CN113105491B - Pyridine diphenoxy boron fluoride compound, application thereof and organic electroluminescent device containing compound - Google Patents
Pyridine diphenoxy boron fluoride compound, application thereof and organic electroluminescent device containing compound Download PDFInfo
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- CN113105491B CN113105491B CN202110395607.4A CN202110395607A CN113105491B CN 113105491 B CN113105491 B CN 113105491B CN 202110395607 A CN202110395607 A CN 202110395607A CN 113105491 B CN113105491 B CN 113105491B
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 69
- -1 Pyridine diphenoxy boron fluoride compound Chemical class 0.000 title claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 127
- 230000000903 blocking effect Effects 0.000 claims abstract description 30
- 229910015900 BF3 Inorganic materials 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims description 37
- 125000001424 substituent group Chemical group 0.000 claims description 14
- 230000005525 hole transport Effects 0.000 claims description 12
- 238000002347 injection Methods 0.000 claims description 11
- 239000007924 injection Substances 0.000 claims description 11
- 125000004093 cyano group Chemical group *C#N 0.000 claims description 8
- 229910052805 deuterium Inorganic materials 0.000 claims description 8
- 125000004431 deuterium atom Chemical group 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 8
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 125000000732 arylene group Chemical group 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 239000010409 thin film Substances 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003277 amino group Chemical group 0.000 claims description 4
- 125000006267 biphenyl group Chemical group 0.000 claims description 4
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 4
- 125000001072 heteroaryl group Chemical group 0.000 claims description 4
- 125000000623 heterocyclic group Chemical group 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001624 naphthyl group Chemical group 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 125000002947 alkylene group Chemical group 0.000 claims description 3
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 claims description 3
- 125000004429 atom Chemical group 0.000 claims description 3
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 3
- 125000003914 fluoranthenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC=C4C1=C23)* 0.000 claims description 3
- 125000005549 heteroarylene group Chemical group 0.000 claims description 3
- 125000003454 indenyl group Chemical group C1(C=CC2=CC=CC=C12)* 0.000 claims description 3
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 3
- 150000002979 perylenes Chemical group 0.000 claims description 3
- 125000005561 phenanthryl group Chemical group 0.000 claims description 3
- 125000001725 pyrenyl group Chemical group 0.000 claims description 3
- 125000001935 tetracenyl group Chemical group C1(=CC=CC2=CC3=CC4=CC=CC=C4C=C3C=C12)* 0.000 claims description 3
- 125000004653 anthracenylene group Chemical group 0.000 claims description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 2
- 125000004957 naphthylene group Chemical group 0.000 claims description 2
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 125000005551 pyridylene group Chemical group 0.000 claims description 2
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 claims 3
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 claims 3
- 125000005264 aryl amine group Chemical group 0.000 claims 2
- 239000003054 catalyst Substances 0.000 claims 2
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 claims 2
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- 230000000052 comparative effect Effects 0.000 description 25
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- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
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- 101100016516 Caenorhabditis elegans hbl-1 gene Proteins 0.000 description 4
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- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 description 4
- XFAZZQREFHAALG-UHFFFAOYSA-N N-{1-amino-6-[(5-nitro-2-furoyl)amino]-1-oxohexan-2-yl}-23-(indol-3-yl)-20-oxo-4,7,10,13,16-pentaoxa-19-azatricosan-1-amide Chemical compound C=1NC2=CC=CC=C2C=1CCCC(=O)NCCOCCOCCOCCOCCOCCC(=O)NC(C(=O)N)CCCCNC(=O)C1=CC=C([N+]([O-])=O)O1 XFAZZQREFHAALG-UHFFFAOYSA-N 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 4
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- 238000007385 chemical modification Methods 0.000 description 4
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 4
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- 238000004770 highest occupied molecular orbital Methods 0.000 description 4
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- 229910000027 potassium carbonate Inorganic materials 0.000 description 4
- AOJFQRQNPXYVLM-UHFFFAOYSA-N pyridin-1-ium;chloride Chemical compound [Cl-].C1=CC=[NH+]C=C1 AOJFQRQNPXYVLM-UHFFFAOYSA-N 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
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- ROEQGIFOWRQYHD-UHFFFAOYSA-N (2-methoxyphenyl)boronic acid Chemical compound COC1=CC=CC=C1B(O)O ROEQGIFOWRQYHD-UHFFFAOYSA-N 0.000 description 3
- RZEMXCXZMMENMI-UHFFFAOYSA-N 1,2-diphenyl-9h-carbazole Chemical compound C1=CC=CC=C1C1=CC=C(C=2C(=CC=CC=2)N2)C2=C1C1=CC=CC=C1 RZEMXCXZMMENMI-UHFFFAOYSA-N 0.000 description 3
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- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 3
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- KZMGYPLQYOPHEL-UHFFFAOYSA-N Boron trifluoride etherate Chemical compound FB(F)F.CCOCC KZMGYPLQYOPHEL-UHFFFAOYSA-N 0.000 description 2
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- 239000011159 matrix material Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 125000001792 phenanthrenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C=CC12)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000000026 trimethylsilyl group Chemical group [H]C([H])([H])[Si]([*])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
The invention discloses a dipyridyl diphenoxy boron fluoride compound, application thereof and an organic electroluminescent device containing the same, wherein the dipyridyl diphenoxy boron fluoride compound has a structure shown in a combination of a formula (1) and a formula (2), and X in the structure shown in the formula (2) 1 ～X 8 Are independently selected from CR 12 Or N; y is Y 1 And Y 2 Are independently selected from CR 13 R 14 、CR 15 CR 16 、SiR 17 R 18 、NR 19 O, S, wherein Y 2 Alternatively, a single bond or a hydrogen bond may be used. The compound provided by the invention can be used as a luminescent material, a main material, a hole blocking material or an electron transport material of an organic electroluminescent device, and the thermally activated delayed fluorescent material has higher radiation rate or/and excellent electron transport performance, so that the efficiency and the service life of the organic electroluminescent device are improved.
Description
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to a novel organic compound and application thereof, and an organic electroluminescent device containing the compound.
Background
An organic electroluminescent device (OLED: organic Light Emitting Devices) is a sandwich-like current driven thin film device with a single or multiple layers of organic functional material sandwiched between an anode and a cathode. Under the action of an electric field, holes generated by the anode and electrons generated by the cathode of the OLED move, are respectively injected into the hole transmission layer and the electron transmission layer and migrate to the light-emitting layer, and when the hole transmission layer and the electron transmission layer meet and are combined at the light-emitting layer, energy excitons are generated, so that light-emitting molecules are excited to finally generate visible light. The OLED has the characteristics of self-luminescence, wide visual angle, wide color gamut, short response time, high luminous efficiency, low working voltage, low cost, simple production process and the like, can be manufactured into a large-size and/or flexible ultrathin panel, is a novel display technology with rapid development and higher process integration level, is widely applied to display products such as televisions, smart phones, tablet computers, vehicle-mounted displays, illumination and the like, and is further applied to creative display products such as large-size displays, flexible screens and the like.
The organic photoelectric material applied to the OLED device can be divided into a luminescent layer material and an auxiliary functional layer material in use, wherein the luminescent layer material comprises a guest material (also known as a luminescent material and a doping material) and a host material (also known as a matrix material), the luminescent material is divided into a fluorescent material, a phosphorescent material and a thermally activated delayed fluorescence (TADF: thermally Activated Delayed Fluorescent) material according to different energy transfer modes, and the auxiliary functional layer material is further divided into an electron injection material, an electron transport material, a hole blocking material, an electron blocking material, a hole transport material and a hole injection material according to the different properties of electron or hole transport speeds.
The fluorescent material has the advantages of low production cost and high emission rate, but only can utilize the energy of a non-spin-symmetrical singlet excitation state, and the energy only accounts for 25% of the energy generated after electron-hole recombination, so that the limit of internal quantum efficiency is 25%. The phosphorescent material can utilize strong spin orbit coupling of heavy metal atoms to effectively promote intersystem crossing of electrons from a singlet state to a triplet state, so that all energy of singlet state and triplet state excitons generated by electric excitation can be fully utilized, the internal quantum efficiency can reach 100%, but the emission rate is low, rare metals such as iridium are generally used, and the production cost is increased. The advantages of the two luminescent materials are combined, the TADF material with smaller singlet-triplet state energy gap is excited by utilizing heat in the surrounding environment, the reverse intersystem crossing of excitons from triplet state to singlet state is realized, the theoretical internal quantum efficiency can reach 100%, and the production cost is low because rare metals are not used.
Although the efficiency of current TADF materials is already comparable to phosphorescent materials, the lifetime of the devices is still not satisfactory for practical applications. Current research shows that besides the factors of the reverse intersystem crossing rate, chemical stability and the like, the fluorescence radiation rate constant (j. Match. Chem. C,2018,6,7728-7733) of TADF molecules and the electron transmissibility (adv. Electron. Match. 2019,5,1800708) have a great influence on the service life of the device.
Therefore, there is a need in the art to develop a novel class of thermally activated delayed fluorescence materials with high radiation rate constants and/or high electron transport properties that can produce organic electroluminescent devices with high efficiency and long lifetime at low driving voltages.
Disclosure of Invention
In order to solve the technical problems, the invention provides a novel pyridine diphenoxy boron fluoride organic compound, which has a structure shown in a combination of a formula (1) and a formula (2):
wherein,,
the substituent represented by formula (2) is represented by R of formula (1) alone 2 、R 3 、R 9 Or R is 10 The position is substituted, and the formula (2) is represented by the formula-R 2 、R 3 、R 9 Or R is 10 The positions are bonded;
in the formula (2), p and q are each independently an integer of 1 to 4;
further, it is required that p and q are each independently represented as an integer of 1 to 2;
in the formula (2), L is independently selected from a single bond, a substituted or unsubstituted straight-chain or branched alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 ring-forming carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 ring-forming carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 ring-forming carbon atoms, a substituted or unsubstituted arylene ring having 10 to 50 ring-forming carbon atoms, and a substituted or unsubstituted heterocycloalkylene ring having 6 to 50 ring-forming carbon atoms;
further, L is independently selected from a single bond, or any one or more of the following substituted or unsubstituted groups: a pyridylene group, a phenylene group, a biphenylene group, a naphthylene group, and an anthracenylene group.
In the formula (2), X 1 ～X 8 Are independently selected from CR 12 Or N;
further, require X 1 ～X 8 The number of nitrogen atoms of (2) is an integer of 0 to 5, preferably an integer of 0 to 3;
in the formula (2), Y 1 And Y 2 Are independently selected from CR 13 R 14 、CR 15 CR 16 、SiR 17 R 18 、NR 19 O, S, wherein Y 2 May also be selected as single bond or hydrogen bond;
r of formula (1) 1 ～R 11 R of formula (2) 12 ～R 19 Each substituent is independently selected from a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, a substituted amine group, a substituted silicon group, a substituted or unsubstituted alkyl group having 1 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 50 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 50 ring-forming carbon atoms, a substituted or unsubstituted aryl group having 6 to 50 ring-forming carbon atoms, or a substituted or unsubstituted 1-valent heterocyclic group having 5 to 50 ring-forming carbon atoms;
adjacent R 1 ～R 19 The substituents may be bonded to each other to form a substituted or unsubstituted saturated or unsaturated ring, or may be bonded to an adjacent aromatic or heteroaromatic ring to form a substituted or unsubstituted saturated or unsaturated fused ring;
further, R 1 ～R 19 Each substituent group is independently any one or more selected from the following groups:hydrogen atom, deuterium atom, halogen atom, cyano group, nitro group, substituted amino group, substituted silicon group, substituted or unsubstituted methyl group, substituted or unsubstituted ethyl group, substituted or unsubstituted n-propyl group, substituted or unsubstituted isopropyl group, substituted or unsubstituted n-butyl group, substituted or unsubstituted tert-butyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted anthryl group, substituted or unsubstituted phenanthryl group, substituted or unsubstituted indenyl group, substituted or unsubstituted fluorenyl group, substituted or unsubstituted spirobifluorenyl group, substituted or unsubstituted indenofluorenyl group, substituted or unsubstituted fluoranthenyl group, substituted or unsubstituted pyrenyl group, substituted or unsubstituted perylene group
A group, a substituted or unsubstituted naphthacene group, a substituted or unsubstituted benzothiophene group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted dibenzosilol group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzoselenophene group, a substituted or unsubstituted carbazolyl group;
further, the condensed ring group described by formula (2) may be preferably selected from the group shown below: :
when the substituent is present in the above groups, the substituent is independently selected from deuterium atom, halogen atom, cyano group, nitro group, hydroxyl group, 1-valent arylamino group having 7 to 30 carbon atoms, 1-valent silicon group having 3 to 30 carbon atoms, 1-valent alkyl or cycloalkyl group having 1 to 10 carbon atoms, 1-valent monocyclic aryl or condensed ring aryl group having 6 to 30 carbon atoms, 1-valent heterocyclic group having 2 to 50 carbon atoms, or condensed ring heteroaryl group;
further, the substituents on the groups are each independently preferably selected from any one or more of the following substituents: deuterium atom, halogen atom, cyano group, nitro group, hydroxyl group, dimethyltriarylamine group, diphenyltriarylamine group, trimethylsilyl group, triphenylsilyl group, methyl group, methoxy group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, 2-methylbutyl group, cyclohexyl group, adamantyl group, 2-ethylhexyl group, trifluoromethyl group, pentafluoroethyl group, 2-trifluoroethyl group, phenyl group, deuterophenyl group, fluorophenyl group, methylphenyl group, n-propylphenyl group, tert-butylphenyl group, trimethylphenyl group, triphenylphenyl group, tetraphenylphenyl group, cyanophenyl group, naphthyl group, anthracenyl group, biphenyl group, terphenyl group, fluorenyl group, spirodibenzofluorenyl group, furyl group, benzofuranyl group, dibenzofuranyl group, azadibenzofuranyl group, thienyl group, benzothienyl group, azadibenzothienyl group, carbazolyl group, azacarbazolyl group.
Further, the compounds represented by the combination of the formula (1) and the formula (2) of the present invention may preferably be represented by the following specific structural compounds 1 to 164, which are merely representative:
another object of the present invention is to provide an organic electroluminescent device. The organic electroluminescent device comprises an anode, a cathode and at least one layer of organic film between the anode and the cathode, wherein the organic film contains one or more organic electroluminescent compounds represented by a combination of formula (1) and formula (2). The organic layer comprises a light-emitting layer and a functional layer, and the compound represented by the combination of the formula (1) and the formula (2) can be used as a main material of the light-emitting layer independently, can be used as a light-emitting material of the light-emitting layer independently, can be used as a mixture of other main materials, can be used as an electron transport layer material, and/or can be used as a hole blocking layer material independently or in a mixture.
In the case where the compound represented by the combination of the formula (1) and the formula (2) is used as the phosphorescent host material in the light-emitting layer, the type or the number of the light-emitting materials is not limited, and the compound may be used as a host of a red phosphorescent material or a host of a green phosphorescent material.
It is a further object of the present invention to provide an organic electroluminescent device. When the compound shown in the formula (1) and the formula (2) is applied to a device, the organic electroluminescent device with higher luminous efficiency and longer service life under low driving voltage is obtained through optimizing the structure of the device.
The beneficial effects of the invention include:
the compound protected by the invention is a dipyridyl diphenoxy boron fluoride compound, and the combination of the dipyridyl diphenoxy boron fluoride unit and the group represented by the formula (2) can realize high-radiation-rate heat activation delayed fluorescence, thereby improving the efficiency and the service life of the organic electroluminescent device.
When the compound disclosed by the invention is applied to an organic electroluminescent device, the dipyridyl diphenoxy boron fluoride group has excellent electron transmission property, so that the compound is used as an electron transmission material, a hole blocking material and/or a main body material, and the organic electroluminescent device manufactured by the compound has the improvement effects of improving the efficiency and prolonging the service life.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this application, illustrate embodiments of the application and together with the description serve to explain the application and do not constitute an undue limitation to the application. In the drawings:
FIG. 1 is a schematic diagram of an organic electroluminescent device to which the compound of the present invention is applied, wherein the structure of each layer of the device is represented as follows:
1. a transparent substrate layer, 2, an ITO anode layer, 3, a hole injection layer, 4, a hole transport layer A,5, a hole transport layer B (or an electron blocking layer), 6, a light emitting layer, 7, an electron transport layer B (or a hole blocking layer), 8, an electron transport layer A,9, an electron injection layer, 10 and a cathode reflection electrode layer;
FIG. 2 is a graph showing fluorescence decay spectra of 2 doped mCBP thin films;
FIG. 3 shows fluorescence decay spectra of the mCBP thin film doped with chemical 11.
Detailed Description
The principles and features of the present invention will be further illustrated by the following examples of various synthetic embodiments, which are provided for purposes of illustration only and are not intended to limit the scope of the invention.
The synthesis of the specific compounds of the combination of formulae (1) and (2) listed below, unless otherwise indicated, is carried out in an anhydrous solvent under a protective gas atmosphere.
Synthesizing an intermediate: synthesis of intermediate 1d
Synthesis of 1 a: 3.2g (20.5 mmol,1.02 eq) of 2-methoxyphenylboronic acid, 3.8g (20 mmol,1.0 eq) of 2-chloro-6-bromopyridine, 0.46g (0.4 mmol,0.02 eq) of palladium tetrakis triphenylphosphine, 5.5g (40 mmol,2.0 eq) of potassium carbonate were weighed into a flask, the flask was purged, purged with nitrogen, 30ml of toluene, 8ml of ethanol and 5ml of water were added and the mixture was refluxed at 90℃for 12 hours. The reaction was stopped, cooled to room temperature, extracted with ethyl acetate, washed three times with water, concentrated in solvent, and separated on a silica gel column to give 3.90g of white solid 1a in 90% yield.
1b synthesis: 3.9g (18 mmol,1.0 eq) of 1a,3.2g (18.9 mmol,1.05 eq) of 4-fluoro-2-methoxyphenylboronic acid, 0.33g (0.36 mmol,0.02 eq) of tris (dibenzylideneacetone) dipalladium, 0.66g (2.16 mmol,0.12 eq) of tri-o-methylphenyl phosphorus, 5.0g (36 mmol,2.0 eq) of potassium carbonate are weighed into a flask, purged with nitrogen, deoxygenated 40ml of tetrahydrofuran, 8ml of water are added and the reaction is refluxed at 80℃for 12h. The reaction was stopped, cooled to room temperature, extracted with ethyl acetate, washed three times with water, concentrated in solvent, and separated on a silica gel column to give 5.4g of white solid 1b in 97% yield.
1c synthesis: 5.4g (17.5 mmol,1.0 eq) 1b,20.0g (175 mmol,10.0 eq) pyridine hydrochloride are weighed into a flask and reacted for 5h under nitrogen with heating and stirring at 180 ℃. Cooling to room temperature, neutralizing with sodium hydroxide solution, precipitating a large amount of solid, filtering, washing with water, collecting filter cake, dispersing in methanol, stirring, filtering, and drying to obtain 4.67g of white solid 1c with a yield of 95%.
1d synthesis: weighing (16.6 mmol,1.0 eq) 1c in 40ml dichloromethane, nitrogen protection, ice water bath, dropwise adding 18.9g (133 mmol,8.0 eq) boron trifluoride diethyl ether, and then 8.56g (66.4 mmol,4.0 eq) N, N-diisopropylethylamine; after the addition was completed, the mixture was stirred at room temperature for 2 hours. The reaction was stopped, and a sodium carbonate solution was added to neutralize the reaction. The reaction solution was extracted with methylene chloride, concentrated by rotary evaporation, methanol was added to precipitate a pale yellow solid, and the solid was collected by filtration and dried to obtain 4.92g of a pale yellow solid 1d in 96% yield.
The same synthesis method replaces 2-methoxyphenylboronic acid with the raw materials in table 1 to obtain other intermediates, as shown in table 1:
TABLE 1
Synthesizing an intermediate: synthesis of intermediate 4c
4a synthesis: 3.81g (20.5 mmol,2.05 eq) of 2-methoxy-4-chlorobenzeneboronic acid, 2.37g (10 mmol,1.0 eq) of 2, 6-dibromopyridine, 0.34g (0.3 mmol,0.03 eq) of tetrakis triphenylphosphine palladium, 5.5g (40 mmol,4.0 eq) of potassium carbonate were weighed into the flask, the flask was purged, purged with nitrogen, 30ml of toluene, 8ml of ethanol and 5ml of water were added and the mixture was refluxed at 90℃for 12 hours. The reaction was stopped, cooled to room temperature, extracted with ethyl acetate, washed three times with water, concentrated in solvent, and separated on a silica gel column to give 3.28g of white solid 4a in 91% yield.
4b synthesis: 3.24g (9 mmol,1.0 eq) of 1b,10.35g (90 mmol,10.0 eq) of pyridine hydrochloride are weighed into a flask, nitrogen protected, heated at 180℃and stirred for 5h. Cooling to room temperature, neutralizing with sodium hydroxide solution, precipitating a large amount of solid, filtering, washing with water, collecting filter cake, dispersing in methanol, stirring, filtering, and drying to obtain 2.84g white solid 4b with a yield of 95%.
4c synthesis: 3.3g (10 mmol,1.0 eq) of 4b are weighed into 40ml of dichloromethane, nitrogen is used for protection, 11.4g (80 mmol,8.0 eq) of boron trifluoride diethyl ether are added dropwise into an ice-water bath, and 5.16g (40 mmol,4.0 eq) of N, N-diisopropylethylamine are added dropwise into the mixture; after the addition was completed, the mixture was stirred at room temperature for 2 hours. The reaction was stopped, and a sodium carbonate solution was added to neutralize the reaction. The reaction solution was extracted with methylene chloride, concentrated by rotary evaporation, methanol was added to precipitate a pale yellow solid, and the solid was collected by filtration and dried to obtain 3.30g of a pale yellow solid 4c, with a yield of 92%.
The same synthesis method replaces 2-methoxyphenylboronic acid with the raw materials in table 2 to obtain other intermediates, as shown in table 2:
TABLE 2
Synthesis example 1: synthesis of chemical formula 2
1.55g (5.0 mmol,1.0 eq) of intermediate 1d,1.75g (5.5 mmol,1.1 eq) of diphenylcarbazole, 3.26g (10.0 mmol,2.0 eq) of cesium carbonate were weighed, 20ml of dry DMF was added and reacted at 120℃for 10h. The reaction was stopped, cooled to room temperature, poured into 100ml of water, yellow solid was precipitated, filtered and washed with water. The filter cake was collected, recrystallised from methylene chloride/methanol, filtered and dried to give 2.74g of a yellow solid in 90% yield, mass spectrum M/z=609.5 (m+h) + 。
The same synthesis method replaces diphenylcarbazole with the raw materials in table 3 to obtain compounds with similar structures, as shown in table 3:
TABLE 3 Table 3
Synthesis example 11: synthesis of chemical modification 10
1.63g (5.0 mmol,1.0 eq) of intermediate 2d,1.84g (5.1 mmol,1.05 eq) of 3-boronic acid-9, 9-spirofluorene, 0.09g (0.10 mmol,0.02 eq) of tris (dibenzylideneacetone) dipalladium, 0.18g (0.40 mmol,0.08 eq) of 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl, 2.1g (10.0 mmol,2.0 eq) of potassium phosphate are weighed, 30ml of tetrahydrofuran and 5ml of deionized water are added and the mixture is reacted at 80℃for 10h under nitrogen protection. The reaction was stopped, cooled to room temperature, poured into 100ml of water and extracted three times with dichloromethane. The organic phase was collected, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. Recrystallisation from methylene chloride/methanol, filtration and drying gave 2.49g of a yellow solid in 82% yield, mass spectrum M/z= 606.5 (m+h) +.
The same synthesis method replaces 3-boric acid-9, 9-spirofluorene with the raw materials in table 4 to obtain compounds with similar structures, as shown in table 4.
TABLE 4 Table 4
Synthesis example 22: synthesis of Compound 11
1.85g (5.0 mmol,1.0 eq) of intermediate 3d,1.84g (5.1 mmol,1.05 eq) of 2-boronic acid-9, 9-spirofluorene, 0.40g (0.40 mmol,0.04 eq) of tetrakis triphenylphosphine palladium, 1.4g (10.0 mmol,2.0 eq) of potassium carbonate, 20ml of toluene, 6ml of ethanol and 3ml of deionized water are weighed and reacted at 90℃for 10h. The reaction was stopped, cooled to room temperature, poured into 100ml of water and extracted three times with dichloromethane. The organic phase was collected, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. Recrystallisation from methylene chloride/methanol, filtration and drying gave 2.73g of a yellow solid in 91% yield. Mass spectrum M/z= 606.5 (m+h) + the same synthesis procedure, 2-boronic acid-9, 9-spirofluorene was replaced with the starting materials in table 5 to obtain compounds of similar structure, as shown in table 5.
TABLE 5
Synthesis example 32: synthesis of chemical modification 66
1.85g (5.0 mmol,1.0 eq) of intermediate 3d,1.88g (5.5 mmol,1.10 eq) of N- [1,1' -biphenyl-4-yl ] -9, 9-dimethyl-9H-fluoren-2-amine, 0.09g (0.1 mmol,0.02 eq) of tris (dibenzylideneacetone) dipalladium, 0.15g (0.4 mmol,0.08 eq) of tri-tert-butylphosphine, 3.26g (10.0 mmol,2.0 eq) of cesium carbonate were weighed and reacted at 120℃for 15H under nitrogen with the addition of 20ml of toluene. The reaction was stopped, cooled to room temperature, poured into 100ml of water and extracted three times with dichloromethane. The organic phase was collected, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. Silica gel column separation and vacuum drying gave 2.66g of yellow solid in 82% yield, mass spectrum M/z= 651.2 (m+h) +.
The same synthesis method replaces 2-boric acid-9, 9-spirofluorene with the raw materials in table 6 to obtain compounds with similar structures, as shown in table 6.
TABLE 6
Synthesis example 37: synthesis of chemical modification 69
1.80g (5.0 mmol,1.0 eq) of intermediate 4c,1.52g (10.5 mmol,2.10 eq) of diphenylamine, 0.09g (0.1 mmol,0.02 eq) of tris (dibenzylideneacetone) dipalladium, 0.18g (0.4 mmol,0.08 eq) of 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl, 3.26g (10.0 mmol,2.0 eq) of cesium carbonate were weighed, and 30ml of toluene was added under nitrogen and reacted at 120℃for 15h. The reaction was stopped, cooled to room temperature, poured into 100ml of water and extracted three times with dichloromethane. The organic phase was collected, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. Silica gel column separation and vacuum drying gave 2.68g of yellow solid in 86% yield, mass spectrum M/z= 626.4 (m+h) + with a concentration of 2.8% by weight
The same synthesis method replaces diphenylamine with the raw materials in table 7 to obtain compounds with similar structures, as shown in table 7.
TABLE 7
Synthesis example 40: synthesis of chemical modification 77
1.80g (5.0 mmol,1.0 eq) of intermediate 5c,2.23g (10.5 mmol,2.10 eq) of dibenzofuran-4-boronic acid, 0.09g (0.1 mmol,0.02 eq) of tris (dibenzylideneacetone) dipalladium, 0.18g (0.4 mmol,0.08 eq) of 2-dicyclohexylphosphorus-2, 4, 6-triisopropylbiphenyl, 3.26g (10.0 mmol,2.0 eq) of cesium carbonate are weighed, 30ml of dioxane is added and the mixture is reacted at 120℃for 15h under nitrogen protection. The reaction was stopped, cooled to room temperature, poured into 100ml of water and extracted three times with dichloromethane. The organic phase was collected, dried over anhydrous sodium sulfate, and the solvent was removed by rotary evaporation. Silica gel column separation and vacuum drying gave 2.65g of yellow solid in 85% yield, mass spectrum M/z= 624.2 (m+h) +.
The same synthesis method replaces dibenzofuran-4-boric acid with raw materials in the table to obtain the compound with similar structure, as shown in the table.
TABLE 8
The fluorescence radiation rate constant of an organic molecule is primarily determined by the degree of overlap of its highest occupied orbitals (HOMO) and lowest unoccupied orbitals (LUMO). For fluorescent molecules of acceptor type structure, the HOMO electron cloud is mainly distributed on the donor unit, such as the aromatic amine and carbazole derivative structure in the invention, while the LUMO electron cloud is mainly distributed on the acceptor unit, such as the pyridine diphenoxy boron fluoride structure in the invention. The rate constant of fluorescence radiation to the acceptor unit is therefore largely determined by the degree of conjugation to the acceptor unit. As shown in the following formula, the molecular REF-2 donor unit and the acceptor unit in the literature (Angew.chem.int.ed.2019, 58, 9088-9094) are connected through phenyl, so that HOMO and LUMO electron clouds have small overlapping and low radiation rate; the molecule 1 of the invention is formed by connecting a donor unit to a phenyl group of an acceptor unit, so that the HOMO and LUMO electron clouds overlap more and have higher fluorescence radiation rate constants. Therefore, the molecular structure of the invention has longer service life when being used as a luminous object in an OLED device.
As previously mentioned, typical TADF molecules are all of the donor/acceptor type structures, with nitrogen-containing strong donor units such as anilines or carbazoles to enhance charge transfer within the molecule to achieve sufficiently small singlet-triplet energy level differences. The 2 molecules of the invention are prepared by connecting the acceptor unit of pyridine diphenoxy boron fluoride with the diphenylcarbazole donor unit. As shown in fig. 2, the fluorescence decay spectrum of the doped film of fig. 2 clearly shows a distinct two-component emission characteristic, demonstrating that fig. 2 has TADF properties. However, strong donor units containing nitrogen generally have good hole transport properties, so that existing TADF molecules exhibit predominantly hole transport electrical properties. Studies (adv. Electron. Mater.2019,5,1800708) have shown that the electron transport properties of the light emitting layer in OLED devices have a greater impact on the lifetime of the device, whereas in the molecular structure provided by the invention, the acceptor units of the pyridine diphenoxyboron fluoride are linked to weak donor units other than nitrogen, such as dibenzofuran, dibenzothiophene, fluorene, phenanthrene units, etc., which also allow for efficient thermally activated delayed fluorescence. As shown in fig. 3, the fluorescence decay spectrum of the doped film of modification 11 clearly shows a distinct two-component emission characteristic, indicating that modification 11 has TADF properties. The molecular structure without strong hole-transporting units provides a TADF material with predominantly electron-transporting properties. Therefore, the TADF material having the main electron transport property is also advantageous for improving the stability of the device.
The following describes the function of the film layer of the organic electroluminescent device according to the preferred embodiment of the present invention.
The organic electroluminescent device according to the present invention comprises an anode layer, a cathode layer, and at least one organic layer between the anode and the cathode. Alternatively, the organic layer is a film layer formed by laminating a plurality of organic compounds. The organic layer may also contain inorganic compounds.
At least one layer of the organic layers of the organic electroluminescent device is a luminescent layer. The organic layer may contain other functional layers in addition to the light-emitting layer, for example, one or more hole injection layers, hole transport layers, or electron blocking layers may be present between the anode layer and the light-emitting layer, it is also possible that an exciton blocking layer or an intermediate layer having a similar function is present between the two light-emitting layers, and one or more hole blocking layers, electron transport layers, or electron injection layers are present between the light-emitting layer and the cathode layer. It should be noted that these functional layers are not necessarily present.
The organic electroluminescent device can be a fluorescent or phosphorescent device or a fluorescent and phosphorescent hybrid device; the light emitting device may be a device having a single light emission, or may be a serial device having a plurality of light emitting units; the light-emitting device may be a single-color light-emitting device, a mixed-color light-emitting device, or a white light-emitting device.
The light emitting layer may include a plurality of guest materials and a plurality of host materials. The guest material may be a fluorescent material, a phosphorescent material, or a thermally activated delayed fluorescent material. The host material is a host material that occupies most of the constituent components in the light-emitting layer, and the host material doped and combined with the fluorescent material is referred to as "fluorescent host", and the host material doped and combined with the phosphorescent material is referred to as "phosphorescent host". The choice of host material is not dependent on its molecular structure, but is distinguished by the host material as guest material.
The compounds of the present invention according to the above embodiments may be used in different organic layers. The compounds of the invention are preferably used as phosphorescent host materials, luminescent materials and/or in electron transport layers and/or in hole blocking layers in organic electroluminescent devices. The use of the compounds of the present invention of the above embodiments is equally applicable to organic electronic devices.
In a preferred embodiment of the present invention, the compound of the present invention is used as a phosphorescent host material in an organic electroluminescent device, and the light-emitting layer of the organic electroluminescent device described herein may be one or more light-emitting layers, at least one of which comprises the compound of the present invention.
In a preferred embodiment of the present invention, the compound of the present invention is used as a light-emitting material in an organic electroluminescent device, and one or more host materials may be selected for use in the light-emitting layer of the organic electroluminescent device described herein.
In another preferred embodiment of the present invention, the compounds of the present invention are used as phosphorescent host materials in organic electroluminescent devices, and one or more phosphorescent materials may be optionally used in combination with the host materials in the light-emitting layer of the organic electroluminescent device described herein.
When the compound is used as a host material, the compound of the invention can be singly used or can be mixed with a plurality of host materials in the light-emitting layer of the organic electroluminescent device. When a plurality of host materials are used together, at least one host material is a compound of the present invention, and other host materials may be other compounds of the present invention, host materials known in the art, or other host materials that have been disclosed or not disclosed. The use mode can adopt a pre-mixing mode or a co-evaporation mode.
In a preferred embodiment of the present invention, the mixture doping ratio of the light emitting material and the host material in the light emitting layer of the organic electroluminescent device, the content of the light emitting material is preferably 0.1 to 30% by weight.
In another preferred embodiment of the present invention, the compounds according to the invention are used as electron transport layer materials in organic electroluminescent devices. The luminescent material in the luminescent layer in the scheme can be a fluorescent material, a phosphorescent material or a thermally activated delayed fluorescent material, or the fluorescent material and the phosphorescent material can be mixed in the luminescent layer.
In this embodiment, the compound of the present invention is used for an electron transport layer, and may be used in a mixture with other electron transport materials. Other electron transporting materials may be other compounds of the present invention, as well as electron transporting materials known in the art or other electron transporting materials that have been disclosed or not. The use mode can adopt a pre-mixing mode or a co-evaporation mode.
In another preferred embodiment of the present invention, the compounds of the present invention are used as hole blocking layer materials in organic electroluminescent devices. The luminescent layer in the scheme can be a fluorescent material, a phosphorescent material or a thermally activated delayed fluorescent material, or the fluorescent material and the phosphorescent material can be mixed in the luminescent layer.
In this embodiment, the compound of the present invention is used for a hole blocking layer, and may be used in a mixture with other hole blocking layer materials. Other hole blocking layer materials may be other compounds of the present invention, as well as hole blocking layer materials known in the art or other hole blocking layer materials that have been disclosed or not. The use mode can adopt a pre-mixing mode or a co-evaporation mode.
Such methods are generally known to those of ordinary skill in the art and can be applied to organic electroluminescent devices comprising the compounds of the present invention without undue inventive effort.
The effect of the use of the compounds of the present invention in organic electroluminescent devices is described in detail below by device examples 1 to 33 and device comparative examples 1 to 17 to verify technical progress and advantageous effects of the compounds of the present invention in the art. The examples and comparative examples merely illustrate the invention in further detail, but the invention is not limited by the technical conditions.
Device example 1: manufacture of organic electroluminescent device as luminescent material for luminescent layer
25mm by 75mm by 1.1mm thick tapeAfter ultrasonic cleaning of a glass substrate of an Indium Tin Oxide (ITO) transparent electrode (anode) in isopropyl alcohol for 5 minutes, ultraviolet (UV) -ozone cleaning was performed for 30 minutes. The film thickness of ITO was 130nm. Mounting the cleaned glass substrate on a substrate frame of a vacuum evaporation device, and vacuumizing to 1×10 -5 ～1×10 -6 Pa, evaporating a Hole Injection Layer (HIL) on the ITO transparent conductive layer, and forming a film thickness of 15nm. A hole transport layer A (HTL) was deposited on the hole injection layer to a film thickness of 60nm. Then, an Electron Blocking Layer (EBL) was deposited on top of the hole transport layer A, with a film thickness of 5nm. Then, an electron blocking layer (EML) was co-deposited on the electron blocking layer to a film thickness of 20nm. The luminescent layer (EML) adopts a multi-source co-evaporation mode to evaporate the luminescent material and the host material of the luminescent layer, wherein the doping concentration of the luminescent material is 5 weight percent. In order to ensure the accuracy of the doping concentration of the luminescent material, the shielding partition plate is opened after the evaporation rates of the luminescent material and the main material are stable, and the multisource co-evaporation is performed. Then, a Hole Blocking Layer (HBL) was deposited on the light-emitting layer to a film thickness of 10nm. Then, an Electron Transport Layer (ETL) was deposited on the hole blocking layer to a film thickness of 25nm. Further, electron injection Electrode (EIL) 8-hydroxyquinoline lithium (Liq) was deposited on the ETL to have a film thickness of 1nm. Then, metal cathode aluminum (Al) was deposited on the EIL to a film thickness of 80nm. The structure of the organic electroluminescent device of example 1 is shown in fig. 1, and fig. 1 also shows the stacking sequence and effect of each functional layer.
TABLE 9 OLED materials
Device example 1:
ITO (130)/HATCN (15)/HTL-1 (60)/EBL-1 (10)/mCBP: chemical 8 (30, 5% by weight)/HBL-1 (10)/ETL-1: liq (25, 50% by weight)/Liq (1)/Al (80).
Device examples 2 to 6 differ from device example 1 only in that the inventive compound chemical 8 used in the light-emitting layer was replaced with another inventive compound, as detailed in table 10.
Comparative examples 1 to 3:
comparative examples 1 to 3 are different from example 1 in that the light emitting layer light emitting materials in the organic electroluminescent device were changed to REF-1 to REF-3 having similar structures reported in the industry, and the obtained device performance test data are shown in table 10.
The OLED was characterized by standard methods. For this purpose, electroluminescence spectra, current efficiency (measured in cd/a), power efficiency (measured in lm/W) and external quantum efficiency (EQE, measured in%) were determined, which were calculated as a function of luminescence density from current/voltage/luminescence density characteristic lines (IUL characteristic lines) exhibiting lambertian emission characteristics. At 1000cd/m 2 The required voltage V1000 is determined at the brightness of (c). CE1000 is shown at 1000cd/m 2 Current efficiency achieved. Finally, EQE1000 is shown at 1000cd/m 2 T95 represents the external quantum efficiency of the device at 1000cd/m 2 The operating time for the device brightness to decrease to 95% at the initial brightness of (1) T98 represents the device at 1000cd/m 2 The operating time for the device brightness to decrease to 98% at the initial brightness of (c).
Table 10
The device properties of examples 1 to 6 and comparative examples 1 to 3 of the present invention as light-emitting objects are summarized in table 10. It can be seen from this that the use of the material of the present invention can improve efficiency while maintaining a low driving voltage, compared to the prior art (comparative examples 1 to 3). As in the EQE1000 of example 6, 17.8% can be achieved, and more importantly, the service life of the OLED is significantly improved, and the lifetime of the device 1-3 is significantly improved compared to the device of comparative example, as compared to the T98 of example 6, which can be achieved for 48 hours.
Examples 7 to 14: manufacture of organic electroluminescent device as phosphorescent host material for green light emitting layer
Example 7: ITO (130)/HATCN (15)/HTL-1 (60)/EBL-1 (10)/chemical 3:GD (30, weight 6%)/HBL-1 (10)/ETL-1:Liq (25, weight 50%)/Liq (1)/Al (80), where the numbers in brackets indicate film thickness (units: nm).
Device examples 8 to 14 differ from device example 7 only in that the inventive compound 3 used in the light-emitting layer was replaced with another inventive compound, as shown in table 11 in detail.
TABLE 11
The device properties of examples 7 to 14 of the present invention and comparative examples 4 to 7 as green host GH are summarized in table 11. The host material of phosphorescent OLED devices is typically the main component of the light-emitting layer, and studies have demonstrated that having balanced bipolar transport capability and a small singlet-triplet energy level difference can facilitate suppression of polaron-triplet interactions in the light-emitting layer, thereby improving device performance, particularly device lifetime (Organic Electronics 2018,5,53-59). As can be seen from table 11, the use of the material of the present invention can improve efficiency while maintaining a low driving voltage, compared to the prior art (comparative examples 4 to 7). Further, by mixing the two host materials, the electron hole transport properties can be further balanced, the device lifetime can be further improved (CN 105579550), the EQE1000 in example 8 is improved by 31.0% compared to comparative example 5 of similar structure, and 19.0% compared to classical CBP (comparative example 7). More importantly, the lifetime of the OLED was significantly improved by 26.1% for T98 of example 9 relative to the device of comparative example 7, while T98 of the hybrid host device example 11 was improved by 53.3% relative to the device of comparative example 7.
Examples 15 to 22: manufacture of organic electroluminescent device as phosphorescent host material for red light emitting layer
Example 15: ITO (130)/HATCN (15)/HTL-1 (60)/EBL-1 (10)/chemical 56:RD (30, weight 6%)/HBL-1 (10)/ETL-1:Liq (25, weight 50%)/Liq (1)/Al (80), where the numbers in brackets indicate film thickness (units: nm).
Device examples 16 to 18 differ from device example 15 only in that the inventive compound 56 used in the light-emitting layer was replaced with another inventive compound, as shown in table 12 in detail.
Device examples 19-22 differ from device example 15 only in that the inventive compound 56 used in the light-emitting layer was replaced with a mixture of the other inventive compound and RH-2 (weight ratio 1:1), as detailed in Table 12.
Table 12
The device properties of examples 15 to 22 and comparative examples 8 to 11 according to the present invention as the red light main body RH are summarized in the table. As can be seen from table 12, the use of the materials of the present invention can increase efficiency by approximately 17% compared to comparative example 9 of similar structure, as compared to the EQE1000 of example 16, while maintaining a lower drive voltage, relative to the prior art (comparative examples 8-11). More importantly, the lifetime of the OLED was significantly improved, as compared to the device of comparative example 10, by 21.9% for T98 of example 17. Further, by employing a mixed mode of the two host materials, the electron hole transport properties can be further balanced, further improving the device lifetime, while T98 of the mixed host device example 22 is improved by 49.6% relative to the device of comparative example 10.
Examples 23 to 28: fabrication of organic electroluminescent devices as hole blocking layer materials
Example 23: ITO (130)/HATCN (15)/HTL-1 (60)/EBL-1 (10)/CBP: GD (30, wt. 6%)/chemical 13 (10)/ETL-1: liq (25, wt. 50%)/Liq (1)/Al (80), wherein the numbers in brackets indicate film thickness (units: nm).
Device examples 24-28 differ from device example 23 only in the replacement of the inventive compound chemical 13 used in the hole blocking layer with other inventive compounds, see in particular table 13.
TABLE 13
The device properties of the hole blocking materials HBL according to examples 23 to 28 of the present invention and comparative examples 12 to 14 are summarized in table 13. It can be seen that the use of the materials of the present invention can maintain a lower drive voltage while improving efficiency, as compared to the prior art (comparative examples 12-14), by 17.2% for EQE1000 in example 26 compared to comparative example 14. More importantly, the lifetime of the OLED was significantly improved, as compared to the device of comparative example 14, by 41.6% for T98 of example 27.
Examples 29 to 33: manufacture of organic electroluminescent devices as electron transport materials
Example 29: ITO (130)/HATCN (15)/HTL-1 (60)/EBL-1 (10)/CBP: GD (30, wt. 6%)/HBL-1 (10)/15:Liq (25, wt. 50%)/Liq (1)/Al (80), where the numbers in brackets indicate film thickness (units: nm).
Device examples 30-33 differ from device example 29 only in the replacement of the inventive compound 15 used in the electron transport layer with other inventive compounds, see in particular table 14.
TABLE 14
The device properties of examples 29 to 33 of the present invention and comparative examples 15 to 17 as electron transport materials ETL are summarized in table 14, from which it can be seen that the use of the materials of the present invention can improve efficiency while maintaining a lower driving voltage, as compared with comparative example 17, by 14.8% as compared with EQE1000 in example 31. More importantly, the service life of the OLED was significantly improved, such as 36.9% improvement in T98 of example 30 over the device of comparative example 17.
Claims (9)
1. A dipicolinate boron fluoride-based compound having a structure represented by a combination of formula (1) and formula (2):
wherein,,
the substituent represented by formula (2) is represented by R of formula (1) alone 2 、R 3 、R 9 Or R is 10 The position is substituted, and the formula (2) is represented by the formula-R 2 、R 3 、R 9 Or R is 10 The positions are bonded;
in the formula (2), p and q are each independently an integer of 1 to 4;
in the formula (2), L is independently selected from a single bond, a substituted or unsubstituted straight-chain or branched alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 ring-forming carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 ring-forming carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 ring-forming carbon atoms, a substituted or unsubstituted arylene group having 10 to 50 ring-forming carbon atoms, and a substituted or unsubstituted heterocyclylene group having 6 to 50 ring-forming atoms;
in the formula (2), X 1 ～X 8 Are independently selected from CR 12 Or N;
in the formula (2), Y 1 And Y 2 Are independently selected from CR 13 R 14 、SiR 17 R 18 、NR 19 O, S, wherein Y 2 May also be selected as single bond or hydrogen bond;
r of formula (1) 1 ～R 11 R of formula (2) 12 ～R 19 The substituents are each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, a substituted amine group, a substituted silicon group, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted n-butyl group, a substituted or unsubstituted t-butyl groupA group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted spirobifluorenyl group, a substituted or unsubstituted indenofluorenyl group, a substituted or unsubstituted fluoranthenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted perylene group
A group, a substituted or unsubstituted naphthacene group, a substituted or unsubstituted dibenzosilol group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzoselenophenyl group, a substituted or unsubstituted carbazolyl group;
the term "substituted" in the term "substituted or unsubstituted" in the above-mentioned compounds means that the substituent is independently selected from deuterium atom, halogen atom, cyano group, nitro group, hydroxyl group, 1-valent arylamine group having 7 to 30 carbon atoms, 1-valent silicon group having 3 to 30 carbon atoms, 1-valent alkyl or cycloalkyl group having 1 to 10 carbon atoms, 1-valent monocyclic aryl or condensed ring aryl group having 6 to 30 carbon atoms, 1-valent heterocyclic group having 2 to 50 carbon atoms, or condensed ring heteroaryl group.
2. The compound according to claim 1, wherein the compound X in formula (2) 1 ～X 8 The total number of nitrogen atoms in the catalyst is an integer of 0 to 5.
3. The compound according to claim 1, wherein the compound X in formula (2) 1 ～X 8 The total number of nitrogen atoms in the catalyst is an integer of 0 to 3.
4. A dipicolinate boron fluoride-based compound having a structure represented by a combination of formula (1) and formula (2):
wherein,,
the substituent represented by formula (2) is represented by R of formula (1) alone 2 、R 3 、R 9 Or R is 10 The position is substituted, and the formula (2) is represented by the formula-R 2 、R 3 、R 9 Or R is 10 The positions are bonded;
in the formula (2), p and q are each independently an integer of 1 to 4;
in the formula (2), L is independently selected from a single bond, a substituted or unsubstituted straight-chain or branched alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkylene group having 3 to 20 ring-forming carbon atoms, a substituted or unsubstituted arylene group having 6 to 30 ring-forming carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 ring-forming carbon atoms, a substituted or unsubstituted arylene group having 10 to 50 ring-forming carbon atoms, and a substituted or unsubstituted heterocyclylene group having 6 to 50 ring-forming atoms;
wherein R of formula (1) 1 ～R 11 Each substituent is independently selected from the group consisting of a hydrogen atom, a deuterium atom, a halogen atom, a cyano group, a nitro group, a substituted amine group, a substituted silicon group, a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted n-propyl group, a substituted or unsubstituted isopropyl group, a substituted or unsubstituted n-butyl group, a substituted or unsubstituted tert-butyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted spirobifluorenyl group, a substituted or unsubstituted indenofluorenyl group, a substituted or unsubstituted fluoranthenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted perylene group, and a substituted or unsubstituted indenofluorenyl group
A group, a substituted or unsubstituted naphthacene group, a substituted or unsubstituted dibenzosilol group, a substituted or unsubstituted dibenzothienyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzoselenophenyl group, a substituted or unsubstituted carbazolyl group;
"substituted" in the "substituted or unsubstituted" in the compound means that the substituent is independently selected from deuterium atom, halogen atom, cyano group, nitro group, hydroxyl group, 1-valent arylamine group of 7 to 30 carbon atoms, 1-valent silicon group of 3 to 30 carbon atoms, 1-valent alkyl or cycloalkyl group of 1 to 10 carbon atoms, 1-valent monocyclic aryl or condensed ring aryl group of 6 to 30 carbon atoms, 1-valent heterocyclic group of 2 to 50 carbon atoms, or condensed ring heteroaryl group;
the condensed ring group in formula (2) may be selected from the group shown below:
5. the compound of claim 1, wherein L in formula (2) is independently selected from any one or more of the following groups: a pyridylene group, a phenylene group, a biphenylene group, a naphthylene group, and an anthracenylene group.
6. A dipicolinate boron fluoride-based compound selected from the group consisting of the following structures:
7. an organic electroluminescent device comprising an anode, a cathode, and at least one organic thin film between the anode and the cathode, wherein the organic thin film comprises the compound according to any one of claims 1 to 6.
8. The organic electroluminescent device according to claim 7, wherein the organic thin film comprises any one or a combination of at least two of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an exciton blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer, and wherein at least one of the light emitting layer, the hole blocking layer, and the electron transport layer contains the compound according to any one of claims 1 to 6.
9. The organic electroluminescent device according to claim 7 or 8, wherein the compound is used as a luminescent material, host material, hole blocking material or electron transport material of a luminescent layer selected in the organic electroluminescent device.
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| CN1245822A (en) * | 1999-09-05 | 2000-03-01 | 吉林大学 | Phenolic group-pyridine or metal coordination compound of its derivative and their application as electroluminescence material |
| CN111333671A (en) * | 2020-03-16 | 2020-06-26 | 清华大学 | Luminescent material, application thereof and organic electroluminescent device comprising luminescent material |
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| US7033681B2 (en) * | 2004-03-18 | 2006-04-25 | Eastman Kodak Company | Organic element for electroluminescent devices |
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