CN110903323A - Organic electrophosphorescent material, preparation method and application thereof, and OLED device comprising organic electrophosphorescent material - Google Patents
Organic electrophosphorescent material, preparation method and application thereof, and OLED device comprising organic electrophosphorescent material Download PDFInfo
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- CN110903323A CN110903323A CN201811081671.XA CN201811081671A CN110903323A CN 110903323 A CN110903323 A CN 110903323A CN 201811081671 A CN201811081671 A CN 201811081671A CN 110903323 A CN110903323 A CN 110903323A
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- 239000000463 material Substances 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 150000001875 compounds Chemical class 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims description 66
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 45
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 239000002904 solvent Substances 0.000 claims description 20
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000001704 evaporation Methods 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 12
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 claims description 10
- 229940093475 2-ethoxyethanol Drugs 0.000 claims description 10
- 239000007818 Grignard reagent Substances 0.000 claims description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 10
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical class CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 10
- 238000004440 column chromatography Methods 0.000 claims description 10
- 239000000539 dimer Substances 0.000 claims description 10
- 150000004795 grignard reagents Chemical class 0.000 claims description 10
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 238000000746 purification Methods 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 10
- 229960000583 acetic acid Drugs 0.000 claims description 8
- 125000002723 alicyclic group Chemical group 0.000 claims description 8
- 229910052741 iridium Inorganic materials 0.000 claims description 8
- 239000003446 ligand Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 5
- 239000012362 glacial acetic acid Substances 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 5
- 229920000137 polyphosphoric acid Polymers 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- -1 amino, silyl Chemical group 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 125000005843 halogen group Chemical group 0.000 claims description 4
- 230000005525 hole transport Effects 0.000 claims description 4
- 238000002347 injection Methods 0.000 claims description 4
- 239000007924 injection Substances 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical group C12=CC=CC=C2C2=CC=CC=C2N1C1=CC=C(N(C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=2C=CC(=CC=2)N2C3=CC=CC=C3C3=CC=CC=C32)C=C1 AWXGSYPUMWKTBR-UHFFFAOYSA-N 0.000 claims description 3
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 claims description 3
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 125000002252 acyl group Chemical group 0.000 claims description 2
- 125000001931 aliphatic group Chemical group 0.000 claims description 2
- 125000003342 alkenyl group Chemical group 0.000 claims description 2
- 125000000304 alkynyl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 claims description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 2
- 125000000392 cycloalkenyl group Chemical group 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- 125000004404 heteroalkyl group Chemical group 0.000 claims description 2
- 125000001072 heteroaryl group Chemical group 0.000 claims description 2
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 2
- 229910052762 osmium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 230000000171 quenching effect Effects 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000010898 silica gel chromatography Methods 0.000 claims description 2
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims description 2
- 229910052723 transition metal Inorganic materials 0.000 claims description 2
- 230000000903 blocking effect Effects 0.000 claims 2
- 238000000034 method Methods 0.000 claims 2
- 150000002148 esters Chemical class 0.000 claims 1
- FVZVCSNXTFCBQU-UHFFFAOYSA-N phosphanyl Chemical group [PH2] FVZVCSNXTFCBQU-UHFFFAOYSA-N 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 238000010992 reflux Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000012043 crude product Substances 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 230000005281 excited state Effects 0.000 description 7
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 229910021638 Iridium(III) chloride Inorganic materials 0.000 description 3
- 238000005481 NMR spectroscopy Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000741 silica gel Substances 0.000 description 3
- 229910002027 silica gel Inorganic materials 0.000 description 3
- 239000012265 solid product Substances 0.000 description 3
- 238000000859 sublimation Methods 0.000 description 3
- 230000008022 sublimation Effects 0.000 description 3
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- RDHPKYGYEGBMSE-UHFFFAOYSA-N bromoethane Chemical compound CCBr RDHPKYGYEGBMSE-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- LKNKAEWGISYACD-UHFFFAOYSA-N 1-bromobuta-1,3-diene Chemical compound BrC=CC=C LKNKAEWGISYACD-UHFFFAOYSA-N 0.000 description 1
- IXHWGNYCZPISET-UHFFFAOYSA-N 2-[4-(dicyanomethylidene)-2,3,5,6-tetrafluorocyclohexa-2,5-dien-1-ylidene]propanedinitrile Chemical compound FC1=C(F)C(=C(C#N)C#N)C(F)=C(F)C1=C(C#N)C#N IXHWGNYCZPISET-UHFFFAOYSA-N 0.000 description 1
- VQGHOUODWALEFC-UHFFFAOYSA-N 2-phenylpyridine Chemical group C1=CC=CC=C1C1=CC=CC=N1 VQGHOUODWALEFC-UHFFFAOYSA-N 0.000 description 1
- DHDHJYNTEFLIHY-UHFFFAOYSA-N 4,7-diphenyl-1,10-phenanthroline Chemical compound C1=CC=CC=C1C1=CC=NC2=C1C=CC1=C(C=3C=CC=CC=3)C=CN=C21 DHDHJYNTEFLIHY-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910019032 PtCl2 Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 125000004093 cyano group Chemical group *C#N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 125000004185 ester group Chemical group 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 125000002462 isocyano group Chemical group *[N+]#[C-] 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 125000000475 sulfinyl group Chemical group [*:2]S([*:1])=O 0.000 description 1
- 125000004149 thio group Chemical group *S* 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic System 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
-
- 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
-
- 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
Abstract
The invention provides an organic electrophosphorescent material, a preparation method and application thereof, and an OLED device containing the organic electrophosphorescent material. The organic electrophosphorescent material is a compound with a structure shown in formula I, formula II or formula III. Wherein the compound with the structure of the formula I is a green luminescent material, and the compounds with the structures of the formula II and the formula III are red luminescent materials. The organic electrophosphorescent material provided by the invention is easy to sublimate and dissolve, and is beneficial to the large-scale production of OLEDs; the OLED device using the organic electrophosphorescent material provided by the invention as the guest material of the light-emitting layer has the advantages of high efficiency and long service life.
Description
Technical Field
The invention belongs to the technical field of OLED (organic light emitting diode) luminescent materials, and particularly relates to an organic electrophosphorescent material, a preparation method and application thereof, and an OLED device containing the organic electrophosphorescent material.
Background
The technology of Organic Light Emitting Diodes (OLEDs) is undergoing rapid development. OLEDs initially emit light using singlet excitons generated by electrically excited molecules. This radiative emission from singlet excited states is called fluorescence, but its luminous efficiency is low. Since the organic electrophosphorescent materials of high-efficiency heavy metal complexes have been proposed, phosphorescent materials emitting light by triplet radiation, especially iridium-based complex phosphorescent materials, have attracted attention for their high luminous efficiency and energy conversion rate, and have been the focus of organic electroluminescence research.
According to simple statistical arguments and experimental determinations, approximately 75% of the excitons (exiton) formed in an OLED are triplet excitons and 25% are singlet excitons. Triplet excitons more readily transfer their energy to triplet excited states that can produce phosphorescence, whereas singlet excitons typically transfer their energy to singlet excited states that can produce fluorescence. Because the lowest emitting singlet excited state of an organic molecule is typically at a slightly higher energy than the lowest triplet excited state, the singlet excited state can intersystem jump to the triplet excited state. This means that all excitons can be utilized as phosphorescent emission. Therefore, electrophosphorescent OLEDs have a theoretical quantum efficiency of 100%.
However, due to the fact that the heavy metal-second ligand complex has a large molecular weight, and the interaction force between the molecules of the used conjugated light-emitting second ligand is large, most organic metal complexes have the problems of sublimation, evaporation temperature close to the decomposition temperature of the complex, difficulty in dissolving and purifying and the like, and the large-scale production of the OLED is influenced.
In addition, the market has continuously raised performance requirements for OLED display and lighting products, and in order to obtain an efficient and long-life OLED device, it is imperative to develop an organic electrophosphorescent material with higher luminous efficiency and easy manufacturing.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide an organic electrophosphorescent material, a preparation method and application thereof and an OLED device containing the organic electrophosphorescent material. The organic electrophosphorescent material is easy to sublimate and dissolve, is beneficial to the large-scale production of the OLED, and the OLED device taking the organic electrophosphorescent material as a light-emitting layer guest material has the advantages of high efficiency and long service life.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an organic electrophosphorescent material, wherein the organic electrophosphorescent material is a compound having a structure of formula I, formula II or formula III;
wherein, Z ring is an alicyclic ring or an alicyclic ring;
Ra、Rband RcIs a substituent group on the Z ring which satisfies the chemical environment;
R1-R22each independently selected from one of a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted heteroalkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted heterocycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryloxy group, an amino group, a silyl group, an alkenyl group, a cycloalkenyl group, a heteroalkenyl group, an alkynyl group, an acyl group, a carbonyl group, a carboxyl group, an ester group, a cyano group, an isocyano group, a thio group, a sulfinyl group, a sulfonyl group, or a phosphino group;
m is a transition metal element, L is a second ligand for M, M is the maximum coordination number for M, d is the degree of denticity for L, and n is an integer from 1 to M/2.
According to the invention, by introducing the alicyclic ring or lipoheterocyclic ring structure into the structures of the formula I, the formula II and the formula III, on one hand, a three-dimensional structure can be formed, and the acting force among molecules is weakened, so that the obtained organic electrophosphorescent material is easier to sublimate; on the other hand, the solubility of the material can be increased. In addition, the introduction of the fat ring can narrow the light-emitting spectrum, thereby improving the light-emitting efficiency.
In the present invention, when n is m/2, (m-2n)/d is 0, that is, the structure of formula I, formula II or formula III does not contain the second ligand L. Ra、RbAnd RcEach independently represents unsubstituted, mono-or polysubstituted, with the understanding that there is only one substituent on the Z ring. One skilled in the art can determine R based on the number of substitutable positions on the Z ringa、RbAnd RcNumber of substituents
In a preferred embodiment of the present invention, the Z ring is a 3-7 membered (for example, 3-, 4-, 5-, 6-or 7-membered) alicyclic or alicyclic ring.
Preferably, R1-R22Are all hydrogen atoms.
Preferably, Ra、RbAnd RcAre independently selected fromOne selected from a hydrogen atom, a halogen atom or an alkyl group.
In a preferred embodiment of the present invention, M is Ir (iridium), Pt (platinum), Os (osmium) or Re (rhenium).
When M is Ir, the maximum coordination number M is 6, n can be 1, 2 or 3;
when M is Pt, the maximum coordination number M is 4, and n can be 1 or 2;
when M is Os, the maximum coordination number M is 6, and n can be 1, 2 or 3;
when M is Re, its maximum coordination number M is 6, and n may be 1, 2 or 3.
In a preferred embodiment of the present invention, L is substituted or unsubstituted acetylacetone.
As a preferred technical scheme of the invention, the organic electrophosphorescent material is a compound with the following structure:
wherein, the Z ring is a 3-7 membered fat ring.
In a second aspect, the present invention provides a preparation method of the above organic electrophosphorescent material, including the following steps:
(1) the compound
Mixing one of the raw materials with phenylboronic acid, an alkaline substance, triphenylphosphine, palladium acetate, water and dioxane, and reacting to obtain a compound
(2) The compound
Mixing with polyphosphoric acid, and reacting to obtain compound
(3) Dissolving n-bromoalkane or 1-bromoolefin in tetrahydrofuran, then dropwise adding the tetrahydrofuran into magnesium powder, and reacting to obtain a Grignard reagent;
(4) the compound
Mixing with the Grignard reagent obtained in the step (3), reacting, and adding water for quenching after the reaction is finished;
(5) mixing the reaction product obtained in the step (4) with glacial acetic acid and concentrated sulfuric acid, and reacting to obtain a compound
With or without substitution to give compounds
(6) Mixing the compound obtained in the step (5), salt of M, water and 2-ethoxyethanol, and reacting to obtain a dimer compound;
(7) and (3) mixing one of the second ligand L or the compound obtained in the step (5), the dimer compound obtained in the step (6), an alkaline substance and 2-ethoxyethanol, and reacting to obtain the organic electrophosphorescent material.
It should be noted that the type of the n-bromoalkane in the step (3) depends on the size of the Z ring, and when the Z ring is an x-membered ring, the carbon atom in the n-bromoalkane is x-1; and (5) when the compound obtained in the step (5) is selected to participate in the reaction in the step (7), obtaining the organic electrophosphorescent material without the second ligand L.
As a preferred technical scheme of the invention, the reaction in the step (1) and the step (6) is carried out under the protection of nitrogen.
Preferably, the alkaline substance in step (1) and step (7) is each independently sodium carbonate and/or potassium carbonate.
Preferably, the reaction temperature in step (1) is 20-40 ℃, for example, 20 ℃, 22 ℃, 23 ℃, 25 ℃, 26 ℃, 28 ℃, 30 ℃, 32 ℃, 33 ℃, 35 ℃, 36 ℃, 38 ℃ or 40 ℃ etc.; the time is 20 to 28 hours, and may be, for example, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, or 28 hours.
Preferably, step (1) further comprises purification: after the reaction, the pH of the reaction mixture was adjusted to 2 to 3, and the mixture was extracted with ethyl acetate, and the solvent was distilled off.
Preferably, the reaction temperature in step (2) is 200-; the time is 4 to 6 hours, and may be, for example, 4 hours, 4.2 hours, 4.5 hours, 4.8 hours, 5 hours, 5.2 hours, 5.5 hours, 5.8 hours, or 6 hours.
Preferably, step (2) further comprises purification: after the reaction is finished, adding ice water into the reaction solution, adjusting the pH to be more than 7, extracting with ethyl acetate, evaporating to remove the solvent, and carrying out column chromatography separation.
As a preferred embodiment of the present invention, the temperature of the reaction in the step (3) is 20 to 40 ℃, and may be, for example, 20 ℃, 22 ℃, 23 ℃, 25 ℃, 26 ℃, 28 ℃, 30 ℃, 32 ℃, 33 ℃, 35 ℃, 36 ℃, 38 ℃ or 40 ℃ or the like; the time is 2 to 4 hours, and may be, for example, 2 hours, 2.2 hours, 2.5 hours, 2.8 hours, 3 hours, 3.2 hours, 3.5 hours, 3.8 hours, or 4 hours.
Preferably, the reaction temperature in step (4) is 20-40 ℃, for example, 20 ℃, 22 ℃, 23 ℃, 25 ℃, 26 ℃, 28 ℃, 30 ℃, 32 ℃, 33 ℃, 35 ℃, 36 ℃, 38 ℃ or 40 ℃ and the like; the time is 8 to 10 hours, and may be, for example, 8 hours, 8.2 hours, 8.5 hours, 8.8 hours, 9 hours, 9.2 hours, 9.5 hours, 9.8 hours, or 10 hours.
Preferably, step (4) further comprises purification: after the reaction, the mixture was extracted with dichloromethane, and the solvent was distilled off.
Preferably, the reaction temperature in step (5) is 20-40 ℃, for example, 20 ℃, 22 ℃, 23 ℃, 25 ℃, 26 ℃, 28 ℃, 30 ℃, 32 ℃, 33 ℃, 35 ℃, 36 ℃, 38 ℃ or 40 ℃ and the like; the time is 4 to 6 hours, and may be, for example, 4 hours, 4.2 hours, 4.5 hours, 4.8 hours, 5 hours, 5.2 hours, 5.5 hours, 5.8 hours, or 6 hours.
Preferably, step (5) further comprises purification: after the reaction is finished, the pH value of the reaction solution is adjusted to be more than 7, dichloromethane is used for extraction, the solvent is distilled off, and column chromatography separation is carried out.
Preferably, the reaction temperature in step (6) is 80-120 ℃, for example, 80 ℃, 82 ℃, 85 ℃, 88 ℃, 90 ℃, 92 ℃, 95 ℃, 98 ℃, 100 ℃, 102 ℃, 105 ℃, 108 ℃, 110 ℃, 112 ℃, 115 ℃, 118 ℃ or 120 ℃ and the like; the time is 12 to 18 hours, and may be, for example, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, or the like.
Preferably, the reaction temperature in step (7) is 20-40 ℃, for example, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃, 29 ℃, 30 ℃, 31 ℃, 32 ℃, 33 ℃, 34 ℃, 35 ℃, 36 ℃, 37 ℃, 38 ℃, 39 ℃ or 40 ℃ and the like; the time is 20 to 28 hours, and may be, for example, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours, 25 hours, 26 hours, 27 hours, or 28 hours.
Preferably, step (6) and step (7) further comprise: after the reaction, the reaction product was filtered and washed.
The reagent used for washing is not particularly limited in the present invention, and washing with an alcohol (e.g., methanol) may be carried out, for example.
Preferably, step (7) further comprises purification: after the reaction was completed, the reaction product was separated by silica gel column chromatography and then eluted with methylene chloride.
In a third aspect, the present invention provides a use of the above organic electrophosphorescent material for an OLED.
In a fourth aspect, the present invention provides an OLED device comprising: the organic light-emitting diode comprises an anode, a cathode and one or more organic thin film layers arranged between the anode and the cathode, wherein the organic thin film layers at least comprise a light-emitting layer;
the host material or the guest material of the light-emitting layer is the organic electrophosphorescent material provided by the first aspect of the present invention.
As a preferred technical scheme of the present invention, the OLED device sequentially includes, from bottom to top: an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and a cathode.
In addition, in each layer of the OLED device, at least the light-emitting layer contains the organic electrophosphorescent material provided by the present invention. The organic electrophosphorescent material provided by the invention can be used as a host material of a luminescent layer and can also be used as a guest material of the luminescent layer.
Preferably, the mass percentage content of the host material in the light-emitting layer is 80-98%, and may be, for example, 80%, 82%, 83%, 85%, 86%, 88%, 90%, 92%, 93%, 95%, 96%, 98%, or the like; the guest material may be contained in an amount of 2 to 20% by mass, for example, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 20% or the like.
Preferably, the host material of the light-emitting layer is TCTA, and the guest material is the organic electrophosphorescent material provided by the first aspect of the present invention.
Compared with the prior art, the invention has the following beneficial effects:
according to the invention, the aliphatic ring or the lipoheterocyclic structure is introduced into the organic electrophosphorescent material molecules, so that on one hand, a three-dimensional structure can be formed, and the acting force among molecules is weakened, thus the obtained organic electrophosphorescent material is easier to sublimate; on the other hand, the solubility of the material can be increased. The organic electrophosphorescent material provided by the invention has the sublimation temperature of 200-220 ℃, is easy to dissolve in organic solvents such as toluene, acetone and the like, and is beneficial to the large-scale production of OLEDs.
The OLED device using the organic electrophosphorescent material provided by the invention as the guest material of the light-emitting layer has the advantages of high efficiency and long service life. The organic electrophosphorescent material with the structure shown in the formula I can emit green light, the current efficiency of an OLED device prepared from the organic electrophosphorescent material is 50-100Cd/A, the driving voltage is 3.2-4.5V, and LT is95170 ℃ for 250 hours; the organic electrophosphorescent materials with the structures of the formula II and the formula III can emit red light, the current efficiency of the OLED device prepared by the organic electrophosphorescent materials is 30-50Cd/A, the driving voltage is 3.2-4.5V, and LT is95170-.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Examples 1 to 5
Examples 1-5 provide iridium-based organic electrophosphorescent materials (denoted as Ir-1 through Ir-5 in the order named) having the structure of formula I, which have the following structural formulas:
taking Ir-3 as an example, the preparation method is as follows:
(1) the compound
(2.02g, 10mmol), phenylboronic acid (1.8g, 15mmol), potassium carbonate (5g, 50mmol), triphenylphosphine (15g, 50mmol), palladium acetate (0.15g, 0.62mmol), water (20mL) and dioxane (50mL) were mixed, the mixture was refluxed at 25 ℃ for 24 hours under nitrogen protection, cooled after the reaction was completed, adjusted to pH 2-3 with 3% acetic acid, extracted with ethyl acetate (3X 20mL), and the solvent was evaporated to give a compound
3g of the crude product of (1); mixing the crude product with 50mL of polyphosphoric acid, reacting at 210 ℃ for 5h, cooling after the reaction is finished, adding 50mL of ice water, and adjusting the pH value with NaOH solution (1mol/L)>Extracting with ethyl acetate (3 × 20mL), evaporating to remove solvent, and separating by column chromatography to obtain compound
(2) Dissolving n-bromobutane (1.35g, 10mmol) in dry tetrahydrofuran (30mL), slowly dropwise adding into magnesium powder (0.3g, 11mmol), and carrying out reflux reaction at 25 ℃ for 2h to obtain a Grignard reagent; then the compound is mixed
(1.80g, 10mmol) was dissolved in tetrahydrofuran (30mL), added to the above Grignard reagent, reacted at 25 ℃ under reflux for 8h, quenched with water (5mL), extracted with dichloromethane (3X 20mL), and then the solvent was evaporated; mixing the obtained crude product, glacial acetic acid (50mL) and two drops of concentrated sulfuric acid, carrying out reflux reaction at 25 ℃ for 5h, and adjusting the pH of the system with NaOH solution (1mol/L)>7, extracting with dichloromethane, evaporating to remove solvent, and separating by column chromatography to obtain compound
(3) The compound
(6.62g，30.0mmol)、IrCl3·H2O (3.7g, 10mmol), water (30mL) and 2-ethoxyethanol (90mL) were mixed and reacted at 120 ℃ under nitrogen for 12h under reflux, the reaction formula is as follows:
after the reaction is finished, filtering, washing with methanol (3X 20mL), and drying in vacuum to obtain a dimer compound;
(4) the compound
(100mmol), the dimer compound obtained in step (3) (9g, 10mmol), sodium carbonate (10.6g, 100mmol) and 2-ethoxyethanol (200mL) were mixed and reacted at 25 ℃ for 24h, the reaction formula being as follows:
after the reaction was complete, filtration was carried out, the precipitate was washed with methanol, and the solid product was further purified by passage through a short column of silica gel (pretreated with 15% TEA in hexane) and eluted with dichloromethane to give the product Ir-3.
The product Ir-3 is subjected to1And (4) detecting by using H NMR (nuclear magnetic resonance),1H NMR(400MHz,CDCl3):δ8.54(d,3H),7.41(d,3H),7.20(m,9H),6.89(m,3H),2.09(m,12H),1.51(m,12H)。
the person skilled in the art can replace n-bromobutane in the step (2) with bromoethane, n-bromopropane, n-bromopentane or n-bromohexane to prepare the compound according to the structure of the target product and the preparation method of Ir-3
Thus obtaining Ir-1, Ir-2, Ir-4 and Ir-5.
Examples 6 to 10
Examples 6-10 provide iridium-based organic electrophosphorescent materials (denoted as Ir-6 through Ir-10 in the order) having the structure of formula I, which have the following structural formulas:
taking Ir-8 as an example, the preparation method is as follows:
(1) preparation of Compounds according to the preparation of Ir-3
(2) The compound
(6.62g，30.0mmol)、IrCl3·H2O (3.7g, 10mmol), water (30mL) and 2-ethoxyethanol (90mL) were mixed and reacted at 120 ℃ under nitrogen for 12h under reflux, the reaction formula is as follows:
after the reaction is finished, filtering, washing with methanol (3X 20mL), and drying in vacuum to obtain a dimer compound;
(3) acetylacetone (10g, 100mmol), the dimer compound obtained in step (2) (9g, 10mmol), sodium carbonate (10.6g, 100mmol) and 2-ethoxyethanol (200mL) were mixed and reacted at 25 ℃ for 24h, the reaction formula being as follows:
after the reaction was complete, filtration was carried out, the precipitate was washed with methanol, and the solid product was further purified by passage through a short column of silica gel (pretreated with 15% TEA in hexane) and eluted with dichloromethane to give the product Ir-8.
The product Ir-8 is subjected to1And (4) detecting by using H NMR (nuclear magnetic resonance),1H NMR(400MHz,DMSO):δ8.54(d,2H),7.45(d,2H),7.20(m,6H),6.89(d,2H),6.10(s,1H),2.09(m,8H),2.03(m,6H),1.51(m,8H)。
the compound can be prepared by the skilled person according to the structure of the target product and the preparation method of Ir-8
Is replaced by
Thus obtaining Ir-6, Ir-7, Ir-9 and Ir-10.
Examples 11 to 16
Examples 11-16 provide iridium-based organic electrophosphorescent materials (denoted as Ir-11 through Ir-16 in the order of formula II) having the following structural formulas:
taking Ir-16 as an example, the preparation method is as follows:
(1) the compound
(2.5g, 10mmol), Phenylboronic acid (1.8g, 15mmol)) Mixing potassium carbonate (5g, 50mmol), triphenylphosphine (15g, 50mmol), palladium acetate (0.15g, 0.62mmol), water (20mL) and dioxane (50mL), refluxing at 25 deg.C for 24h under nitrogen protection, cooling after reaction, adjusting pH to 2-3 with 3% acetic acid, extracting with ethyl acetate (3 × 20mL), and evaporating to remove solvent to obtain compound
3g of the crude product of (1); mixing the crude product with 50mL of polyphosphoric acid, reacting at 210 ℃ for 5h, cooling after the reaction is finished, adding 50mL of ice water, and adjusting the pH value with NaOH solution (1mol/L)>Extracting with ethyl acetate (3 × 20mL), evaporating to remove solvent, and separating by column chromatography to obtain compound
(2) Dissolving n-bromobutane (1.35g, 10mmol) in dry tetrahydrofuran (30mL), slowly dropwise adding into magnesium powder (0.3g, 11mmol), and carrying out reflux reaction at 25 ℃ for 2h to obtain a Grignard reagent; then the compound is mixed
(2.3g, 10mmol) in tetrahydrofuran (30mL), the mixture was added to the above Grignard reagent, the reaction was refluxed at 25 ℃ for 8 hours, water (5mL) was added to quench the reaction, and after extraction with dichloromethane (3X 20mL), the solvent was distilled off; mixing the obtained crude product, glacial acetic acid (50mL) and two drops of concentrated sulfuric acid, carrying out reflux reaction at 25 ℃ for 5h, and adjusting the pH of the system with NaOH solution (1mol/L)>7, extracting with dichloromethane, evaporating to remove solvent, and separating by column chromatography to obtain compound
(3) The compound
(8.42g，30.0mmol)、IrCl3·H2O (3.7g, 10mmol), water (30mL) and 2-ethoxyethanol (90mL) were mixed and reacted at 80 ℃ under nitrogen for 18h under reflux, the reaction formula is as follows:
after the reaction is finished, filtering, washing with methanol (3X 20mL), and drying in vacuum to obtain a dimer compound;
(4) acetylacetone (10g, 100mmol), the dimer compound obtained in step (3) (10g, 10mmol), sodium carbonate (10.6g, 100mmol) and 2-ethoxyethanol (200mL) were mixed and reacted at 25 ℃ for 24h, the reaction formula being as follows:
after the reaction was complete, filtration was performed, the precipitate was washed with methanol, and the solid product was further purified by passing through a short column of silica gel (pretreated with 15% TEA in hexane) and eluting with dichloromethane to give the product Ir-16.
The product Ir-16 is subjected to1And (4) detecting by using H NMR (nuclear magnetic resonance),1H NMR(400MHz,DMSO):δ8.13(d,1H),7.75(d,1H),7.62(d,1H),7.52(d,1H),7.46(m,1H),7.20(m,3H),6.40(m,1H)，2.07(m,4H),2.03(m,6H),1.51(m,4H)。
one skilled in the art can prepare the compound by replacing n-bromobutane in the step (2) with n-bromohexane, n-bromopentane, 1-bromobutadiene, bromoethane or n-bromopropane according to the structure of the target product and the preparation method of Ir-16
Thus obtaining Ir-11 to Ir-15.
Examples 17 to 20
Examples 17 to 20 provide iridium-based organic electrophosphorescent materials (denoted as Ir-17 to Ir-20 in the order named) having the structure of formula II, which are respectively as follows:
the person skilled in the art can replace acetylacetone in the step (4) with a compound according to the preparation method of Ir-11-Ir-16 and the structure of the target compound
Thus obtaining Ir-17 to Ir-20.
Examples 21 to 25
Examples 21-24 provide iridium-based organic electrophosphorescent materials (denoted as Ir-21 through Ir-24 in the order of formula III) having the following structural formulas:
taking Ir-21 as an example, the preparation method is as follows:
(1) the compound
(2.5g, 10mmol), phenylboronic acid (1.8g, 15mmol), potassium carbonate (5g, 50mmol), triphenylphosphine (15g, 50mmol), palladium acetate (0.15g, 0.62mmol), water (20mL) and dioxane (50mL) were mixed, the mixture was refluxed at 25 ℃ for 24 hours under nitrogen protection, cooled after the reaction was completed, adjusted to pH 2-3 with 3% acetic acid, extracted with ethyl acetate (3X 20mL), and the solvent was evaporated to give a compound
3g of the crude product of (1); mixing the crude product with 50mL of polyphosphoric acid, reacting at 210 ℃ for 5h, cooling after the reaction is finished, adding 50mL of ice water, and adjusting the pH value with NaOH solution (1mol/L)>Extracting with ethyl acetate (3 × 20mL), evaporating to remove solvent, and separating by column chromatography to obtain compound
(2) Dissolving n-bromobutane (1.35g, 10mmol) in dry tetrahydrofuran (30mL), slowly dropwise adding into magnesium powder (0.3g, 11mmol), and carrying out reflux reaction at 25 ℃ for 2h to obtain a Grignard reagent; then the compound is mixed
(2.3g, 10mmol) in tetrahydrofuran (30mL), the mixture was added to the above Grignard reagent, the reaction was refluxed at 25 ℃ for 8 hours, water (5mL) was added to quench the reaction, and after extraction with dichloromethane (3X 20mL), the solvent was distilled off; mixing the obtained crude product, glacial acetic acid (50mL) and two drops of concentrated sulfuric acid, carrying out reflux reaction at 25 ℃ for 5h, and adjusting the pH of the system with NaOH solution (1mol/L)>7, extracting with dichloromethane, evaporating to remove solvent, and separating by column chromatography to obtain compound
(3) According to the preparation method of Ir-3, the compound
Is replaced by
To obtain Ir-21.
The skilled person can substitute the reaction raw materials according to the structure of the target compound and the preparation method of Ir-21 to obtain Ir-22, Ir-23 and Ir-24.
Examples 25 to 28
Examples 25-28 provide platinum group organic electrophosphorescent materials (sequentially identified as Pt-1 to Pt-4) having the following structural formulas:
according to the preparation methods of Ir-3, Ir-8, Ir-19 and Ir-16, the IrCl in the step (2)3·H2Replacement of O by PtCl2Thus obtaining Pt-1 to Pt-4.
Application examples 1 to 28
The OLED device is provided and sequentially comprises the following components from bottom to top: an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and a cathode;
the constituent materials of the layers were as follows:
anode: ITO (indium tin oxide) with a thickness of 80 nm;
hole injection layer: a host material NPB and a guest material F4-TCNQ (mass content is 2-10%);
hole transport layer: NPB;
light-emitting layer: the material comprises a host material TCTA and an object material Ir-1-Ir-24 and Pt-1-Pt-4 (the mass content is 5%) in sequence, and the thickness is 20 nm;
electron transport layer: BPhen (40% by mass) and LiQ (60% by mass), 30nm thick;
cathode: Mg/Ag with a thickness of 20 nm.
Comparative example 1
The only difference from application example 1 is: the guest material of the light-emitting layer is Ir (ppy)3。
The structural formulas of the respective materials in the application examples and comparative examples are as follows:
the sublimation temperatures of Ir-1 to Ir-28 were measured, and the current efficiency (LE), the driving voltage (V), and the Lifetime (LT) of the OLED devices provided in the above application examples and comparative examples were measured using a B-J-V measuring instrument95Time for brightness to decay to 95%);
wherein LE and V are measured at a brightness of 1000nits, LT95At a current density of 40mA/cm2Under the condition ofAnd (4) calculating.
The results of the performance tests are shown in table 1 below:
TABLE 1
As can be seen from the properties in Table 1, the organic electrophosphorescent material provided by the invention is easy to sublimate and dissolve, and is beneficial to the large-scale production of OLEDs; and compared with an organic electrophosphorescent material Ir (ppy)3The OLED device using the organic electrophosphorescent material provided by the invention as a guest material of a light-emitting layer has higher current efficiency, lower driving voltage and longer service life.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. An organic electrophosphorescent material, wherein the organic electrophosphorescent material is a compound having a structure of formula I, formula II or formula III;
wherein, Z ring is an alicyclic ring or an alicyclic ring;
Ra、Rband RcIs a substituent group on the Z ring which satisfies the chemical environment;
R1-R22each independently selected from the group consisting of a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted heteroalkyl group, a substituted or unsubstituted cycloalkyl group, and a substituted or unsubstitutedOne of heterocycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aralkyl, substituted or unsubstituted aryloxy, amino, silyl, alkenyl, cycloalkenyl, heteroalkenyl, alkynyl, acyl, carbonyl, carboxyl, ester, cyano, isocyano, thio, sulfinyl, sulfonyl, or phosphino;
m is a transition metal element, L is a second ligand for M, M is the maximum coordination number for M, d is the degree of denticity for L, and n is an integer from 1 to M/2.
2. The organic electrophosphorescent material of claim 1, wherein the Z ring is a 3-7 membered aliphatic ring or an alicyclic ring;
preferably, Ra、RbAnd RcEach is independently selected from one or at least two of hydrogen atom, halogen atom or alkyl;
preferably, R1-R22Are all hydrogen atoms.
3. The organic electrophosphorescent material of claim 1 or 2, wherein M is Ir, Pt, Os or Re;
preferably; l is substituted or unsubstituted acetylacetone.
4. The organic electrophosphorescent material of any one of claims 1 to 3, wherein the organic electrophosphorescent material is a compound having the following structure:
wherein, the Z ring is a 3-7 membered fat ring.
5. A method for preparing an organic electrophosphorescent material according to any one of claims 1 to 4, comprising the steps of:
(1) the compound
Mixing one of the raw materials with phenylboronic acid, an alkaline substance, triphenylphosphine, palladium acetate, water and dioxane, and reacting to obtain a compound
(2) The compound
Mixing with polyphosphoric acid, and reacting to obtain compound
(3) Dissolving n-bromoalkane or 1-bromoolefin in tetrahydrofuran, then dropwise adding the tetrahydrofuran into magnesium powder, and reacting to obtain a Grignard reagent;
(4) the compound
Mixing with the Grignard reagent obtained in the step (3), reacting, and adding water for quenching after the reaction is finished;
(5) mixing the reaction product obtained in the step (4) with glacial acetic acid and concentrated sulfuric acid, and reacting to obtain a compound
With or without substitution to give compounds
(6) Mixing the compound obtained in the step (5), salt of M, water and 2-ethoxyethanol, and reacting to obtain a dimer compound;
(7) and (3) mixing one of the second ligand L or the compound obtained in the step (5), the dimer compound obtained in the step (6), an alkaline substance and 2-ethoxyethanol, and reacting to obtain the organic electrophosphorescent material.
6. The preparation method according to claim 5, wherein the reaction in step (1) and step (6) is carried out under nitrogen protection;
preferably, the alkaline substance in step (1) and step (7) is each independently sodium carbonate and/or potassium carbonate;
preferably, the reaction in the step (1) is carried out at the temperature of 20-40 ℃ for 20-28 h;
preferably, step (1) further comprises purification: after the reaction is finished, adjusting the pH value of the reaction solution to 2-3, extracting with ethyl acetate, and evaporating to remove the solvent;
preferably, the temperature of the reaction in the step (2) is 200-220 ℃, and the time is 4-6 h;
preferably, step (2) further comprises purification: after the reaction is finished, adding ice water into the reaction solution, adjusting the pH to be more than 7, extracting with ethyl acetate, evaporating to remove the solvent, and carrying out column chromatography separation.
7. The process according to claim 5 or 6, wherein the reaction in step (3) is carried out at a temperature of 20 to 40 ℃ for 2 to 4 hours;
preferably, the reaction in the step (4) is carried out at the temperature of 20-40 ℃ for 8-10 h;
preferably, step (4) further comprises purification: after the reaction is finished, extracting by using dichloromethane, and evaporating to remove the solvent;
preferably, the reaction in the step (5) is carried out at the temperature of 20-40 ℃ for 4-6 h;
preferably, step (5) further comprises purification: after the reaction is finished, adjusting the pH value of the reaction solution to be more than 7, extracting with dichloromethane, evaporating to remove the solvent, and carrying out column chromatography separation;
preferably, the reaction in the step (6) is carried out at the temperature of 80-120 ℃ for 12-18 h;
preferably, the reaction in the step (7) is carried out at the temperature of 20-40 ℃ for 20-28 h;
preferably, step (6) and step (7) further comprise: filtering and washing a reaction product after the reaction is finished;
preferably, step (7) further comprises purification: after the reaction was completed, the reaction product was separated by silica gel column chromatography and then eluted with methylene chloride.
8. Use of the organic electrophosphorescent material according to any one of claims 1 to 4, wherein the organic electrophosphorescent material is used in an OLED.
9. An OLED device, comprising: the organic light-emitting diode comprises an anode, a cathode and one or more organic thin film layers arranged between the anode and the cathode, wherein the organic thin film layers at least comprise a light-emitting layer;
the host material or guest material of the light-emitting layer is the organic electrophosphorescent material according to any one of claims 1 to 4.
10. The OLED device of claim 9, wherein the OLED device comprises, in order from bottom to top: an anode, a hole injection layer, a hole transport layer, optionally an electron blocking layer, a light emitting layer, optionally a hole blocking layer, an electron transport layer, a cathode, and a light extraction layer;
preferably, the mass percentage content of the host material in the light-emitting layer is 80-98%, and the mass percentage content of the guest material is 2-20%;
preferably, the host material of the light emitting layer is TCTA, and the guest material is the organic electrophosphorescent material according to any one of claims 1 to 4.
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| CN114773397A (en) * | 2022-04-29 | 2022-07-22 | 北京八亿时空液晶科技股份有限公司 | Metal complex, organic electroluminescent element containing metal complex and consumer product |
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