CN115636822A - Electron transport material and preparation method and application thereof - Google Patents
Electron transport material and preparation method and application thereof Download PDFInfo
- Publication number
- CN115636822A CN115636822A CN202110812825.3A CN202110812825A CN115636822A CN 115636822 A CN115636822 A CN 115636822A CN 202110812825 A CN202110812825 A CN 202110812825A CN 115636822 A CN115636822 A CN 115636822A
- Authority
- CN
- China
- Prior art keywords
- electron transport
- substituted
- unsubstituted
- transport material
- group
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 239000000463 material Substances 0.000 title claims abstract description 76
- 238000002360 preparation method Methods 0.000 title abstract description 18
- 150000001875 compounds Chemical class 0.000 claims abstract description 15
- 239000010410 layer Substances 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 20
- 238000002347 injection Methods 0.000 claims description 11
- 239000007924 injection Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical group [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 claims description 10
- 125000001424 substituent group Chemical group 0.000 claims description 10
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 125000001072 heteroaryl group Chemical group 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- 230000005525 hole transport Effects 0.000 claims description 5
- 239000002346 layers by function Substances 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 125000006736 (C6-C20) aryl group Chemical group 0.000 claims description 4
- 125000000732 arylene group Chemical group 0.000 claims description 4
- 150000007514 bases Chemical class 0.000 claims description 4
- 230000000903 blocking effect Effects 0.000 claims description 4
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 3
- 239000004305 biphenyl Substances 0.000 claims description 3
- 125000005956 isoquinolyl group Chemical group 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 125000004076 pyridyl group Chemical group 0.000 claims description 3
- 125000000714 pyrimidinyl group Chemical group 0.000 claims description 3
- 125000005493 quinolyl group Chemical group 0.000 claims description 3
- 125000004306 triazinyl group Chemical group 0.000 claims description 3
- 230000009471 action Effects 0.000 claims description 2
- 125000002529 biphenylenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3C12)* 0.000 claims description 2
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 2
- 125000002993 cycloalkylene group Chemical group 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000005549 heteroarylene group Chemical group 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 125000004957 naphthylene group Chemical group 0.000 claims description 2
- 125000000843 phenylene group Chemical group C1(=C(C=CC=C1)*)* 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- PXXJHWLDUBFPOL-UHFFFAOYSA-N benzamidine Chemical group NC(=N)C1=CC=CC=C1 PXXJHWLDUBFPOL-UHFFFAOYSA-N 0.000 claims 1
- 229910052801 chlorine Inorganic materials 0.000 claims 1
- 239000000460 chlorine Substances 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 26
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 12
- 239000007858 starting material Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- 239000012300 argon atmosphere Substances 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000004896 high resolution mass spectrometry Methods 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 6
- 238000000746 purification Methods 0.000 description 6
- 238000001953 recrystallisation Methods 0.000 description 6
- 238000010898 silica gel chromatography Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- UJOBWOGCFQCDNV-UHFFFAOYSA-N 9H-carbazole Chemical compound C1=CC=C2C3=CC=CC=C3NC2=C1 UJOBWOGCFQCDNV-UHFFFAOYSA-N 0.000 description 4
- 238000005401 electroluminescence Methods 0.000 description 4
- 239000011368 organic material Substances 0.000 description 4
- 229940125904 compound 1 Drugs 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 230000002035 prolonged effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 125000000641 acridinyl group Chemical class C1(=CC=CC2=NC3=CC=CC=C3C=C12)* 0.000 description 2
- TXVHTIQJNYSSKO-UHFFFAOYSA-N benzo[e]pyrene Chemical class C1=CC=C2C3=CC=CC=C3C3=CC=CC4=CC=C1C2=C34 TXVHTIQJNYSSKO-UHFFFAOYSA-N 0.000 description 2
- -1 benzopyridindole Chemical compound 0.000 description 2
- TXCDCPKCNAJMEE-UHFFFAOYSA-N dibenzofuran Chemical compound C1=CC=C2C3=CC=CC=C3OC2=C1 TXCDCPKCNAJMEE-UHFFFAOYSA-N 0.000 description 2
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 125000003983 fluorenyl group Chemical class C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 2
- 238000004020 luminiscence type Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- GHYOCDFICYLMRF-UTIIJYGPSA-N (2S,3R)-N-[(2S)-3-(cyclopenten-1-yl)-1-[(2R)-2-methyloxiran-2-yl]-1-oxopropan-2-yl]-3-hydroxy-3-(4-methoxyphenyl)-2-[[(2S)-2-[(2-morpholin-4-ylacetyl)amino]propanoyl]amino]propanamide Chemical compound C1(=CCCC1)C[C@@H](C(=O)[C@@]1(OC1)C)NC([C@H]([C@@H](C1=CC=C(C=C1)OC)O)NC([C@H](C)NC(CN1CCOCC1)=O)=O)=O GHYOCDFICYLMRF-UTIIJYGPSA-N 0.000 description 1
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 1
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 1
- MYKQKWIPLZEVOW-UHFFFAOYSA-N 11h-benzo[a]carbazole Chemical compound C1=CC2=CC=CC=C2C2=C1C1=CC=CC=C1N2 MYKQKWIPLZEVOW-UHFFFAOYSA-N 0.000 description 1
- MALZYBOXBVXCSN-UHFFFAOYSA-N 11h-pyrido[3,2-a]carbazole Chemical compound C1=CC2=NC=CC=C2C2=C1C1=CC=CC=C1N2 MALZYBOXBVXCSN-UHFFFAOYSA-N 0.000 description 1
- NJBMMMJOXRZENQ-UHFFFAOYSA-N 6H-pyrrolo[2,3-f]quinoline Chemical compound c1cc2ccc3[nH]cccc3c2n1 NJBMMMJOXRZENQ-UHFFFAOYSA-N 0.000 description 1
- BGEVROQFKHXUQA-UHFFFAOYSA-N 71012-25-4 Chemical compound C12=CC=CC=C2C2=CC=CC=C2C2=C1C1=CC=CC=C1N2 BGEVROQFKHXUQA-UHFFFAOYSA-N 0.000 description 1
- MZXDPTWGJXNUMW-UHFFFAOYSA-N 7h-pyrido[3,2-c]carbazole Chemical compound C1=CC=NC2=C3C4=CC=CC=C4NC3=CC=C21 MZXDPTWGJXNUMW-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229940027998 antiseptic and disinfectant acridine derivative Drugs 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 description 1
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000000609 carbazolyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3NC12)* 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229940125797 compound 12 Drugs 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- 229940126214 compound 3 Drugs 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 125000004987 dibenzofuryl group Chemical group C1(=CC=CC=2OC3=C(C21)C=CC=C3)* 0.000 description 1
- 125000004988 dibenzothienyl group Chemical group C1(=CC=CC=2SC3=C(C21)C=CC=C3)* 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001194 electroluminescence spectrum Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 125000002541 furyl group Chemical group 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 125000002883 imidazolyl group Chemical group 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- VVVPGLRKXQSQSZ-UHFFFAOYSA-N indolo[3,2-c]carbazole Chemical compound C1=CC=CC2=NC3=C4C5=CC=CC=C5N=C4C=CC3=C21 VVVPGLRKXQSQSZ-UHFFFAOYSA-N 0.000 description 1
- 229960005544 indolocarbazole Drugs 0.000 description 1
- 125000001041 indolyl group Chemical group 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N o-biphenylenemethane Natural products C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 description 1
- 125000002971 oxazolyl group Chemical group 0.000 description 1
- 125000005561 phenanthryl group Chemical group 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 125000003373 pyrazinyl group Chemical group 0.000 description 1
- 125000002098 pyridazinyl group Chemical group 0.000 description 1
- 125000000168 pyrrolyl group Chemical group 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940066767 systemic antihistamines phenothiazine derivative Drugs 0.000 description 1
- 125000000335 thiazolyl group Chemical group 0.000 description 1
- 125000001544 thienyl group Chemical group 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Landscapes
- Electroluminescent Light Sources (AREA)
Abstract
The invention provides an electron transport material, a preparation method and application thereof, wherein the electron transport material has a structure shown as a formula I and is a compound with a condensed ring-carbazolyl parent nucleus structure.
Description
Technical Field
The invention belongs to the technical field of organic photoelectric materials, and particularly relates to an electron transport material and a preparation method and application thereof.
Background
Organic Electroluminescence (EL) was discovered 50 years ago by exciting an organic material to emit light by electric energy, but it was not until 1987 when an Organic Light Emitting Diode (OLED) was produced. The OLED is a device for generating electroluminescence by utilizing a multi-layer organic thin film structure, and has the advantages of easy manufacture and low required driving voltage. Compared with the liquid crystal display, the organic electroluminescent display does not need a backlight source, has large visual angle and low power, has the response speed which is 1000 times that of the liquid crystal display, and has the manufacturing cost which is lower than that of the liquid crystal display with the same resolution, so the organic electroluminescent device has wide application prospect.
The generation of organic electroluminescence depends on the recombination of carriers, i.e., electrons and holes, transmitted in organic electroluminescent materials, and organic materials are classified into hole-transporting materials, light-emitting materials, electron-transporting materials, and the like, according to the functions performed in OLED devices. Organic materials are less conductive than inorganic semiconductors.
Therefore, in order to improve the performance of the OLED device, the problems of poor charge injection and transport capability of the organic electroluminescent material must be solved. In the current research, in order to further improve the service life of the OLED device, improvements and innovations on organic materials used for the OLED device are often needed. For example, CN106243014A discloses a benzopyrene derivative, and by optimizing the molecular structure design, the benzopyrene derivative obtained by the present invention has higher electron transport efficiency, and can be used to prepare organic electroluminescent devices, especially as an electron transport material in organic electroluminescent devices, and can effectively improve the luminescent efficiency of OLED devices, and the maximum luminance of the devices reaches 1000cd/m 2 . CN109734648A discloses a compound for an organic electroluminescent device, the general formula of the molecular structure of which is Z 1 -L-Z 2 Wherein, Z 1 、Z 2 Independently selected from substituted or unsubstituted C6-C30 carbazole, benzocarbazole, dibenzocarbazole, pyridoindole, benzopyridindole, indoloquinoline, pyridocarbazole, indolocarbazole or bicarbazole derivatives; in the same structural formula Z 1 、Z 2 Can not have the same parent structure at the same time; l is selected from substituted or unsubstituted fluorene, dibenzothiophene, dibenzofuran, carbazole, phenothiazine and acridine derivatives. The organic photoelectric material can solve the technical problems of low luminous efficiency, higher driving voltage, short service life and the like of an organic photoelectric material in the prior art.
Although the prior art has disclosed the electron transport material and its application in the OLED device, the electron transport material still has few kinds, and there are also problems that the driving voltage is high, the transport efficiency is low, and the service life is shortened.
Therefore, it is of great practical significance to develop a wider variety of electron transport materials with excellent stability and high transport efficiency to meet the requirements of OLEDs with low driving voltage, high efficiency and long lifetime.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide an electron transport material, a preparation method and an application thereof, wherein the electron transport material endows the electron transport material with excellent electron transport performance by utilizing the synergistic effect of a mother nucleus with a specific structure and a substituent on a special site, and when the electron transport material is applied to an OLED device, the driving voltage can be effectively reduced, the luminous efficiency of the device can be improved, and the service life can be prolonged.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides an electron transport material having a structure represented by formula I:
wherein A is 1 、A 2 Each independently selected from any one of a single bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heteroarylene group, and a substituted or unsubstituted C3-C30 cycloalkylene group.
L 1 、L 2 Each independently selected from a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group, and a substituted or unsubstituted C3-C30 cycloalkyl group.
m is an integer of 0 to 4 (for example, 1, 2, 3, etc.), and p is an integer of 1 to 4 (for example, 2, 3, etc.).
The C6-C30 can be C6, C7, C8, C9, C10, C12, C15, C18, C20, C22, C24, C25, C27 or C29, etc.
The C3-C30 can be C4, C5, C6, C8, C10, C12, C15, C18, C20, C22, C24, C25, C27 or C29, etc.
According to the invention, the parent nucleus of the electron transport material is a condensed ring-carbazolyl compound and is of a large conjugated structure, the electron cloud distribution is more uniform due to the structure, the electron transport is facilitated, the molecular internal energy is reduced, the molecular stability is improved, the material is less prone to deterioration in the evaporation process, the parent nucleus structure and a substituent group have synergistic effect, the electron transport material is endowed with excellent electron transport performance, and the electron transport material is applied to an OLED device, so that the luminous efficiency of the device can be effectively improved, the driving voltage is reduced, and the service life is prolonged.
In the present invention, A 1 、A 2 、L 1 、L 2 Wherein each of said substituted substituents is independently selected from at least one of C6-C30 (e.g., C6, C8, C10, C12, C15, C18, C20, C22, C24, C27, or C29, etc.) aryl, C3-C30 (e.g., C4, C5, C6, C8, C10, C13, C15, C18, C20, C23, C25, C27, or C29, etc.) heteroaryl, or C3-C30 (e.g., C4, C5, C6, C8, C10, C13, C15, C18, C20, C23, C25, C27, or C29, etc.) cycloalkyl.
Preferably, m is 0 or 1.
Preferably, p is 1.
In the present invention, said A 1 、A 2 Each independently represents a single bond or a C6-C18 arylene group.
Said "A" is 1 Is a single bond ", meaning that the substituent L 1 Is connected with the parent nucleus structure through a single bond, said' A 2 Is a single bond "means the substituent L 2 Attached to the parent nuclear structure by a single bond, as described below in relation to the same ("A) 1 Is a single bond "or" A 2 Single bond ") have the same meaning.
Preferably, said A is 1 、A 2 Each independently selected from a single bond, phenylene, biphenylene, or naphthylene.
In the present invention, said L 1 Is selected from any one of C6-C20 aryl.
The C6 to C20 aryl group, for example, may be a C6, C8, C9, C10, C12, C16, or C18 aryl group, and exemplary include, but are not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, fluorenyl, or the like.
Preferably, said L 1 Is phenyl or biphenyl.
Preferably, said L 2 And (b) any one selected from substituted or unsubstituted C3-C30 heteroaryl.
The C3 to C30 heteroaryl group, for example, may be a heteroaryl group of C4, C5, C6, C7, C8, C9, C10, C13, C15, C18, C20, C23, C25, C27, or C29, etc., and the heteroatoms of the heteroaryl group include N, O, or S, etc., and exemplarily include but are not limited to: n-phenylcarbazolyl, furyl, thienyl, pyrrolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, carbazolyl, acridinyl, imidazolyl, oxazolyl, thiazolyl, indolyl, benzofuryl, benzothienyl, dibenzofuryl, dibenzothienyl, benzimidazolyl, quinolyl, isoquinolyl and the like.
Preferably, said L 2 And any one selected from the group consisting of benzazepinyl, dibenzacridinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted pyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted quinolyl, and substituted or unsubstituted isoquinolyl.
The substituted substituents are each independently selected from at least one of C6-C20 aryl or C3-C20 heteroaryl.
Preferably, said L 2 Any one selected from the following groups:
In the present invention, the electron transport material includes any one or a combination of at least two of the following compounds 1 to 15:
in a second aspect, the present invention provides a method for preparing an electron transport material as described in the first aspect, the method comprising: will be provided with
And U-L 2 And reacting under the action of a catalyst to obtain the electron transport material.
A 1 、A 2 、L 1 、L 2 M, p each independently have the same defined ranges as in formula 1.
U is selected from halogen.
Preferably, said U is chloro.
Preferably, the catalyst comprises a combination of a palladium catalyst and a basic compound.
Preferably, the palladium catalyst is tetrakis (triphenylphosphine) palladium.
Preferably, the basic compound is sodium hydroxide.
Preferably, the reaction is carried out in a solvent.
Preferably, the solvent is a mixed solution of water and tetrahydrofuran.
Preferably, the volume ratio of tetrahydrofuran to water is 1 (0.3-0.6), and can be, for example, 1.
In the present invention, the reaction temperature is 110 to 130 ℃, and may be, for example, 112 ℃, 115 ℃, 116 ℃, 118 ℃, 120 ℃, 122 ℃, 124 ℃, 126 ℃, 128 ℃ or 129 ℃.
Preferably, the reaction time is 12 to 16 hours, for example, 13 hours, 13.2 hours, 13.5 hours, 14 hours, 14.2 hours, 14.5 hours, 15 hours, 15.2 hours or 15.5 hours, and the specific values therebetween are not exhaustive, and the invention is not limited to the specific values included in the ranges for brevity and conciseness.
In a third aspect, the present invention provides an OLED device, which includes an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport functional layer, and a cathode, which are sequentially disposed; the material of the electron transport functional layer comprises the electron transport material according to the first aspect.
Preferably, the electron transport functional layer comprises any one of a hole blocking layer, an electron transport layer or an electron injection layer or a combination of at least two of the two; the hole blocking layer and/or the electron transport layer comprises an electron transport material as described in the first aspect.
In a fourth aspect, the present invention provides an electronic device comprising an OLED device as described in the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
the electron transport material provided by the invention is a compound with a condensed ring-carbazolyl parent nucleus structure, has excellent electron transport performance through the synergistic effect between the specific parent nucleus structure and a plurality of substituents at specific sites, can effectively reduce the driving voltage to 3.74-3.8V when being applied to an OLED device, improves the luminous efficiency of the device to 7.5-8.7 Cd/A, can prolong the service life of the OLED device at the same time, and can reach 203-240 h.
Detailed Description
The technical solution of the present invention is further described below by way of specific embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention.
The compound starting materials (including compounds A1, A2, A3, A4, A5, A6, A7, A8, A9) in the following examples of the present invention are all commercially available.
Example 1
The embodiment provides an electron transport material and a preparation method thereof, wherein the electron transport material has the following structure:
the preparation method of the electron transport material comprises the following steps:
3g of starting material A1, 4g of starting material A2, 0.16mmol of palladium acetate, 0.32mmol of tetrakis (triphenylphosphine), 9.6mmol of sodium hydroxide, 34ml of tetrahydrofuran and 16ml of water are mixed together under an argon atmosphere, stirred at 125 ℃ for 12h, the reaction is ended and, after separation by silica gel column chromatography and purification by recrystallization, 4.1g of the expected product compound 1 are obtained, in a yield of 61%.
And (3) structural test of a target product: high resolution Mass Spectrometry test, C 52 H 30 N 4 Calculated O: 726.84, test value: 726.24; c 52 H 30 N 4 C, N, H and O element analysis theoretical values in O: c,85.93; n,7.97; h,4.30; o,2.20; elemental analysis test value: c,85.85; n,7.95; h,4.67; o,2.23.
Example 2
The embodiment provides an electron transport material and a preparation method thereof, wherein the electron transport material has the following structure:
the preparation method of the electron transport material comprises the following steps:
3g of starting material A3, 4g of starting material A4, 0.16mmol of palladium acetate, 0.32mmol of tetrakis (triphenylphosphine), 9.6mmol of sodium hydroxide, 34ml of tetrahydrofuran and 16ml of water are mixed together under an argon atmosphere, stirred at 125 ℃ for 12h, the reaction is ended and, after separation by silica gel column chromatography and purification by recrystallization, 4.3g of the expected product compound 2 are obtained, in 60% yield.
Structural test of the target product: high resolution Mass Spectrometry test, C 52 H 32 N 4 Calculated values are: 712.86, test value: 712.26; c 50 H 32 N 4 C, N and H in elements are analyzed and calculated according to the following theoretical values: c,87.03; n,7.83; h,4.63; elemental analysis test value: c,87.62; n,7.86; h,4.52.
Example 3
The embodiment provides an electron transport material and a preparation method thereof, wherein the electron transport material has the following structure:
the preparation method of the electron transport material comprises the following steps:
3g of starting material A1, 4g of starting material A4, 0.16mmol of palladium acetate, 0.32mmol of tetrakis (triphenylphosphine), 9.6mmol of sodium hydroxide, 34ml of tetrahydrofuran and 16ml of water are mixed together under an argon atmosphere, stirred at 125 ℃ for 12h, the reaction is ended and, after separation by silica gel column chromatography and purification by recrystallization, 4.3g of the target compound 3 are obtained, in 62% yield.
Structural test of the target product: high resolution Mass Spectrometry test, C 46 H 28 N 4 Calculated values are: 636.23, test value: 636.76; c 46 H 28 N 4 Analysis theoretical values of C, N and H elements: c,86.77; n,8.80; h,4.43; elemental analysis test value: c,86.67; n,8.85; h,4.47.
Example 4
The embodiment provides an electron transport material and a preparation method thereof, wherein the electron transport material has the following structure:
the preparation method of the electron transport material comprises the following steps:
under argon atmosphere, 3g of raw material A5, 4g of raw material A6, 0.16mmol of palladium acetate, 0.32mmol of tetrakis (triphenylphosphine), 9.6mmol of sodium hydroxide, 34ml of tetrahydrofuran and 16ml of water are mixed together, stirred at 125 ℃ for 12 hours, and after the reaction is finished, the target product compound 4 is obtained by silica gel column chromatography separation and recrystallization purification, wherein the yield is 58%;
and (3) structural test of a target product: high resolution Mass Spectrometry test, C 52 H 32 N 2 Calculating the value: 684.26, test value: 684.84; c 52 H 32 N 2 Analysis theoretical values of C, N and H elements: c,91.2; n,4.09; h,4.73; elemental analysis test value: c,91.3; n,4.06; h,4.71.
Example 5
The embodiment provides an electron transport material and a preparation method thereof, wherein the electron transport material has the following structure:
the preparation method of the electron transport material comprises the following steps:
3g of starting material A1, 4g of starting material A7, 0.16mmol of palladium acetate, 0.32mmol of tetrakis (triphenylphosphine), 9.6mmol of sodium hydroxide, 34ml of tetrahydrofuran and 16ml of water are mixed together under an argon atmosphere, stirred at 125 ℃ for 12h, the reaction is ended and, after purification by silica gel column chromatography and recrystallization, 4.5g of the expected product compound 5 are obtained, in 58% yield.
And (3) structural test of a target product: high resolution Mass Spectrometry test, C 54 H 32 N 2 Calculated values: 708.26, test value: 708.26; c 54 H 32 N 2 And analysis theoretical values of medium C, N and H elements: c,91.5; n,3.95; h,4.55; elemental analysis test value: c,91.4; n,3.98; h,4.45.
Example 6
The embodiment provides an electron transport material and a preparation method thereof, wherein the electron transport material has the following structure:
the preparation method of the electron transport material comprises the following steps:
3g of the starting material A8, 4g of the starting material A9, 0.16mmol of palladium acetate, 0.32mmol of tetrakis (triphenylphosphine), 9.6mmol of sodium hydroxide, 34ml of tetrahydrofuran and 16ml of water are mixed together under an argon atmosphere, stirred at 125 ℃ for 12h, the reaction is ended, and after separation by silica gel column chromatography and purification by recrystallization, 4.6g of the target product compound 6 are obtained, the yield being 63%.
Structural test of the target product: high resolution Mass Spectrometry test, C 64 H 38 N 4 Calculated value of O: 878.3, test value: 879.03; c 62 H 38 N 4 C, N and H element analysis theoretical values in O: c,87.45; o,1.82; n,6.37; h,4.36; elemental analysis test value: c,87.47; o,1.72; n,6.47; h,4.33.
Application examples 1 to 6
Application examples 1-6 and comparative application examples each provide an OLED device comprising, in order: an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and a cathode; the material composition of each layer is as follows:
anode: indium Tin Oxide (ITO) with a thickness of 80nm;
hole injection layer: the thickness is 60nm; the material is HIL;
hole transport layer: the thickness is 80nm; the material is HTL;
light-emitting layer: the thickness is 30nm; the host material is BH, the object material is BD, and the mass percentage of the object material is 5%;
electron transport layer: the thickness is 10nm; the materials were the electron transport materials provided in examples 1-6, respectively;
electron injection layer: the thickness is 2nm; the material is LiF;
cathode: the thickness is 150nm; the material is an Al electrode;
the hole injection layer, the hole transport layer, the light emitting layer, the electron transport layer, the electron injection layer and the cathode of the OLED device are prepared by an evaporation method.
Application examples 7 and 8
Application examples 7 and 8 provide an OLED device which is different from application example 1 in that the electron transport materials in the electron transport layer are compound 8 and compound 12, respectively.
Comparative example 1
This comparative example provides an OLED device which differs from application example 1 in that compound 1 of the hole-blocking layer was used as compound D1
And (6) replacing.
Comparative example 2
This comparative example provides an OLED device which differs from application example 1 in that compound 1 of the hole-blocking layer is used as compound D2
And (6) replacing.
Performance testing of the OLED devices:
the OLED devices provided in application examples 1-6 and comparative application example 1 were tested at 1000cd/m 2 Measuring an electroluminescence spectrum at the luminescence density of (a) to obtain a driving voltage and a luminescence efficiency, as shown in table 1; at 40mA/cm 2 The device lifetime T95 was calculated, T95 being the time for the luminance to drop to 95% of its initial value in operation, and the test results are shown in table 1:
TABLE 1
As can be seen from the data in Table 1, when the electron transport material provided by the invention is used in an OLED device, the driving voltage is lower, only 3.74-3.81V, the luminous efficiency is higher, 7.5-8.7 Cd/A, the service life of the OLED device is prolonged, and the service life can reach 203-240 h. It can be seen from comparative examples 1 and 2 that when the parent nucleus structure of the compound is changed or the substituent in the compound is absent, the application of the compound to an OLED device can increase the driving voltage and reduce the luminous efficiency, and simultaneously greatly reduce the service life of the device and influence the performance of the device.
The applicant states that the present invention is illustrated by the above embodiments of the electron transport material of the present invention, and the preparation method and application thereof, but the present invention is not limited to the above embodiments, that is, it does not mean that the present invention must be implemented by the above embodiments. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. An electron transport material having a structure according to formula I:
wherein A is 1 、A 2 Each independently selected from any one of a single bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heteroarylene group and a substituted or unsubstituted C3-C30 cycloalkylene group;
L 1 、L 2 each independently selected from any one of substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, and substituted or unsubstituted C3-C30 cycloalkyl;
m is an integer of 0 to 4, and p is an integer of 1 to 4.
2. The electron transport material of claim 1, wherein a is 1 、A 2 、L 1 、L 2 Wherein each of the substituted substituents is independently at least one selected from C6-C30 aryl, C3-C30 heteroaryl or C3-C30 cycloalkyl;
preferably, m is 0 or 1;
preferably, p is 1.
3. The electron transport material of claim 1 or 2, wherein a is 1 、A 2 Each independently is a single bond or any one of C6-C18 arylene;
preferably, A is 1 、A 2 Each independently selected from a single bond, phenylene, biphenylene, or naphthylene.
4. The electron transport material of any of claims 1-3, wherein L is 1 Any one selected from C6-C20 aryl;
preferably, said L 1 Is phenyl or biphenyl;
preferably, said L 2 Any one selected from substituted or unsubstituted C3-C30 heteroaryl;
preferably, said L 2 Any one selected from the group consisting of a benzamidine group, a dibenzacridinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidyl group, a substituted or unsubstituted quinolyl group, and a substituted or unsubstituted isoquinolyl group;
the substituted substituents are respectively and independently selected from at least one of C6-C20 aryl or C3-C20 heteroaryl;
preferably, said L 2 Any one selected from the following groups:
5. The electron transport material of any of claims 1 to 4, wherein the electron transport material comprises any one of or a combination of at least two of the following compounds 1 to 15:
6. a method for producing an electron transport material according to any of claims 1 to 5, comprising: will be provided with
And U-L 2 Reacting under the action of a catalyst to obtain the electron transport material;
A 1 、A 2 、L 1 、L 2 m, p each independently have the same limitations as in claim 1;
u is selected from halogen.
7. The method according to claim 6, wherein U is chlorine;
preferably, the catalyst comprises a combination of a palladium catalyst and a basic compound;
preferably, the palladium catalyst is tetrakis (triphenylphosphine) palladium;
preferably, the basic compound is sodium hydroxide;
preferably, the reaction is carried out in a solvent;
preferably, the solvent is a mixed solution of water and tetrahydrofuran;
preferably, the volume ratio of the tetrahydrofuran to the water is 1 (0.3-0.6).
8. The method according to claim 6 or 7, wherein the reaction temperature is 110 to 130 ℃;
preferably, the reaction time is 12 to 16 hours.
9. The OLED device is characterized by comprising an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport function layer and a cathode which are sequentially arranged; the material of the electron transport functional layer comprises the electron transport material according to any one of claims 1 to 5;
preferably, the electron transport functional layer comprises any one of a hole blocking layer, an electron transport layer or an electron injection layer or a combination of at least two of the two; the hole blocking layer and/or the electron transport layer comprises the electron transport material according to any one of claims 1 to 5 in a material thereof.
10. An electronic device characterized in that it comprises an OLED device as claimed in claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110812825.3A CN115636822A (en) | 2021-07-19 | 2021-07-19 | Electron transport material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110812825.3A CN115636822A (en) | 2021-07-19 | 2021-07-19 | Electron transport material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115636822A true CN115636822A (en) | 2023-01-24 |
Family
ID=84940371
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110812825.3A Withdrawn CN115636822A (en) | 2021-07-19 | 2021-07-19 | Electron transport material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115636822A (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1403427A (en) * | 2001-08-29 | 2003-03-19 | 富士通株式会社 | Condensed octocyclic aromatic compound, organic electroluminescent element and organic electroluminescent display |
| CN1412864A (en) * | 2001-10-18 | 2003-04-23 | 日本电气株式会社 | Organic thin film transistor |
-
2021
- 2021-07-19 CN CN202110812825.3A patent/CN115636822A/en not_active Withdrawn
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1403427A (en) * | 2001-08-29 | 2003-03-19 | 富士通株式会社 | Condensed octocyclic aromatic compound, organic electroluminescent element and organic electroluminescent display |
| CN1412864A (en) * | 2001-10-18 | 2003-04-23 | 日本电气株式会社 | Organic thin film transistor |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113004189B (en) | Compound and application thereof | |
| CN113004153B (en) | Compound and application thereof | |
| CN112939946A (en) | Compound and application thereof | |
| CN114773210B (en) | Organic compound and application thereof | |
| CN112490391B (en) | Organic electroluminescent device and display device | |
| CN115626914B (en) | Carbazole compound and application thereof | |
| KR101627743B1 (en) | Compound, light emitting diode, organic optoelectric device, and display device | |
| CN111018855A (en) | Organic compound and application thereof | |
| CN113735848B (en) | Electroluminescent compound and preparation method and application thereof | |
| CN111354855A (en) | Organic electroluminescent device | |
| CN111574505B (en) | Compound with benzo [ c ] cinnoline as receptor and application thereof | |
| CN112759524A (en) | Aromatic amine derivative and organic electroluminescent device thereof | |
| CN111499650A (en) | Charge transport material and preparation method and application thereof | |
| CN112778139A (en) | Compound and application thereof | |
| CN115160273A (en) | Compound containing dibenzo heterocycle and preparation method and application thereof | |
| CN115636822A (en) | Electron transport material and preparation method and application thereof | |
| CN110194720B (en) | Compound, organic photoelectric device and electronic equipment | |
| CN109438469B (en) | Organic photoelectric material containing thiophene structure and application thereof | |
| CN115504890A (en) | Compound, application thereof and organic electroluminescent device | |
| CN115636813A (en) | Electron transport material and preparation method and application thereof | |
| CN113121407A (en) | Compound and application thereof | |
| CN112480133A (en) | Compound with benzospiroanthracene as core and application thereof | |
| CN113527302B (en) | Compound and application thereof | |
| CN114621203B (en) | Ketone-containing TADF organic compound and its application | |
| CN114149333B (en) | Compound containing spirobifluoreno adamantane main structure and application of compound in organic electroluminescent device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WW01 | Invention patent application withdrawn after publication | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20230124 |