CN107325084A - A kind of spiro fluorene oxa anthracene compound and its luminescent device - Google Patents
A kind of spiro fluorene oxa anthracene compound and its luminescent device Download PDFInfo
- Publication number
- CN107325084A CN107325084A CN201710573192.9A CN201710573192A CN107325084A CN 107325084 A CN107325084 A CN 107325084A CN 201710573192 A CN201710573192 A CN 201710573192A CN 107325084 A CN107325084 A CN 107325084A
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- China
- Prior art keywords
- spirofluorene
- formula
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- xanthene compound
- hydrogen
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- -1 anthracene compound Chemical class 0.000 title claims abstract description 13
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 title abstract 7
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Natural products C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 title abstract 3
- 125000003003 spiro group Chemical group 0.000 title abstract 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 55
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 34
- 239000001257 hydrogen Substances 0.000 claims abstract description 34
- 125000001424 substituent group Chemical group 0.000 claims abstract description 25
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- 229910052736 halogen Inorganic materials 0.000 claims description 22
- 150000002367 halogens Chemical class 0.000 claims description 22
- 150000002431 hydrogen Chemical class 0.000 claims description 20
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 17
- 125000003118 aryl group Chemical group 0.000 claims description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 13
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 9
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- 125000006575 electron-withdrawing group Chemical group 0.000 claims description 8
- 150000003254 radicals Chemical class 0.000 claims description 8
- 239000012044 organic layer Substances 0.000 claims description 7
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 3
- 150000001975 deuterium Chemical group 0.000 claims description 3
- 229910052805 deuterium Inorganic materials 0.000 claims description 3
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000004432 carbon atom Chemical group C* 0.000 claims 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 53
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 abstract description 19
- 238000004770 highest occupied molecular orbital Methods 0.000 abstract description 7
- 125000001834 xanthenyl group Chemical group C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 4
- 238000004020 luminiscence type Methods 0.000 abstract description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 17
- 230000008020 evaporation Effects 0.000 description 16
- 238000001704 evaporation Methods 0.000 description 16
- 230000006872 improvement Effects 0.000 description 16
- 238000001228 spectrum Methods 0.000 description 14
- 238000005481 NMR spectroscopy Methods 0.000 description 13
- LULAYUGMBFYYEX-UHFFFAOYSA-N 3-chlorobenzoic acid Chemical compound OC(=O)C1=CC=CC(Cl)=C1 LULAYUGMBFYYEX-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- PCLIMKBDDGJMGD-UHFFFAOYSA-N N-bromosuccinimide Chemical compound BrN1C(=O)CCC1=O PCLIMKBDDGJMGD-UHFFFAOYSA-N 0.000 description 12
- 239000011259 mixed solution Substances 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 150000001721 carbon Chemical group 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- 239000011368 organic material Substances 0.000 description 10
- 239000000758 substrate Substances 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000000034 method Methods 0.000 description 8
- 238000000103 photoluminescence spectrum Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- 230000003111 delayed effect Effects 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- 238000005893 bromination reaction Methods 0.000 description 6
- 235000011089 carbon dioxide Nutrition 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- QDLAGTHXVHQKRE-UHFFFAOYSA-N lichenxanthone Natural products COC1=CC(O)=C2C(=O)C3=C(C)C=C(OC)C=C3OC2=C1 QDLAGTHXVHQKRE-UHFFFAOYSA-N 0.000 description 6
- YMWUJEATGCHHMB-UHFFFAOYSA-N methylene chloride Substances ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- GJCOSYZMQJWQCA-UHFFFAOYSA-N 9H-xanthene Chemical compound C1=CC=C2CC3=CC=CC=C3OC2=C1 GJCOSYZMQJWQCA-UHFFFAOYSA-N 0.000 description 5
- 230000009477 glass transition Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- DLEDOFVPSDKWEF-UHFFFAOYSA-N lithium butane Chemical compound [Li+].CCC[CH2-] DLEDOFVPSDKWEF-UHFFFAOYSA-N 0.000 description 5
- MZRVEZGGRBJDDB-UHFFFAOYSA-N n-Butyllithium Substances [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- AWXGSYPUMWKTBR-UHFFFAOYSA-N 4-carbazol-9-yl-n,n-bis(4-carbazol-9-ylphenyl)aniline Chemical compound 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 description 4
- 101000837344 Homo sapiens T-cell leukemia translocation-altered gene protein Proteins 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- 102100028692 T-cell leukemia translocation-altered gene protein Human genes 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 0 CC(C)(*N)C=C=C*=C(*)C=C=C Chemical compound CC(C)(*N)C=C=C*=C(*)C=C=C 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 125000004431 deuterium atom Chemical group 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000003292 glue Substances 0.000 description 3
- 230000005525 hole transport Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 3
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 3
- 125000004076 pyridyl group Chemical group 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Substances ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000005274 electronic transitions Effects 0.000 description 2
- 238000000295 emission spectrum Methods 0.000 description 2
- 230000005281 excited state Effects 0.000 description 2
- 238000002189 fluorescence spectrum Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 125000000623 heterocyclic group Chemical group 0.000 description 2
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- XOFYZVNMUHMLCC-ZPOLXVRWSA-N prednisone Chemical compound O=C1C=C[C@]2(C)[C@H]3C(=O)C[C@](C)([C@@](CC4)(O)C(=O)CO)[C@@H]4[C@@H]3CCC2=C1 XOFYZVNMUHMLCC-ZPOLXVRWSA-N 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Chemical group COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 125000001174 sulfone group Chemical group 0.000 description 2
- 125000003375 sulfoxide group Chemical group 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- 238000004506 ultrasonic cleaning Methods 0.000 description 2
- GEQBRULPNIVQPP-UHFFFAOYSA-N 2-[3,5-bis(1-phenylbenzimidazol-2-yl)phenyl]-1-phenylbenzimidazole Chemical compound C1=CC=CC=C1N1C2=CC=CC=C2N=C1C1=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=CC(C=2N(C3=CC=CC=C3N=2)C=2C=CC=CC=2)=C1 GEQBRULPNIVQPP-UHFFFAOYSA-N 0.000 description 1
- JJHHIJFTHRNPIK-UHFFFAOYSA-N Diphenyl sulfoxide Chemical compound C=1C=CC=CC=1S(=O)C1=CC=CC=C1 JJHHIJFTHRNPIK-UHFFFAOYSA-N 0.000 description 1
- 238000003848 UV Light-Curing Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- KZTYYGOKRVBIMI-UHFFFAOYSA-N diphenyl sulfone Chemical compound C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005401 electroluminescence Methods 0.000 description 1
- 238000001194 electroluminescence spectrum Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000012736 patent blue V Nutrition 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 150000003462 sulfoxides Chemical group 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 239000004557 technical material Substances 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
Classifications
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- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
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- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
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- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/547—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom
- C07F9/655—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms
- C07F9/6552—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a six-membered ring
- C07F9/65522—Heterocyclic compounds, e.g. containing phosphorus as a ring hetero atom having oxygen atoms, with or without sulfur, selenium, or tellurium atoms, as the only ring hetero atoms the oxygen atom being part of a six-membered ring condensed with carbocyclic rings or carbocyclic ring systems
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Abstract
The present invention relates to technical field of organic luminescence materials, and in particular to a kind of spiro fluorene compound and its luminescent device.The spiro fluorene oxa anthracene compound of the present invention is selected from the compound of the I as shown in formula：Y1、Y2Respective independent expression hydrogen, electron withdraw group or electron-donating group；X1、X2In at least one substituent be Formula II shown in substituent.Spiro fluorene structure and the dihedral angle of xanthene structure structure left and right in 90 ° in the compounds of this invention, M groups have the effect for further disperseing LUMO tracks, so that HOMO LUMO tracks are separated, obtain preferable Δ EST.Meanwhile, spiro fluorene oxa anthracene compound of the invention is a stable rigid structure, material is had preferable stability of molecule.
Description
Technical Field
The invention relates to the technical field of organic luminescent materials, in particular to a spirofluorene-xanthene compound and a luminescent device thereof.
Background
OLED materials are classified into fluorescent OLED materials and phosphorescent OLEDs according to an electroluminescence mechanism. In the prior OLED technical material, the phosphorescent luminescent material contains heavy metal effect, so that the quantum luminescent efficiency of 100 percent can be theoretically achieved, and particularly, the material has been greatly developed in the aspects of red and green phosphorescent materials. However, since triplet excitons of phosphorescent materials are easily quenched at high concentrations, it is necessary to maintain a certain host-guest doping ratio in order to improve performance.
Fluorescent OLED materials are purely organic materials and do not contain heavy metals, so theoretically only 25% internal quantum efficiency can be achieved, resulting in an upper limit of theoretically 5% maximum external quantum efficiency for fluorescence. At present, the red light OLED material and the green light OLED material have been developed greatly, and the performance of the fluorescent blue OLED material can not be compared favorably with other red and green light materials.
Recently, a Thermally Activated Delayed Fluorescence (TADF) material, which can obtain internal quantum efficiency close to 100% due to HOMO-LUMO orbital separation such that triplet excitons can be Thermally hopped to singlet orbitals, has been receiving much attention.
The current blue light TADF material is still a difficulty at present because the triplet state of the organic material is required to reach more than 2.6eV and maintain higher performance to obtain the fluorescent blue with high color purity. Most classically, 2CzPN developed at kyushu university of japan, which has an EL electroluminescence spectrum of 480nm, is a sky blue material with an external quantum efficiency of 10%, and is not sufficient for display applications. At present, if a deep blue light TADF material is to be obtained, the molecular design needs to be carried out again.
In view of this, the invention is particularly proposed.
Disclosure of Invention
A first object of the present invention is to provide a spirofluorene-xanthene compound as a fluorescent blue material.
A second object of the present invention is to provide a light-emitting device using the spirofluorene-xanthene compound.
In order to achieve the purpose of the invention, the technical scheme is as follows:
in order to achieve the first object of the present invention, the present invention proposes a spirofluorene-xanthene compound selected from compounds represented by the general formula I:
wherein, Y1、Y2Each independently represents hydrogen, an electron withdrawing group or an electron donating group;
X1、X2wherein at least one substituent is a substituent represented by the general formula II:
m represents-S-, -P-, -SO2-、-S(＝S)-、-S(＝S)(＝S)-、-PO-、-PO2-、-P(＝S)-、-P(＝S)(＝S)-、-C(＝O)-；
N1、N2、N3、N4Each independently represents a carbon atom or a nitrogen atom;
Raselected from hydrogen, halogen, C1～30Alkyl, hydroxy substituted C1～30Alkyl or C6～48An alkylaryl group;
j. k and n are each independently an integer of 0 to 4, and p and q are each independently an integer of 1 to 4.
In order to achieve the second object of the present invention, the present invention proposes a light emitting device comprising an anode, a cathode and at least one organic layer disposed between the anode and the cathode, the organic layer comprising the spirofluorene-xanthene compound according to the present invention.
The technical scheme of the invention at least has the following beneficial effects:
the invention provides a thermally activated delayed fluorescent material based on a spirofluorene-xanthene structure, wherein the spirofluorene structure and the xanthene structure form a dihedral angle of about 90 degrees to form a basis for HOMO-LUMO separation, and meanwhile, a bond connecting a xanthene group and an M group of an aromatic ring (or heterocyclic ring) can form a spatial angle of about 90 degrees and further disperse LUMO orbitals, so that the HOMO-LUMO orbitals are thoroughly separated, and delta E isSTClose to 0 eV.
Meanwhile, the spirofluorene-xanthene compound is a stable rigid structure, and can ensure that the material has a high enough glass transition temperature, so that the material can keep better molecular stability in the vacuum thermal evaporation process.
Drawings
Fig. 1 is a schematic view of a light emitting device of the present invention;
FIG. 2 is a nuclear magnetic resonance carbon spectrum of the compound FXT-DPYSO 2;
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of the compound FXT-DPYSO 2;
FIG. 4 is the NMR spectrum of FXT-DPYSO compound
FIG. 5 is a nuclear magnetic resonance hydrogen spectrum of the compound FXT-DPYSO;
FIG. 6 is a nuclear magnetic resonance carbon spectrum of the compound FXT-PYSOcl 2;
FIG. 7 is a NMR spectrum of the compound FXT-PYSOcl 2;
FIG. 8 is a NMR carbon spectrum of FXT-4 PySO;
FIG. 9 is a NMR spectrum of FXT-4 PySO;
FIG. 10 is a light-emitting graphic representation of the compounds FXT-4PySO, FXT-DPYSO2, FXT-DPYSO and FXT-PYSOcl 2.
Wherein:
10-a light emitting device;
11-an anode;
12-a hole transport layer;
13-a light-emitting layer;
14-an electron transport layer;
15-cathode.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
The invention relates to a spirofluorene-xanthene compound, which is selected from compounds shown as a general formula I:
wherein, Y1、Y2Each independently represents hydrogen, an electron withdrawing group or an electron donating group;
X1、X2wherein at least one substituent is a substituent represented by formula II:
m represents-S-, -P-, -SO2-、-S(＝S)-、-S(＝S)(＝S)-、-PO-、-PO2-、-P(＝S)-、-P(＝S)(＝S)-、-C(＝O)-；
N1、N2、N3、N4Each independently represents a carbon atom or a nitrogen atom;
Raselected from hydrogen, halogen, C1～30Alkyl, hydroxy substituted C1～30Alkyl or C6～48An alkylaryl group;
j. k and n are each independently an integer of 0 to 4, and p and q are each independently an integer of 1 to 4.
More preferably, p and q are both 1.
The spirofluorene structure and the xanthene structure in the spirofluorene-xanthene compound provided by the invention form a dihedral angle of about 90 degrees, which is the basis for ensuring that HOMO free in spirofluorene is effectively separated from the group shown in the general formula II and part of LUMO free in a xanthene unit. At the same time, the bond connecting the xanthene group and the M group of the aromatic ring (or heterocycle) can form a space angle larger than 100 degrees, and further disperse the LUMO orbital, so that the HOMO-LUMO orbital is separated completely, and the delta EST is close to 0 ev.
The spirofluorene-xanthene compound has high triplet state energy level, complete HOMO-LUMO separation and high fluorescence light emitting efficiency, so that deep blue light spectrum is obtained.
As an improvement of the spirofluorene-xanthene compound of the present invention, the electron donating group is selected from substituted or unsubstituted C1～30An alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenylyl group, or a substituent represented by the following structural formula:
wherein R is1、R2、R3、R4Each independently selected from hydrogen atom, amino, halogen, substituted or unsubstituted C1～12Alkyl, substituted or unsubstituted C1～12Alkoxy, substituted or unsubstituted C6～12Aryl, substituted or unsubstituted C6～12An aryloxy group;
the substituent is a halogen atom, C1～12Alkyl group of (2), halogen atom substituted C1～12Alkyl group of (2), halogen atom substituted C1～12Alkoxy group of (a);
m is an integer of 0 to 4;
any hydrogen atom on the benzene ring in the groups represented by formula Y-6, formula Y-7, formula Y-11, formula Y-12, formula Y-17 and formula Y-18 may be substituted to form a substituent.
When M is sulfonyl or sulfoxide, the synthesis yield of the phenyl sulfone or phenyl sulfoxide and other similar substituents is higher, thereby improving the market prospect of the compound.
As an improvement of the spirofluorene-xanthene compound of the present invention, the electron-withdrawing group is selected from the group of substituents represented by the general formula II.
As an improvement of the spirofluorene-xanthene compound of the present invention, in formula I, X1Selected from hydrogen or a substituent of formula IIa, X2A substituent selected from the group consisting of formula IIa;
k represents a carbon atom or a nitrogen atom. RaThe meaning is shown in the formula II.
As an improvement of the spirofluorene-xanthene compound of the present invention, in formula IIa, M represents-SO-, -SO2-、-PO-。
As an improvement of the spirofluorene-xanthene compound of the present invention, when Y is1、Y2When hydrogen, the spirofluorene-xanthene compound is selected from compounds of formula IA or formula IB:
wherein,
M1、M2each independently represents-SO-, -SO2-、-PO-；
Ra1、Ra2Each independently selected from hydrogen, halogen, C1～12Alkyl radical, C6～24An aryl group;
K1、K2each independently represents a carbon atom or a nitrogen atom.
Further preferably, Ra1、Ra2Each independently selected from a hydrogen atom or a halogen.
More preferably, in IA, M1、M2The same; ra1、Ra2The same; k1、K2The same is true.
When Y is1、Y2In the case of hydrogen, two or one specific electron-withdrawing functional group in the compounds of formula IA or formula IB are located on either side or both sides of the xanthene molecule, so that the HOMO can be left entirely on the spirofluorene molecule, while the LUMO alone is biased towards a specific electron-withdrawing group, thereby separating the HOMO-LUMO orbital.
As an improvement of the spirofluorene-xanthene compound of the present invention, M1、M2Each independently represents a sulfone group or a sulfoxide group, selected from those of the general formula IA1Or of the formula IB1A compound shown in the formula (I):
wherein,
M1、M2each independently represents-SO-, -SO2-；
Ra1、Ra2Each independently selected from hydrogen, halogen;
K1、K2each independently represents a carbon atom or a nitrogen atom.
Preferably, in IA1In, M1、M2The same; ra1、Ra2The same; k1、K2The same is true.
When M is1、M2When representing a sulfone group, the sulfone bond linking the phenyl (or pyridyl) group and the xanthene is at a steric angle of 110.5 deg., so that the LUMO orbital can be further dispersed.
When M is1、M2When it represents a sulfoxide group, the sulfoxide bond linking the phenyl group (or pyridyl group) and the xanthene group may form a space angle of about 90 °, and the LUMO orbital may be further dispersed.
As an improvement of the spirofluorene-xanthene compound of the present invention, M1、M2When represents-PO-, is selected from the group consisting of formula IA2A compound shown in the formula (I):
wherein,
Ra11、Ra12、Ra21、Ra22each independently selected from hydrogen, halogen;
K11、K12、K21、K22each independently represents a carbon atom or a nitrogen atom.
Preferably, in IA2In, M1、M2The same; ra1、Ra2The same; k1、K2The same is true.
When M is1、M2when-PO-is represented, the bond linking the phenyl group (or pyridyl group) and the xanthene may form a space angle of about 90 degrees, whereby the LUMO orbital can be further dispersed.
As an improvement of the spirofluorene-xanthene compound of the present invention, when Y is1、Y2When it is an electron donating group, it is selected from compounds represented by the general formula IC:
wherein,
M1、M2each independently represents-SO-, -SO2-；
Ra1、Ra2、Rb、Rc、Rd、ReEach independently selected from hydrogen, halogen, C1～12Alkyl radical, C6～24An aryl group;
K1、K2each independently represents a carbon atom or a nitrogen atom.
Preferably, in IC, M1、M2The same; ra1、Ra2The same; k1、K2The same is true.
As an improvement of the spirofluorene-xanthene compound of the present invention, when Y is1、Y2When the electron-donating group is an electron-donating group, the compound can be selected from compounds shown in a general formula ID:
wherein,
M1、M2each independently represents-SO-, -SO2-；
Ra1、Ra2、Rb、Rc、Rd、ReEach independently selected from hydrogen, halogen, C1～12Alkyl radical, C6～24An aryl group;
K1、K2each independently represents a carbon atom or a nitrogen atom.
Preferably, in ID, M1、M2The same; ra1、Ra2The same; k1、K2The same is true.
As an improvement of the spirofluorene-xanthene compound of the present invention, when Y is1、Y2When it is an electron-donating group, it can be selected from compounds represented by the general formula IE:
wherein,
M1、M2each independently represents-SO-, -SO2-；
Ra1、Ra2、Rb、Rc、Rd、ReEach independently selected from hydrogen, halogen, C1～12Alkyl radical, C6～24An aryl group;
K1、K2each independently represents a carbon atom or a nitrogen atom.
Preferably, in IE, M1、M2The same; ra1、Ra2The same; k1、K2The same is true.
In the compounds shown in the general formulas IC, ID and IE, two or one specific electron-withdrawing group is positioned at two sides or one side of a xanthene molecule, an electron-donating group is connected to one side of HOMO, HOMO electron cloud dissociated on spirofluorene can further dissociate to a newly added electron-donating unit, and thus the HOMO distribution region is wider.
As an improvement of the spirofluorene-xanthene compound of the present invention, the compound represented by the general formula IC is more preferably represented by the general formula IC1A compound shown in the formula (I):
as an improvement of the spirofluorene-xanthene compound of the present invention, the compound represented by the general formula ID is more preferably represented by the general formula ID1A compound shown in the formula (I):
as an improvement of the spirofluorene-xanthene compound of the present invention, the compound represented by the general formula IE is more preferably represented by the general formula IE1A compound shown in the formula (I):
as the spirofluorene of the present inventionAn improvement of the xanthene compound when Y is1、Y2When an electron withdrawing group, is selected from compounds of formula IF:
wherein M is1、M2、M3、M4Each independently represents-SO-, -SO2-、-PO-；
Ra11、Ra12、Ra21、Ra22Each independently selected from hydrogen, halogen, C1～12Alkyl radical, C6～24An aryl group;
K11、K12、K21、K22each independently represents a carbon atom or a nitrogen atom;
n1、n2、n3、n4each independently selected from integers of 0 to 4.
In the compounds of the formula IF, X1、X2、Y1、Y2All electron-withdrawing substituents form four electron-withdrawing units, the LUMO orbital component can be split into four parts and separated by virtue of the more than 100 ° spatial angle between the electron-withdrawing unit and the spirofluorene or xanthene molecule. Thus, the LUMO orbital is more delocalized, more dispersed, and has less overlap with the HOMO orbital, further reducing Δ EST。
As an improvement of the spirofluorene-xanthene compound of the present invention,
Ra1、Ra2、Ra11、Ra12、Ra21、Ra22each independently selected from a hydrogen atom, a deuterium atom or a halogen; further independently from each other, is selected from a hydrogen atom or a chlorine atom;
Rb、Rc、Rd、Reeach independently selected from hydrogen atomsDeuterium atom, halogen, alkyl, aryl, heteroaryl, deuterated alkyl, deuterated aryl, or deuterated heteroaryl.
Wherein, deuterated alkyl refers to a substituent formed after deuterium atoms replace hydrogen atoms in alkyl, deuterated aryl refers to a substituent formed after deuterium atoms replace hydrogen atoms in aryl, and deuterated heteroaryl refers to a substituent formed after deuterium atoms replace hydrogen atoms in heteroaryl.
As an improvement of the spirofluorene-xanthene compounds of the present invention, according to the general formula IA1And general formula IB1Specific compounds may be selected from:
according to the general formula IA2Specific compounds may be selected from:
according to formula IC, a particular compound may be selected from:
according to formula ID, a particular compound may be selected from:
according to general formula IE, a particular compound may be selected from:
according to the general formula IF, a particular compound can be selected from:
the invention also relates to a light emitting device which is an Organic Light Emitting Diode (OLED). Comprising an anode, a cathode and at least one organic layer disposed between the anode and the cathode, the organic layer comprising the aromatic compound of the present invention. Fig. 1 is a schematic structural diagram of a light emitting device according to the present invention. The light-emitting device 10 includes an anode 11, a hole transport layer 12, a light-emitting layer 13, an electron transport layer 14, and a cathode 15, which are sequentially deposited. The hole transport layer 12, the light emitting layer 13, and the electron transport layer 14 are all organic layers, and the anode 11 and the cathode 15 are electrically connected.
The synthetic route of the spirofluorene-xanthene compound is as follows:
(one) Y1、Y2Synthesis of spirofluorene-xanthene compound when hydrogen:
Y1、Y2the general synthesis for hydrogen is:
and (3) dropwise adding a mixed solution of NBS (N-bromosuccinimide)/THF (tetrahydrofuran) into the reaction bottle filled with the A, heating to 35-45 ℃ under the protection of nitrogen, preserving heat for a certain time, and carrying out bromination reaction to obtain the B. Then, a disubstituted disulfide compound R-S-S-R is added as n-BuLiThe mixture is fully stirred in a low-temperature dry ice bath for a certain time by taking THF as a catalyst to obtain a compound C. Finally, introducing m-chlorobenzoic acid mCPBA/CH2Cl2And (3) fully stirring the mixed solution for a certain time, adding water, separating out a solid, washing by using n-hexane and recrystallizing by using ethanol in sequence to obtain a product D.
Wherein, R can be benzene ring, pyridine, para-chlorobenzene and meta-chloropyridine.
If R' is H orThen
If R' is H orThen
If R' is H orThen
If R' is H orThen
If R' is H orThen
If R' is H orThen
If R' is H orThen
If R' is H orThen
(II) Y1、Y2Synthesis of spirofluorene-xanthene compound when hydrogen is absent:
r can be benzene ring, pyridine, para-chlorobenzene and meta-chloropyridine.
Y1、Y2The general synthesis when hydrogen is absent is:
adding Br dropwise into a reaction flask filled with A2/CH3And carrying out bromination reaction on the mixed solution of COOH under the protection of nitrogen to obtain B. Then adding a di-meta-chloropyridine substituted disulfide compound Py-S-S-Py, taking n-BuLi/THF as a catalyst, and fully stirring for a certain time in a low-temperature dry ice bath to obtain a compoundAnd (C) a compound. Finally, introducing m-chlorobenzoic acid mCPBA/CH2Cl2And (3) fully stirring the mixed solution for a certain time, adding water, separating out a solid, washing by using n-hexane and recrystallizing by using ethanol in sequence to obtain a product D.
If it is notThen
If it is notThen
If it is notThen
If it is notThen
If R' is H orThen
If it is notThen
If it is notThen
If it is notThen
Synthesis example 1: synthesis and characterization of FXT-DPYSO2
And (3) dropwise adding a mixed solution of NBS (N-bromosuccinimide)/THF into a reaction bottle containing 1mol of A, heating to 40 ℃ under the protection of nitrogen, and keeping the temperature for 1 hour to perform bromination reaction to obtain B. Then, the bipyridine substituted disulfide compound Py-S-S-Py is added, and n-BuLi/THF is used as a catalyst, and the mixture is fully stirred for half an hour in a low-temperature dry ice bath to obtain a compound C. Finally, introducing m-chlorobenzoic acid mCPBA/CH2Cl2And (3) fully stirring the mixed solution for 1 hour, adding water, separating out a solid, washing by using n-hexane and recrystallizing by using ethanol in sequence to obtain FXT-DPYSO2 with the yield of 48%.
The nuclear magnetic resonance carbon spectrum and the nuclear magnetic resonance hydrogen spectrum are shown in fig. 2 and 3, respectively.
The main peak of photoluminescence spectrum (PL spectrum) is 460nm, and the material is a deep blue material.
Synthesis example 2: synthesis and characterization of FXT-DPYSO
And (3) dropwise adding a mixed solution of NBS (N-bromosuccinimide)/THF into a reaction bottle containing 1mol of A, heating to 40 ℃ under the protection of nitrogen, and keeping the temperature for 1 hour to perform bromination reaction to obtain B. Then, the bipyridine substituted disulfide compound Py-S-S-Py is added, and n-BuLi/THF is used as a catalyst, and the mixture is fully stirred for half an hour in a low-temperature dry ice bath to obtain a compound C. Finally, introducing m-chlorobenzoic acid mCPBA/CH2Cl2And (3) fully stirring the mixed solution for 1 hour, adding water, separating out a solid, washing by using normal hexane and recrystallizing by using ethanol in sequence to obtain FXT-DPYSO with the yield of 51 percent.
The nuclear magnetic resonance carbon spectrum and the nuclear magnetic resonance hydrogen spectrum are shown in fig. 4 and 5, respectively.
The main peak of the photoluminescence spectrum (PL spectrum) is 465nm, and the material is a deep blue material.
Synthetic example 3: synthesis and characterization of FXT-PYSOcl2
Adding Br dropwise into a reaction flask filled with 1mol of A2/CH3And carrying out bromination reaction on the mixed solution of COOH under the protection of nitrogen to obtain B. Then, adding a di-meta-chloropyridine substituted disulfide compound PyCl-S-S-PyCl, taking n-BuLi/THF as a catalyst, and fully stirring for half an hour in a low-temperature dry ice bath to obtain a compound C. Finally, introducing m-chlorobenzoic acid mCPBA/CH2Cl2The mixed solution was sufficiently stirred for 1 hour, water was added to precipitate a solid, which was washed with n-hexane and recrystallized with ethanol in this order to obtain FXT-PYSOcl2 in a yield of 60%.
The nuclear magnetic resonance carbon spectrum and the nuclear magnetic resonance hydrogen spectrum are shown in fig. 6 and 7, respectively.
The main peak of photoluminescence spectrum (PL spectrum) is 446nm, and the material is a deep blue material.
Synthetic example 4: synthesis and characterization of FXT-4PySO
Adding Br dropwise into a reaction flask filled with A2/CH3And carrying out bromination reaction on the mixed solution of COOH at the temperature of 40 ℃ under the protection of nitrogen to obtain B. Then, adding a di-meta-chloropyridine substituted disulfide compound Py-S-S-Py, taking n-BuLi/THF as a catalyst, and fully stirring for half an hour in a low-temperature dry ice bath to obtain a compound C. Finally, introducing m-chlorobenzoic acid mCPBA/CH2Cl2And (3) fully stirring the mixed solution for 1 hour, adding water, separating out a solid, washing by using normal hexane and recrystallizing by using ethanol in sequence to obtain FXT-PYSO with the yield of 60%.
The nuclear magnetic resonance carbon spectrum and the nuclear magnetic resonance hydrogen spectrum are shown in fig. 8 and 9, respectively.
The main peak of photoluminescence spectrum (PL spectrum) is 440nm, and the material is a deep blue material.
Delta E of the spirofluorene-xanthene Compound of the present inventionSTTesting
The organic material has different energies of S1 excited state and T1 excited state due to different degrees of spontaneous rotation, and ES1Energy ratio of ET1The energy is 0.5-1.0 eV, which results in low luminous efficiency of the pure organic fluorescent material. The thermal delayed fluorescence TADF material separates the HOMO-LUMO orbitals due to unique molecular design, reduces the electron exchange energy of the HOMO-LUMO orbitals and can theoretically realize Delta EST0-0. To effectively evaluate the thermally delayed fluorescence effect of the materials described in the present invention, Δ E was performedSTAnd (6) evaluating.
The mCBP film is doped with 1 wt% of the compound, and fluorescence emission spectrum and phosphorescence emission spectrum measurement are carried out under the 77K condition, and the fluorescence emission spectrum and phosphorescence emission spectrum measurement are converted into S1 and T1 values (E is 1240/lambda em) through the relation of wavelength and energy. Then, Δ EST＝ES1-ET1The splitting energy of the singlet body and the triplet state is obtained. Specific experimental data are shown in table 1, and a luminescence mechanism diagram thereof is shown in fig. 10.
Table 1:
| test items | FXT-DPYSO2 | FXT-DPYSO | FXT-PYSOcl2 | FXT-4PySO |
| ES1(eV) | 2.77 | 2.75 | 2.72 | 2.70 |
| ET1(eV) | 2.67 | 2.63 | 2.59 | 2.62 |
| ΔEST(eV) | 0.10 | 0.12 | 0.13 | 0.08 |
As can be seen from Table 1, the compounds of the present invention all have a relatively small Δ ESTThe values are all less than 0.2eV, and therefore, the effect of thermally delayed fluorescence is exhibited.
As shown in the light-emitting mechanism diagram of fig. 10, the T1 → S1 electronic transition in the fluorescent light-emitting mechanism is forbidden, because the triplet state and the singlet state are different spintronic states, and when the energy level difference between the singlet state and the triplet state of the light-emitting material is continuously reduced, the probability of the electronic transition between T1 → S1 is also significantly increased, and the delayed fluorescence DF can be obtained under the action of energy applied in the external environment, so that the addition of the delayed fluorescence DF to the fluorescence F in the light-emitting material leads to a significant increase in the light-emitting efficiency of the fluorescent light-emitting material.
From Delta ESTFrom the viewpoint of size, the splitting energy between the singlet state and the triplet state of the above compound is ordered as: FXT-PYSOCL2>FXT-DPYSO>FXT-DPYSO2>The FXT-4PySO has obviously improved luminous efficiency.
Glass transition temperature test of spirofluorene-xanthene compound of the present invention
To further illustrate that the compounds of the present invention have a stable rigid structure and can increase the glass transition temperature of the material, the following experiment was performed:
the experimental method comprises the following steps: adopting DSC thermal differential scanner, equipment model Perkin Elmer Pyris 1, instrument function: the energy change condition of the sample at a specific temperature is measured, the sample passes through a controllable temperature-rising and temperature-lowering furnace, and when the sample is evaporated, melted, crystallized and the like, the sample can absorb and release heat along with energy, so that the reaction heat, the melting point, the glass transition temperature, the crystallization temperature and the thermal stability of the sample can be judged.
And (3) testing conditions are as follows: 1. temperature range: RT-500 ℃;
2. the temperature rising and falling speed is 5 v/min;
3. ambient gas N2；
Sample conditions were as follows: 1. each sample having a weight of at least about 2 to 3 mg;
2. the sample is pre-treated to remove water, solvents or other impurities that interfere with the experimental results.
The results of the experiment are shown in table 2:
table 2:
as can be seen from Table 2, the compounds of the present invention all have a higher glass transition temperature, so that the material maintains better molecular stability during the vacuum thermal evaporation process.
Performance evaluation of spirofluorene-xanthene compound for OLED device
The ITO substrate is bottom emission glass with the size of 30mm multiplied by 30mm, and has four light emitting areas, the light emitting area AA area is 2mm multiplied by 2mm, the light transmittance of the ITO film is 90% @550nm, the surface roughness Ra is less than 1nm, the thickness of the ITO film is 1300A, and the square resistance is 10 ohm per square.
The ITO substrate cleaning method comprises the following steps: firstly, placing the ITO glass into a container containing acetone solution, placing the container into an ultrasonic cleaning machine for ultrasonic cleaning for 30 minutes, and mainly dissolving and removing organic matters attached to the surface of the ITO glass; then taking out the cleaned ITO substrate, placing the cleaned ITO substrate on a hot plate, and baking the cleaned ITO substrate for half an hour at a high temperature of 120 ℃, wherein organic solvents and water vapor on the surface of the ITO substrate are mainly removed; then, quickly transferring the baked ITO substrate to UV-ZONE equipment for O3Plasma treatment, in which organic matters or foreign matters difficult to be removed from the ITO surface are further treated by Plasma for 15 minutes, and the treated ITO is rapidly transferred toAnd the OLED evaporation equipment is arranged in the film forming chamber.
Preparing an OLED before evaporation: the method comprises the following steps of cleaning OLED evaporation equipment, and wiping the inner wall of a cavity of a film forming chamber by using IPA (isopropyl alcohol), so as to ensure that no foreign matter or dust exists in the whole film forming cavity. Then, a crucible containing the OLED organic material and a crucible containing metal aluminum particles were placed in this order on the organic evaporation source and the inorganic evaporation source positions. Closing the cavity, and performing primary vacuumizing and high vacuumizing steps to ensure that the evaporation degree in the OLED evaporation equipment reaches 10E-7Torr。
And (3) OLED evaporation film forming: and opening the OLED organic evaporation source, and preheating the OLED organic material for 100 ℃ for 15 minutes to ensure that the water vapor in the OLED organic material is further removed. And then carrying out rapid heating treatment on the organic material to be evaporated, opening a baffle above an evaporation source until the organic material runs out of the evaporation source of the material, and slowly raising the temperature when a crystal oscillator piece detector detects the evaporation rate, wherein the temperature rise amplitude is 1-5 ℃, opening the baffle right below the mask plate until the evaporation rate is stabilized at 1A/s, carrying out OLED film formation, closing the mask plate baffle and the baffle right above the evaporation source when a computer end detects that the organic film on the ITO substrate reaches a preset film thickness, and closing an evaporation source heater of the organic material. The evaporation process for the other organic materials and the cathode metal material is as described above.
And (3) OLED packaging process: a cleaning method for a 20mm × 20mm package cover is, for example, an ITO substrate pretreatment method. Coating or dispensing UV glue materials around the extension of the cleaned packaging cover, transferring the packaging cover with the dispensed UV glue materials into vacuum laminating equipment, carrying out vacuum lamination with an ITO (indium tin oxide) substrate of a film-forming OLED (organic light emitting diode) organic film, transferring into a UV curing cavity, and carrying out photocuring by using ultraviolet light with a 365nm waveband. The light-cured ITO device also needs to be subjected to post-heat treatment at 80 ℃ for half an hour so as to completely cure the UV glue material.
1. As guest light-emitting materials (device nos. a to E): the electroluminescent property of FXT-4PySO as a guest luminescent material is that the OLED device structure is designed as follows:
ITO/NPB(30nm)/TCTA(30nm)/PPF:FXT-4PySO(x wt％,30nm,x＝2–10)/PPF(10nm)/TPBi(30nm)/LiF(0.8nm)/Al(150nm)。
2. as a host material (device No. G): FXT-4PySO is used as a bipolar main material, and the structure of the OLED device is designed as follows:
ITO/NPB/TCTA/FXT-4PySO:FIrN4(10wt％)/PPF(10nm)/TPBI(30nm)/Li F(0.8nm)/Al(150nm)。
3. comparative example (device No. F): the performance comparison is carried out by adopting a classic phosphorescent blue FIRN4 material, and the structure of the OLED device is designed as follows:
ITO/NPB(30nm)/TCTA(30nm)/PPF:FIrN4(10wt％,30nm)/PPF(10nm)/TPBi(30nm)/LiF(0.8nm)/Al(150nm)。
the device fabrication process is as described above.
The encapsulated samples were tested for IVL performance using an IVL instrument using Mc Science M6100, the test data is shown in Table 3:
table 3:
as can be seen from table 2, the FXT-4 PySO-based device performance tends to improve with increasing doping ratio, and the device performance tends to decrease with continued increase in doping ratio. But FXT-4PySO with a doping ratio of 8 wt% already outperforms the performance of phosphorescent blue materials.
The discovery that the device performance of G is much better than that of F when FXT-4PySO is used as a host material is because the FXT-4PySO material has the ability to transport both electrons and holes, and the carriers in the device are balanced, so that the luminous efficiency is good.
And (3) taking the optimal doping proportion of the FXT-4PySO as a reference, manufacturing the following device structure:
ITO/NPB (30nm)/TCTA (30nm)/PPF luminescent material (8 wt%, 30nm)/PPF (10nm)/TPBi (30nm)/LiF (0.8nm)/Al (150 nm).
Wherein the luminescent materials are FXT-4PySO, FXT-DPYSO2, FXT-DPYSO and FXT-PYSOcl2, so as to further evaluate the photoelectric properties of the luminescent materials.
The device fabrication process is as described above.
The encapsulated samples were tested for IVL performance using an IVL instrument using Mc Science M6100, the test data is shown in Table 4:
table 4:
as can be seen from Table 3, the maximum external quantum efficiency of FXT-4PySO is the best, probably due to its Δ ESTMinimum, the maximum exciton utilization.
Although the present invention has been described with respect to the preferred embodiments, it is not intended to be limited to the embodiments disclosed, and many modifications and variations are possible to those skilled in the art without departing from the spirit of the invention.
Claims (15)
1. A spirofluorene-xanthene compound, wherein the spirofluorene-xanthene compound is selected from compounds represented by the general formula I:
wherein, Y1、Y2Each independently represents hydrogen, an electron withdrawing group or an electron donating group;
X1、X2in which at least one substituent is of the formula IIThe substituent (b):
m represents-S-, -P-, -SO2-、-S(＝S)-、-S(＝S)(＝S)-、-PO-、-PO2-、-P(＝S)-、-P(＝S)(＝S)-、-C(＝O)-；
N1、N2、N3、N4Each independently represents a carbon atom or a nitrogen atom;
Raselected from hydrogen, halogen, C1～30Alkyl, hydroxy substituted C1～30Alkyl or C6～48An alkylaryl group;
j. k and n are each independently an integer of 0 to 4, and p and q are each independently an integer of 1 to 4.
2. The spirofluorene-xanthene compound according to claim 1, wherein the electron donating group is selected from substituted or unsubstituted C1～30An alkyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenylyl group, or a substituent represented by the following structural formula:
wherein R is1、R2、R3、R4Each independently selected from hydrogen atom, amino, halogen, substituted or unsubstituted C1～12Alkyl, substituted or unsubstituted C1～12Alkoxy, substituted or unsubstituted C6～12Aryl, substituted or unsubstituted C6～12An aryloxy group;
the substituent is a halogen atom, C1～12Alkyl group of (2), halogen atom substituted C1～12Alkyl group of (2), halogen atom substituted C1～12Alkoxy group of (a);
m is an integer of 0 to 4;
any hydrogen atom on the benzene ring in the group represented by the formula Y-6, the formula Y-7, the formula Y-11, the formula Y-12, the formula Y-17 and the formula Y-18 is substituted to form a substituent.
3. The spirofluorene-xanthene compound according to claim 1, wherein the electron-withdrawing group is selected from substituents represented by general formula II.
4. The spirofluorene-xanthene compound according to claim 1, wherein in formula I, X is1Selected from hydrogen or a substituent of the formula IIa, X2Is selected from substituent groups shown in a general formula IIa;
k represents a carbon atom or a nitrogen atom.
5. The spirofluorene-xanthene compound according to claim 1, wherein the spirofluorene-xanthene compound is selected from compounds as represented by general formula IA or formula IB:
wherein,
M1、M2each independently represents-SO-, -SO2-、-PO-；
Ra1、Ra2Each independently selected from hydrogen, halogen, C1～12Alkyl radical, C6～24An aryl group;
K1、K2each independently represents a carbon atom or a nitrogen atom.
6. The spirofluorene-xanthene compound according to claim 5, whereinThe spirofluorene-xanthene compound is selected from the general formula IA1Or of the formula IB1A compound shown in the formula (I):
wherein,
M1、M2each independently represents-SO-, -SO2-；
Ra1、Ra2Each independently selected from hydrogen, halogen;
K1、K2each independently represents a carbon atom or a nitrogen atom.
7. The spirofluorene-xanthene compound according to claim 5, wherein the spirofluorene-xanthene compound is selected from the group consisting of compounds of general formula IA2A compound shown in the formula (I):
wherein,
Ra11、Ra12、Ra21、Ra22each independently selected from hydrogen, halogen;
K11、K12、K21、K22each independently represents a carbon atom or a nitrogen atom.
8. The spirofluorene-xanthene compound according to claim 1, wherein the spirofluorene-xanthene compound is selected from compounds as represented by general formula IC, general formula ID or general formula IE:
wherein,
M1、M2each independently represents-SO-, -SO2-；
Ra1、Ra2、Rb、Rc、Rd、ReEach independently selected from hydrogen, halogen, C1～12Alkyl radical, C6～24An aryl group;
K1、K2each independently represents a carbon atom or a nitrogen atom.
9. The spirofluorene-xanthene compound according to claim 8, wherein the spirofluorene-xanthene compound is selected from the group consisting of compounds of the general formula IC1A compound shown in the formula (I):
10. the spirofluorene-xanthene compound according to claim 1, wherein the spirofluorene-xanthene compound is selected from the group consisting of compounds of the general formula ID1A compound shown in the formula (I):
11. the spirofluorene-xanthene compound according to claim 10, wherein the spirofluorene-xanthene compound is selected from the group consisting of compounds of the general formula IE1A compound shown in the formula (I):
12. the spirofluorene-xanthene compound according to claim 1, wherein the spirofluorene-xanthene compound is selected from compounds represented by general formula IF:
wherein M is1、M2、M3、M4Each independently represents-SO-, -SO2-、-PO-；
Ra11、Ra12、Ra21、Ra22Each independently selected from hydrogen, halogen, C1～12Alkyl radical, C6～24An aryl group;
K11、K12、K21、K22each independently represents a carbon atom or a nitrogen atom;
n1、n2、n3、n4each independently selected from integers of 0 to 4.
13. The spirofluorene-xanthene compound according to any one of claims 5 to 12, wherein the spirofluorene-xanthene compound is a spirofluorene-xanthene compound,
Ra1、Ra2、Ra11、Ra12、Ra21、Ra22each independently selected from a hydrogen atom, a deuterium atom or a halogen;
Rb、Rc、Rd、Reeach independently selected from a hydrogen atom, a deuterium atom, a halogen, an alkyl group, an aryl group, a heteroaryl group, a deuterated alkyl group, a deuterated aryl group, or a deuterated heteroaryl group.
14. The spirofluorene-xanthene compound according to claim 1, wherein the spirofluorene-xanthene compound is selected from compounds represented by the following structural formula:
15. a light-emitting device comprising an anode, a cathode, and at least one organic layer disposed between the anode and the cathode, the organic layer comprising the spirofluorene-xanthene compound of any one of claims 1 to 14.
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