminescent layer, and the luminescent layer contains organic shown in chemical formula 1 of the present invention
Phosphorus luminescent material.
The luminescent layer of the organic electroluminescence device includes material of main part and dopant material, and the dopant material is this hair
Organic phosphorus luminescent material shown in bright chemical formula 1.It is preferred that the mixed proportion of luminescent layer material of main part and dopant material is 90:10
~99.5:0.5.
Device of the present invention can be used for organic luminescent device, organic photovoltaic cell, Electronic Paper, Organophotoreceptor or have
Machine thin film transistor (TFT).
The beneficial effects of the present invention are:
New structural organic phosphorus luminescent material provided by the invention is adjusted by selecting the ligand binding of specific heterocycle
The wavelength of nodal compound, obtained organo-metallic compound is after for organic electroluminescence device, so that the luminous effect of device
Rate improves, and long service life.
The preparation method of organic phosphorus luminescent material provided by the invention, simple and easy, product purity is high.
Specific embodiment
In order to which method of the invention is further described, it is exemplified below more detailed embodiment and is illustrated.
1 prepare compound L001 of embodiment
Step 1, under nitrogen protection system, weigh A-001 (2- phenylpyridine 64.5mmol, 10g), IrC13·3H2O
(24.8mmo1,8.75g) is put into reaction system, and the mixed solution of 300mL ethylene glycol ethyl ether and 100mL pure water, nitrogen is added
It flows back 24 hours under gas shielded, is then cooled to room temperature, there is Precipitation, precipitating is filtered, with water, dehydrated alcohol, petroleum ether
Drying is successively rinsed, the bridge ligand B-001 (6.64g, yield 50%) of yellow powder is obtained.
Step 2 weighs intermediate B -001 (4.67mmol, 5g), is added trifluoro-methane sulfonic acid silver (14mmol, 3.6g), then
Methylene chloride 100mL is added into system, isopropanol 40mL is added, under nitrogen protection, flows back 24 hours, is cooled to room temperature,
Column chromatography (short column) filtrate is concentrated into solid precipitation, obtains complex of iridium intermediate C-001 (6.2g, the yield of yellow greenish powder
93%).
Step 3 weighs intermediate C-001 (8.4mmol, 6g), is added ligand D-001 (25.5mmol, 6.6g), then to body
It in system plus dehydrated alcohol 120mL, under nitrogen protection, flows back 24 hours, filters, alcohol is washed, and is dried, is made solvent with methylene chloride, is used
Silica gel column chromatography, filtrate are concentrated into solid precipitation, obtain 001 1.9g of compound L of final yellow, yield 30%).
HPLC purity: greater than 99%.
Mass spectrum: calculated value 760.88；Test value is 760.85.
Elemental analysis: calculated value C:59.99%；H:3.44%；N:9.20%；O:2.10%；Ir:25.26%；Test value
Are as follows: C:59.97%；H:3.42%；N:9.22%；O:2.11%；Ir:25.25%.
2 prepare compound L019 of embodiment
Step 1, under nitrogen protection system, claim raw material A -019 (59.10mmol, 10g), IrC13·3H2O
(19.7mmo1,7g) is put into reaction system, and the mixed solution of 300mL ethylene glycol ethyl ether and 100mL pure water, nitrogen is added
The lower reflux of protection 18 hours, is then cooled to room temperature, there is Precipitation, and precipitating is filtered, with water, dehydrated alcohol, petroleum ether according to
Secondary flushing drying, obtains yellow powder bridge ligand B-019 (5.4g, yield 50%).
Then step 2 weighs intermediate B -019 (4.6mmol, 5g), addition trifluoro-methane sulfonic acid silver (10.1mmol,
2.6g), methylene chloride 100mL is added then into system, is added isopropanol 30mL, under nitrogen protection, flows back 24 hours, it is cooling
To room temperature, column chromatography (short column) filtrate is concentrated into solid precipitation, obtains intermediate C-019 (5.36g, the yield of yellow greenish powder
80%).
Then step 3 weighs intermediate C-019 (6.9mmol, 5g), be added ligand D-019 (20.7mmol, 5.5g), then
It into system plus dehydrated alcohol 200mL, under nitrogen protection, flows back 12 hours, filters, alcohol is washed, and is dried, is made of methylene chloride molten
Agent, with silica gel column chromatography, filter is concentrated into solid precipitation, obtains final bright orange compound L 019 (1.6g, yield 29%).
HPLC: purity is greater than 99%.
Mass spectrum: calculated value 791.95: test value 791.90.
Elemental analysis: calculated value C:60.67%；H:4.20%；N:8.84%；O:2.02%；Ir:24.27%；Test value
Are as follows: C:60.65%；H:4.24%；N:8.85%；O:2.00%；Ir:24.30%.
3 prepare compound L037 of embodiment
Step 1, under nitrogen protection system, claim raw material A -037 (59.10mmol, 10g), IrC13·3H2O
(19.7mmo1,7g) is put into reaction system, and the mixed solution of 300mL ethylene glycol ethyl ether and 100mL pure water, nitrogen is added
The lower reflux of protection 18 hours, is then cooled to room temperature, there is Precipitation, and precipitating is filtered, with water, dehydrated alcohol, petroleum ether according to
Secondary flushing drying, obtains yellow powder bridge ligand B-037 (5.4g, yield 50%).
Then step 2 weighs intermediate B -037 (4.6mmol, 5g), addition trifluoro-methane sulfonic acid silver (10.1mmol,
2.6g), methylene chloride 100mL is added then into system, is added isopropanol 30mL, under nitrogen protection, flows back 24 hours, it is cooling
To room temperature, column chromatography (short column) filtrate is concentrated into solid precipitation, obtains intermediate C-037 (5.36g, the yield of yellow greenish powder
80%).
Then step 3 weighs intermediate C-037 (6.9mmol, 5g), be added ligand D-037 (20.7mmol, 5.7g), then
It into system plus dehydrated alcohol 200mL, under nitrogen protection, flows back 12 hours, filters, alcohol is washed, and is dried, is made of methylene chloride molten
Agent, with silica gel column chromatography, filter is concentrated into solid precipitation, obtains final bright orange compound L 037 (1.5g, yield 27%).
HPLC: purity is greater than 99%.
Mass spectrum: calculated value 802.96: test value 803.
Elemental analysis: calculated value C:61.33%；H:4.02%；N:8.72%；O:1.99%；Ir:23.94%；Test value
Are as follows: C:61.30%；H:4.04%；N:8.75%；O:2.00%；Ir:24.00%.
4 prepare compound L053 of embodiment
Step 1, under nitrogen protection system, claim raw material A -053 (58.40mmol, 10g), IrC13·3H2O
(19.5mmo1,6.90g) is put into reaction system, and the mixed solution of 300mL ethylene glycol ethyl ether and 100mL pure water, nitrogen is added
It flows back 18 hours under gas shielded, is then cooled to room temperature, there is Precipitation, precipitating is filtered, with water, dehydrated alcohol, petroleum ether
Drying is successively rinsed, yellow powder bridge ligand B-053 (5.0g, yield 45%) is obtained.
Then step 2 weighs intermediate B -053 (4.4mmol, 5g), addition trifluoro-methane sulfonic acid silver (11mmol, 2.5g,
Methylene chloride 100mL is added into system again, isopropanol 35mL is added, under nitrogen protection, flows back 24 hours, is cooled to room temperature,
Column chromatography (short column) filtrate is concentrated into solid precipitation, obtains the intermediate C-053 (6g, yield 91%) of yellow greenish powder.
Then step 3 weighs intermediate C-053 (8mmol, 6g), be added ligand D-053 (24mmol.6.3g), then to body
It in system plus dehydrated alcohol 120mL, under nitrogen protection, flows back 12 hours, filters, alcohol is washed, and is dried, is made solvent with methylene chloride, is used
Silica gel column chromatography, filter are concentrated into solid precipitation, obtain final bright orange compound L 053 (2g, yield 31.3%).
HPLC: purity is greater than 99%.
Mass spectrum: calculated value 797.99: test value 798.00.
Elemental analysis: calculated value C:60.21%；H:4.92%；N:8.78%；O:2.00%；Ir:24.09%；Test value
Are as follows: C:60.22%；H:4.94%；N:8.76%；O:2.00%；Ir:24.08%.
5 prepare compound L089 of embodiment
Step 1, under nitrogen protection system, weigh A-089 (52.84mmol, 10g), IrC13·3H2O(21.12mmo1,
It 7.45g) is put into reaction system, the mixed solution of 300mL ethylene glycol ethyl ether and 100mL pure water is added, nitrogen protection is next time
Stream 24 hours, is then cooled to room temperature, there is Precipitation, and precipitating is filtered, successively rinses baking with water, dehydrated alcohol, petroleum ether
It is dry, obtain the bridge ligand B-089 (6.8g, yield 53%) of yellow powder.
Step 2 weighs intermediate B -089 (4.96mmol, 6g), is added trifluoro-methane sulfonic acid silver (14.8mmol, 3.8g),
Methylene chloride 120mL is added into system again, isopropanol 40mL is added, under nitrogen protection, flows back 24 hours, is cooled to room temperature,
Column chromatography (short column) filtrate is concentrated into solid precipitation, obtains complex of iridium intermediate C-089 (7g, the yield of yellow greenish powder
90%).
Step 3 weighs intermediate C-089 (7.67mmol, 6g), is added ligand D-089 (23mmol, 7.4g), then to body
It in system plus dehydrated alcohol 120mL, under nitrogen protection, flows back 24 hours, filters, alcohol is washed, and is dried, is made of methylene chloride and toluene
Solvent, with silica gel column chromatography, filtrate is concentrated into solid precipitation, obtains final bright orange compound L 089 (2.3g, yield
33.8%).
HPLC purity is greater than 99%.
Mass spectrum: calculated value 888.18: test value 888.20.
Elemental analysis: calculated value C:62.21%；H:6.47%；N:7.89%；O:1.80%；Ir:21.64%；Test value
Are as follows: C:62.23%；H:6.46%；N:7.88%；O:1.81%；Ir:21.62%.
6 prepare compound L126 of embodiment
Step 1, under nitrogen protection system, weigh A-126 (2- phenylpyridine 64.5mmol, 10g), IrC13·3H2O
(24.8mmo1,8.75g) is put into reaction system, and the mixed solution of 300mL ethylene glycol ethyl ether and 100mL pure water, nitrogen is added
It flows back 24 hours under gas shielded, is then cooled to room temperature, there is Precipitation, precipitating is filtered, with water, dehydrated alcohol, petroleum ether
Drying is successively rinsed, the bridge ligand B-126 (6.64g, yield 50%) of yellow powder is obtained.
Step 2 weighs intermediate B -126 (4.67mmol, 5g), is added trifluoro-methane sulfonic acid silver (14mmol, 3.6g), then
Methylene chloride 100mL is added into system, isopropanol 40mL is added, under nitrogen protection, flows back 24 hours, is cooled to room temperature,
Column chromatography (short column) filtrate is concentrated into solid precipitation, obtains complex of iridium intermediate C-126 (6.2g, the yield of yellow greenish powder
93%).
Step 3 weighs intermediate C-126 (8.4mmol, 6g), is added ligand D-126 (25.5mmol, 9.7g), then to body
It in system plus dehydrated alcohol 200mL, under nitrogen protection, flows back 24 hours, filters, alcohol is washed, and is dried, is made of methylene chloride and toluene
Solvent, with silica gel column chromatography, filtrate is concentrated into solid precipitation, obtains final bright orange compound L 126 (2.3g, yield
31%).
HPLC purity is greater than 99%.
Mass spectrum: calculated value is that 881.09 test values are 881.10.
Elemental analysis: calculated value C:62.71%；H:3.89%；N:7.95%；S:3.64%；Ir:21.82%；Test value
Are as follows: C:62.70%；H:3.90%；N:7.96%；S:3.62%；Ir:21.84%.
The present invention also provides a kind of organic electroluminescence device, the organic electroluminescence device is by described organic phosphorus
Luminescent material is made, more specifically by being made of the organic phosphorus luminescent material in chemical formula 1.
In order to which the present invention is described in further detail, it is exemplified below more specific embodiment.
Embodiment 7
The organic phosphorus luminescent material of the compound L 001 prepared using embodiment prepares organic electroluminescence device, has more
Body:
It is by coating layer thicknessIto glass substrate be placed in distilled water and clean 2 times, ultrasonic washing 30 minutes,
It is cleaned repeatedly with distilled water 2 times, ultrasonic washing 10 minutes, after distilled water cleans, isopropanol, acetone, methanol equal solvent
It is dry after ultrasonic washing in order, it is transferred in plasma washing machine, aforesaid substrate is washed 5 minutes, vapor deposition is sent to
In machine.N1- (2- naphthalene)-N4, N4- bis- (4- (2- naphthalene (phenyl) amino) phenyl)-N1- is deposited in ITO first (anode) above
And then NPB60nm, main substance 4,4'-N, two click of N'- biphenyl is deposited in phenyl benzene-Isosorbide-5-Nitrae-diamines (" 2-TNATA ") 60nm
Azoles (" CBP ") and 001 90:10 weight ratio of dopant compound L mixing vapor deposition 30nm, vapor deposition hole blocking layer (" BAlq ")
10nm thickness, vapor deposition electron transfer layer " Alq3 " 40nm thickness, vapor deposition electron injecting layer LiF0.2nm, evaporation cathode Al are
Organic electroluminescence device is prepared in 150nm form.Performance characteristics of luminescence test to obtained device, measurement use
2400 type source measuring unit of KEITHLEY, CS-2000 spectroradio luminance meter, to evaluate driving voltage, light emission luminance shines
Efficiency.
Referring to the above method, compound L 001 is replaced with into L019, L037, L053, L089, L126 respectively, is prepared
The organic electroluminescence device of respective compound.
Comparative example 1
Organic electroluminescence device is prepared according to the identical method of embodiment 7, luminescent layer green light doped compound structure is such as
Under:
Detection same as Example 7 is carried out to the organic electroluminescence device of preparation, the results are shown in Table 1.
Organic electroluminescence device testing result in 1 embodiment 7 of table and comparative example 1
As can be seen from Table 1, use organic phosphorus luminescent material provided by the invention as prepared by luminescent layer dopant material
Organic electroluminescence device compared with using compound Ir (ppy) 3 as organic electroluminescence prepared by luminescent layer dopant material
Luminescent device is compared, and driving voltage and current density are substantially reduced, and luminous efficiency and service life are significantly improved.
The above description of the embodiment is only used to help understand the method for the present invention and its core ideas.It should be pointed out that pair
For those skilled in the art, without departing from the principle of the present invention, the present invention can also be carried out
Some improvements and modifications, these improvements and modifications also fall within the scope of protection of the claims of the present invention.
Claims (10)
1. a kind of organic phosphorus luminescent material, which is characterized in that its structural formula as described in chemical formula 1:
Wherein:
R1、R2、R3、R4And R5Be each independently selected from hydrogen, deuterium, halogen, cyano, substituted or non-substituted C1-C6 alkyl, replace or
Non-substituted C6-C18 aryl, substituted or non-substituted C4-C12 aromatic heterocyclic radical, substituted or non-substituted C8~C16 condensed ring
Base；
R1、R2、R3、R4、R5The position of substitution is any position of place ring；R1、R2The quantity of substituent group is 0~4, R3Substituent group
Quantity be 0~2, R4、R5The quantity of substituent group is 0~3；
X is O or S.
2. organic phosphorus luminescent material according to claim 1, which is characterized in that the alkyl is straight chained alkyl, branched alkane
The branched alkyl or at least one of direct-connected alkyl, the substitution of at least one substituent group that base, naphthenic base, at least one substituent group replace take
The naphthenic base replaced for base；Wherein, the substituent group is independent selected from one of halogen, deuterium, cyano, hydroxyl and sulfydryl or several
Kind.
3. organic phosphorus luminescent material according to claim 1, which is characterized in that the aryl is for unsubstituted aryl or extremely
The aryl that few 1 substituent group replaces；Wherein, the substituent group it is independent selected from halogen, deuterium, amino, cyano, nitro, hydroxyl or
Sulfydryl.
4. organic phosphorus luminescent material according to claim 1, which is characterized in that the aromatic heterocyclic radical is unsubstituted miscellaneous
The aromatic heterocyclic radical that aryl or at least one substituent group replace；Wherein, the hetero atom in heteroaryl is nitrogen, sulphur or oxygen；The substitution
Base is independent to be selected from halogen, deuterium, amino, cyano, nitro, hydroxyl or sulfydryl.
5. organic phosphorus luminescent material according to claim 1, which is characterized in that R1、R2、R3、R4、R5Independent and institute
Other substituent groups mutually form substituted or non-substituted C3~C30 aliphatic ring, substituted or non-substituted C6~C60 virtue on ring
Ring, substituted or non-substituted C2~C60 heteroaromatic, substituted or non-substituted C6~C60 condensed ring or substituted or non-substituted C5~
C60 loop coil；Substituent group in foregoing substituents group is at least selected from hydrogen, deuterium, halogen, cyano, substituted or non-substituted C1-C6 alkane
Base, substituted or non-substituted C6-C18 aryl, substituted or non-substituted C4-C12 aromatic heterocyclic radical, substituted or non-substituted C8~
One of the condensed ring radical of C16, substituted or non-substituted C5~C60 loop coil.
6. organic phosphorus luminescent material according to claim 1, which is characterized in that R1、R2、R3、R4Between mutually form substitution
Or non-substituted C3~C30 aliphatic ring, substituted or non-substituted C6~C60 aromatic ring, substituted or non-substituted C2~C60 virtue are miscellaneous
Ring, substituted or non-substituted C6~C60 condensed ring or substituted or non-substituted C5~C60 loop coil；Substitution in foregoing substituents group
Base is at least selected from hydrogen, deuterium, halogen, cyano, substituted or non-substituted C1-C6 alkyl, substituted or non-substituted C6-C18 aryl, takes
Generation or non-substituted C4-C12 aromatic heterocyclic radical, the condensed ring radical of substituted or non-substituted C8~C16, substituted or non-substituted C5~
One of C60 loop coil.
7. organic phosphorus luminescent material according to claim 1, which is characterized in that it is selected from any one in flowering structure
Kind:
8. a kind of preparation method of organic phosphorus luminescent material described in claim 1-7 any one, which is characterized in that including with
Lower step:
Step 1 sufficiently reacts raw material A with iridous chloride, and bridge ligand intermediate B is made；
Step 2 sufficiently reacts intermediate B with trifluoro-methane sulfonic acid silver, and intermediate C is made；
Step 3 sufficiently reacts intermediate C with intermediate D, and organic phosphorus luminescent material described in chemical formula 1 is made；
Its synthetic route is as follows:
9. a kind of organic electroluminescence device comprising organic phosphorus luminescent material described in claim 1-7 any one.
10. organic electroluminescence device according to claim 9, which is characterized in that the organic phosphorescent material is as hair
Photosphere dopant material.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111004289A (en) * | 2019-12-05 | 2020-04-14 | 吉林奥来德光电材料股份有限公司 | Iridium metal complex and preparation method thereof |
| CN111233935A (en) * | 2019-12-24 | 2020-06-05 | 吉林奥来德光电材料股份有限公司 | Metal iridium complex, preparation method thereof and organic electroluminescent device comprising metal iridium complex |
| CN112939990A (en) * | 2021-02-04 | 2021-06-11 | 吉林奥来德光电材料股份有限公司 | Luminescent compound with organic condensed rings, preparation method thereof and organic electroluminescent device |
| CN113788847A (en) * | 2021-08-24 | 2021-12-14 | 陕西莱特迈思光电材料有限公司 | Organic compound, and electronic element and electronic device using same |
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2019
- 2019-07-10 CN CN201910619070.8A patent/CN110498816A/en not_active Withdrawn
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111004289A (en) * | 2019-12-05 | 2020-04-14 | 吉林奥来德光电材料股份有限公司 | Iridium metal complex and preparation method thereof |
| CN111233935A (en) * | 2019-12-24 | 2020-06-05 | 吉林奥来德光电材料股份有限公司 | Metal iridium complex, preparation method thereof and organic electroluminescent device comprising metal iridium complex |
| CN112939990A (en) * | 2021-02-04 | 2021-06-11 | 吉林奥来德光电材料股份有限公司 | Luminescent compound with organic condensed rings, preparation method thereof and organic electroluminescent device |
| CN112939990B (en) * | 2021-02-04 | 2022-08-12 | 吉林奥来德光电材料股份有限公司 | Luminescent compound with organic condensed rings, preparation method thereof and organic electroluminescent device |
| CN113788847A (en) * | 2021-08-24 | 2021-12-14 | 陕西莱特迈思光电材料有限公司 | Organic compound, and electronic element and electronic device using same |
| CN113788847B (en) * | 2021-08-24 | 2023-11-03 | 陕西莱特迈思光电材料有限公司 | Organic compound, and electronic component and electronic device using same |
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