CN116082167A - Organic compound and application thereof in organic photoelectric device - Google Patents

Organic compound and application thereof in organic photoelectric device Download PDF

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CN116082167A
CN116082167A CN202211146416.5A CN202211146416A CN116082167A CN 116082167 A CN116082167 A CN 116082167A CN 202211146416 A CN202211146416 A CN 202211146416A CN 116082167 A CN116082167 A CN 116082167A
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王鹏
王湘成
何睦
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Shanghai Yaoyi Electronic Technology Co ltd
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Abstract

The invention relates to the field of organic electroluminescent materials, in particular to an organic compound and application thereof in an organic photoelectric device. The chemical structure of the organic compound is shown as a formula (I):

Description

Organic compound and application thereof in organic photoelectric device
Technical Field
The invention relates to the field of organic electroluminescent materials, in particular to an organic compound and application thereof in an organic photoelectric device.
Background
An organic electroluminescent (OLED: organic Light Emission Diodes) device is a device with a sandwich-like structure, comprising positive and negative electrode layers and an organic functional material layer sandwiched between the electrode layers. At present, the technology is widely applied to display panels of products such as novel illumination lamps, smart phones and tablet computers, and further expands the application field of large-size display products such as televisions, and is a novel display technology with rapid development and high technical requirements. The application of the organic electroluminescent (OLED) material in the fields of information display materials, organic optoelectronic materials and the like has great research value and good application prospect. With the development of multimedia information technology, the requirements on the performance of flat panel display devices are increasing. The main display technologies currently exist as plasma display devices, field emission display devices, and organic electroluminescent display devices (OLEDs). Compared with a liquid crystal display device, the OLED does not need a backlight source, has wider visual angle and low power consumption, and has response speed 1000 times that of the liquid crystal display device, so that the OLED has wider application prospect. Since OLEDs were first reported, many scholars have been devoted to research on how to improve device efficiency and stability. At present, OLED display and illumination are widely applied in commercialization, the requirements of a client terminal on the photoelectricity and the service life of an OLED screen body are continuously improved, and in order to meet the requirements, the development of OLED materials capable of meeting higher device indexes is very important besides the elaboration of OLED panel manufacturing processes. The development of the existing OLED photoelectric functional material is far behind the requirement of panel manufacturing enterprises on the OLED material so far, so that the development of the organic functional material with better performance is particularly urgent to meet the development requirement of the current industry. For example, at present, aromatic amine compounds having good hole transport properties are mainly used as hole transport materials. N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (NPB) is widely used in organic electroluminescent devices for multiple colors due to its moderate highest occupied orbital level and good hole mobility. However, the glass transition temperature of the molecules is low (98 ℃), and the devices are easy to change phase under the action of accumulated joule heat when the devices are operated for a long time, so that the service lives of the devices are greatly influenced. It is necessary to design a hole transport material having both higher mobility and glass transition temperature. In addition, the main material is used as a key luminescent substance in the device, has more severe performance requirements, such as thermal stability and electrical stability, and has high luminous efficiency and service life. Therefore, the development of stable and efficient main materials, the reduction of driving voltage, the improvement of the luminous efficiency of the device and the prolongation of the service life of the device have important practical application values.
Disclosure of Invention
The invention aims to provide a stable and efficient hole transport material or electron transport material and a novel organic main material which can be used for a phosphorescence organic electroluminescent device, wherein the material has higher triplet state energy level, better carrier mobility, can be matched with adjacent energy levels, and has higher thermal stability and film forming stability. The material can be applied to corresponding OLED devices, so that the driving voltage can be reduced, and the luminous efficiency of the devices can be improved.
To achieve the above and other related objects, according to one aspect of the present invention, there is provided an organic compound having a chemical structure represented by formula (i):
Figure BDA0003855463420000021
wherein: R1-R8 are the same or different and are each independently selected from hydrogen, deuterium, cyano, a group containing a fluorine atom, a substituted or unsubstituted straight or branched C1-C30 alkyl group; substituted or unsubstituted C1-C30 heteroalkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C6-C60 aryl, or substituted or unsubstituted C5-C60 heteroaryl, or a ring is bonded to an adjacent atom.
In another aspect, the present invention provides an organic layer comprising an organic compound as described above.
In another aspect, the present invention provides the use of an organic compound according to the present invention and/or an organic layer according to the present invention in an organic optoelectronic device.
In another aspect, the present invention provides an organic optoelectronic device, which includes a first electrode, a second electrode, and an organic layer as described above, wherein the organic layer is at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, or an electron transport layer.
In another aspect the invention provides a display or lighting device comprising an organic optoelectronic device as hereinbefore described.
Compared with the prior art, the invention has the beneficial effects that:
the organic compound provided by the invention can regulate the HOMO energy level of molecules on one hand because of using rigid spirocycloalkane compounds, enhance the electron transport capacity because of the power supply property of alkane, and enhance the rigidity of the compound because of introducing rigid spirocycloalkane compounds, so that the compound has good thermal stability. In addition, the intermolecular accumulation is more loose, and the vapor deposition temperature can be reduced. Meanwhile, the compound disclosed by the invention is applied to an organic device, so that the device has higher efficiency, and meanwhile, molecules have high stability, so that the luminous efficiency of the device can be further improved, and the service life of the device can be prolonged.
Detailed Description
Embodiments of the specifically disclosed compounds and their use in organic optoelectronic devices are described in detail below. Other advantages and effects of the present invention will be readily apparent to those skilled in the art from the present disclosure. The invention may be practiced or carried out in other embodiments that depart from the specific details, and the details of the present description may be modified or varied from the spirit and scope of the present invention.
Before the embodiments of the invention are explained in further detail, it is to be understood that the invention is not limited in its scope to the particular embodiments described below; it is also to be understood that the terminology used in the examples of the invention is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the invention; in the description and claims of the invention, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise.
Where numerical ranges are provided in the examples, it is understood that unless otherwise stated herein, both endpoints of each numerical range and any number between the two endpoints are significant both in the numerical range. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, materials used in the embodiments, any methods, devices, and materials of the prior art similar or equivalent to those described in the embodiments of the present invention may be used to practice the present invention according to the knowledge of one skilled in the art and the description of the present invention.
Through a great deal of research and study, the inventor provides a spiro compound based on fluorene derivatives, and the compound is applied to an organic device, so that the device has higher device efficiency, and meanwhile, molecules have high stability, so that the luminous efficiency and the service life of the device can be further improved. On this basis, the present invention has been completed.
In one aspect, the invention provides an organic compound, wherein the chemical structure of the organic compound is shown as a formula (I):
Figure BDA0003855463420000031
wherein R is 1 -R 8 The groups are identical or different and are each independently selected from hydrogen, deuterium, cyano, fluorine atom-containing groups, substituted or unsubstituted linear or branched C1-C30 alkyl groups; substituted or unsubstituted C1-C30 heteroalkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C6-C60 aryl, or substituted or unsubstituted C5-C60 heteroaryl, or a ring is bonded to an adjacent atom.
In particular, substituted or unsubstituted means substituted with one or more substituents selected from the group consisting of: deuterium, halogen groups, nitrile groups, nitro groups, hydroxyl groups, carbonyl groups, ester groups, imide groups, amino groups, phosphine oxide groups, alkoxy groups, aryloxy groups, alkylthio groups, arylthio groups, alkylsulfonyl groups, arylsulfonyl groups, silyl groups, boron groups, alkyl groups, cycloalkyl groups, alkenyl groups, aryl groups, aralkyl groups, aralkenyl groups, alkylaryl groups, alkylamino groups, aralkylamino groups, heteroarylamino groups, arylamino groups, arylphosphine groups, and heteroaryl groups, acenaphthylene groups, compound groups, or unsubstituted groups; or substituted with a substituent linking two or more of the substituents exemplified above, or unsubstituted. For example, "a substituent linking two or more substituents" may include a biphenyl group, i.e., the biphenyl group may be an aryl group, or a substituent linking two phenyl groups.
The alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited. In some embodiments, alkyl groups include, but are not limited to, methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2-dimethylheptyl, 1-ethyl-propyl, 1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl.
The above description of alkyl groups also applies to alkyl groups in aralkyl groups, aralkylamine groups, alkylaryl groups, and alkylamino groups.
The heteroalkyl group may be a straight-chain or branched alkyl group containing a heteroatom, and the number of carbon atoms is not particularly limited. In some embodiments, heteroalkyl groups include, but are not limited to, can be alkoxy, alkylthio, alkylsulfonyl, and the like. Alkoxy groups may include, for example, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, t-butoxy, sec-butoxy, n-pentoxy, neopentoxy, isopentoxy, n-hexoxy, 3-dimethylbutoxy, 2-ethylbutoxy, n-octoxy, n-nonoxy, n-decoxy, benzyloxy, p-methylbenzoxy, and the like. Alkylthio groups may include, for example, but are not limited to, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, t-butylthio, sec-butylthio, n-pentylthio, neopentylthio, isopentylthio, n-hexylthio, 3-dimethylbutylthio, 2-ethylbutylthio, n-octylthio, n-nonylthio, n-decylthio, benzylthio, and the like.
Cycloalkyl groups may be cyclic, and the number of carbon atoms is not particularly limited. In some embodiments, cycloalkyl includes, but is not limited to, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2, 3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2, 3-dimethylcyclohexyl, 3,4, 5-trimethylcyclohexyl, 4-t-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like.
The heterocycloalkyl group may be a cycloalkyl group containing a heteroatom, and the number of carbon atoms is not particularly limited. In some embodiments, heterocycloalkyl includes, but is not limited to
Figure BDA0003855463420000041
Etc.
The aryl group is not particularly limited, and the aryl group may be a monocyclic aryl group or a polycyclic aryl group. In some embodiments, monocyclic aryl groups include, but are not limited to, phenyl, biphenyl, terphenyl, tetrabiphenyl, pentabiphenyl, and the like. Polycyclic aryl groups include, but are not limited to, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, fluorenyl, and the like. Fluorenyl groups can be substituted, such as 9,9 '-dimethylfluorenyl, 9' -dibenzofluorenyl, and the like. In addition, two of the substituents may combine with each other to form a spiro structure, for example, 9' -spirobifluorenyl, and the like.
The above description of aryl groups applies to arylene groups, except that arylene groups are divalent.
The above description of aryl groups applies to aryl groups in aryloxy, arylthio, arylsulfonyl, arylphosphinyl, aralkyl, aralkylamino, aralkenyl, alkylaryl, arylamino and arylheteroarylamino groups.
Heteroaryl groups contain one or more of N, O, P, S, si and Se as heteroatoms. Heteroaryl groups include, but are not limited to, pyridyl, pyrrolyl, pyrimidinyl, pyridazinyl, furyl, thienyl, imidazolyl, pyrazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, triazolyl, diazolyl, thiadiazolyl, dithiazolyl, tetrazolyl, pyranyl, thiopyranyl, pyrazinyl, oxazinyl, thiazinyl, dioxanyl, triazinyl, tetrazinyl, quinolinyl, isoquinolinyl, quinolinyl, quinazolinyl, quinoxalinyl, naphthyridinyl, acridinyl, xanthenyl, phenanthridinyl, naphthyridinyl, triazaindenyl, indolyl, indolizinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl pyrazinopyrazinyl, benzothiazolyl, benzoxazolyl, benzimidazolyl, benzothienyl, benzofuranyl, dibenzothiophenyl, dibenzofuranyl, carbazolyl, benzocarbazolyl, dibenzocarbazolyl, indolocarbazolyl, indenocarbazolyl, phenazinyl, imidazopyridinyl, phenazinyl, phenanthridinyl, phenanthrolinyl, phenothiazinyl, imidazopyridinyl, imidazophenanthridinyl, benzimidazolazolyl, benzimidazolophenidinyl, spiro [ fluorene-9, 9' -xanthene ], benzobinaphthyl, dinaphthyl, naphthyfuranyl, dinaphthylthiophenyl, naphthybenzothiophenyl, triphenylphosphine oxide, triphenylborane, and the like.
The above description of heteroaryl groups applies to heteroaryl groups in heteroaryl amine groups and arylheteroaryl amine groups.
The above description of heteroaryl groups applies to heteroarylene groups, except that the heteroarylene group is divalent.
Bonded to adjacent atoms to form a ring, e.g. R 1 And R is R 2 And after the bonding, a ring structure is formed.
Further options for alkyl, heteroalkyl, cycloalkyl, heterocycloalkyl, aryl, heteroaryl may be as described above.
In the organic compound provided by the invention, R is 1 -R 8 At least one selected from the following structures:
Figure BDA0003855463420000051
wherein:
R 9 -R 12 identical or different, each independently selected from hydrogen, deuterium, substituted or unsubstituted linear or branched C1-C30 alkyl; a substituted or unsubstituted C1-C30 heteroalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C3-C30 heterocycloalkyl group, a substituted or unsubstituted C6-C60 aryl group, or a substituted or unsubstituted C5-C60 heteroaryl group.
A. B is independently selected from substituted or unsubstituted C6-C60 aryl or substituted or unsubstituted C5-C60 heteroaryl.
Ar 1 -Ar 2 Are identical or different and are each independently selected from substituted or unsubstituted C6-C60 aryl or substituted or unsubstituted C5-C60 heteroaryl.
L 1 -L 9 Identical or different, independently selected from single bonds, substituted or unsubstituted straight or branched C1-C30 alkyl groups, substitutedOr unsubstituted C1-C30 heteroalkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C6-C60 aryl, or substituted or unsubstituted C5-C60 heteroaryl.
E is selected from an electron withdrawing group containing a fluorine atom, an electron withdrawing group containing a nitrogen atom or an electron withdrawing group containing oxygen.
* Is a junction site.
In the organic compound provided by the invention, further, A and B are independently selected from the following groups:
Figure BDA0003855463420000061
Ar 3 -Ar 8 is the same or different and is independently selected from substituted or unsubstituted C6-C60 aryl or substituted or unsubstituted C5-C60 heteroaryl.
X 1 -X 13 Identical or different, independently selected from O, S, CR 13 R 14 、NR 15 Or SiR 16 R 17 ；R 13 -R 17 Identical or different, each independently selected from hydrogen, deuterium, substituted or unsubstituted linear or branched C1-C30 alkyl; a substituted or unsubstituted C1-C30 heteroalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C3-C30 heterocycloalkyl group, a substituted or unsubstituted C6-C60 aryl group, or a substituted or unsubstituted C5-C60 heteroaryl group.
In the organic compound provided by the invention, further, L 1 、L 2 、L 3 、L 5 、L 7 、L 8 And L 9 The groups are the same or different and are each independently selected from the following groups:
Figure BDA0003855463420000062
wherein is the site of attachment.
The organic compound provided by the inventionIn the formula (I), the L 4 、R 11 、L 6 、R 12 And E, which are identical or different, are each independently selected from the following groups:
Figure BDA0003855463420000071
wherein R is 11 ～R 14 The choices of (2) are the same or different; the R is 11 ～R 12 R is as previously described 11 ～R 12 The method comprises the steps of carrying out a first treatment on the surface of the The R is 13 ～R 14 R is as previously described 13 ～R 14 。
In the organic compound provided by the invention, R is 1 -R 8 At least one of which is selected from the following structures:
Figure BDA0003855463420000072
Figure BDA0003855463420000081
Figure BDA0003855463420000091
CN。
X 14 、X 15 independently selected from O, S, CR 15 R 16 、NR 17 Or SiR 18 R 19 ；R 15～ R 19 Each independently selected from hydrogen, deuterium, substituted or unsubstituted straight or branched chain C1-C30 alkyl; a substituted or unsubstituted C1-C30 heteroalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C3-C30 heterocycloalkyl group, a substituted or unsubstituted C6-C60 aryl group, or a substituted or unsubstituted C5-C60 heteroaryl group. Preferably, R 15～ R 19 Independently selected from hydrogen, deuterium, methyl, ethyl, propyl, isopropyl, tert-butyl, phenyl, biphenyl, naphthyl, and the like. * To connect toA site.
The following are exemplified by some of the groups:
Figure BDA0003855463420000101
for example, it may be +.>
Figure BDA0003855463420000102
Etc.
Figure BDA0003855463420000103
For example, it may be +.>
Figure BDA0003855463420000104
Etc.
Figure BDA0003855463420000105
For example, it may be +. >
Figure BDA0003855463420000106
Etc.
Figure BDA0003855463420000107
For example, it may be +.>
Figure BDA0003855463420000108
Etc.
Figure BDA0003855463420000109
For example, it may be +.>
Figure BDA00038554634200001010
Etc.
In the organic compound provided by the invention, the organic compound is selected from one or more of the following chemical structures:
Figure BDA00038554634200001011
Figure BDA0003855463420000111
Figure BDA0003855463420000121
Figure BDA0003855463420000131
Figure BDA0003855463420000141
Figure BDA0003855463420000151
Figure BDA0003855463420000161
Figure BDA0003855463420000171
specifically, the above structure may be unsubstituted or substituted with one or more substituents selected from the group consisting of. Examples of the group include deuterium, halogen group, nitrile group, nitro group, hydroxyl group, carbonyl group, ester group, imide group, amine group, phosphine oxide group, alkoxy group, aryloxy group, alkylthio group, arylthio group, alkylsulfonyl group, arylsulfonyl group, silyl group, boron group, alkyl group, cycloalkyl group, alkenyl group, aryl group, aralkyl group, aralkenyl group, alkylaryl group, alkylamino group, aralkylamino group, heteroarylamino group, arylamino group, arylheteroarylamino group, arylphosphine group, and heteroaryl group.
The organic compound takes the derivative of fluorene as a matrix, and the matrix structure has good thermal stability, proper HOMO and LUMO energy levels and Eg, high triplet energy level, good carrier mobility, capability of matching with adjacent energy levels, and high thermal stability and film forming stability. The organic light emitting diode can be applied to OLED devices, can be used as a hole transmission material or an electron transmission material and a main body material, and can effectively improve the efficiency and the service life of the devices.
In a second aspect, the invention provides an organic layer comprising the compound described above.
A third aspect of the present invention provides the use of a compound according to the first aspect of the present invention and/or an organic layer according to the second aspect of the present invention in an organic optoelectronic device.
A fourth aspect of the present invention provides an organic photoelectric device including a first electrode, a second electrode, and one or more organic layers disposed between the first electrode and the second electrode, which may be a single-layer structure or a multi-layer tandem structure in which two or more organic layers are laminated, such as having at least one layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, or an electron transport layer, as a bottom or top light emitting device structure. Can be prepared using common methods and materials for preparing organic photovoltaic devices. The organic photoelectric device of the invention adopts the compound as an organic layer of the organic photoelectric device.
In the organic photoelectric device provided by the invention, the first electrode is used as the anode layer, and the anode material can be a material with a large work function, for example, so that holes are smoothly injected into the organic layer. More for example, metals, metal oxides, combinations of metals and oxides, conductive polymers, and the like. The metal oxide may be, for example, indium Tin Oxide (ITO), zinc oxide, indium Zinc Oxide (IZO), or the like.
In the organic photoelectric device provided by the invention, the second electrode is used as the cathode layer, and the cathode material can be a material with a small work function, for example, so that electrons are smoothly injected into the organic layer. The cathode material may be, for example, a metal or a multi-layer structural material. The metal may be, for example, magnesium, silver, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, tin, and lead, or alloys thereof. The cathode material is preferably selected from magnesium and silver.
In the organic photoelectric device provided by the present invention, a material of the hole injection layer, preferably a material having a Highest Occupied Molecular Orbital (HOMO) between a work function of the anode material and a HOMO of the surrounding organic layer, is used as a material that advantageously receives holes from the anode at a low voltage.
In the organic photoelectric device provided by the invention, the material of the hole transport layer is a material having high mobility to holes and is suitable as a material for receiving holes from the anode or the hole injection layer and transporting the holes to the light emitting layer. The material of the hole transport layer includes, but is not limited to, an organic material of arylamine, a conductive polymer, a block copolymer having both conjugated and non-conjugated portions, and the like. The compound provided by the invention can be applied to a hole transport layer of a device. I.e., the hole transport layer contains one or more organic compounds of the present invention.
In the organic photoelectric device provided by the invention, the organic compound provided by the invention can be applied to a light-emitting layer of the device. I.e. the light emitting layer comprises one or more organic compounds according to the invention.
In the organic photoelectric device provided by the present invention, the material of the electron transport layer is a material having high mobility to electrons and is suitable as a material that favorably receives electrons from the cathode and transports the electrons to the light emitting layer. The organic compound provided by the invention can be applied to an electron transport layer of a device. I.e. the electron transport layer comprises one or more organic compounds according to the invention.
In the organic photoelectric device provided by the invention, the material of the cover layer generally has a high refractive index, so that the light efficiency of the organic light-emitting device can be improved, and the improvement of external light-emitting efficiency is particularly facilitated.
In the organic photoelectric device provided by the invention, the organic photoelectric device is an organic photovoltaic device, an organic light-emitting device, an organic solar cell, electronic paper, an organic photoreceptor, an organic thin film transistor and the like.
In another aspect, the invention provides a display or lighting device comprising an organic optoelectronic device according to the invention.
Embodiments of the present invention are described below by way of specific examples.
Synthetic examples:
the synthesis of the compound represented by the above formula (I) can be carried out by a known method. For example, cross-coupling reactions using transition metals such as nickel, palladium, and the like. Other synthetic methods are C-C, C-N coupling reactions using transition metals such as magnesium or zinc. The reaction is limited to mild reaction conditions, excellent selectivity of various functional groups, and the like, and is preferably a Suzuki reaction or a Buchwald reaction. The compounds of the present invention are illustrated by the following examples, but are not limited to the compounds and synthetic methods illustrated by these examples. The initial raw materials, the solvent, some common OLED intermediates and other products are purchased from domestic OLED intermediate manufacturers; various palladium catalysts, ligands, etc. are available from sigma-Aldrich. 1 H-NMR data were determined using a JEOL (400 MHz) nuclear magnetic resonance apparatus; HPLC data were determined using a Shimadzu LC-20AD high performance liquid meter.
The materials used in the examples are:
Figure BDA0003855463420000191
example 1
Synthesis of Compound D-4
Figure BDA0003855463420000192
1) Synthesis of intermediate D-4-1
To a reaction vessel were charged 36.5 g (100 mmol) of compound D-4-A, 9.3 g (100 mmol) of compound D-4-B, 23.1 g (240 mmol) of sodium t-butoxide, 575 mg (1 mmol) of bis-dibenzylideneacetone palladium, 953 mg (2 mmol%) of 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl and 1000mL of xylene (xylene) under an argon atmosphere, and the mixture was heated and stirred at 140℃for 20 hours. The reaction mixture was cooled to room temperature, 1000ml of water was added, filtered, the filter cake was washed with a large amount of water, dried in vacuo, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to give 26.0 g of compound D-4-1, 99.3% purity by HPLC, yield 69%. LC MS: M/Z377.21 (M+).
1 H NMR(400MHz,DMSO-d6)δ1.17(m,1H),1.28–1.76(m,7H),1.79–1.96(m,2H),2.04–2.15(m,2H),2.25–2.35(m,2H),6.95–7.10(m,5H),7.30–7.45(m,4H),7.46(m,1H),7.50–7.57(m,1H),7.81–7.92(m,2H)。
2) Synthesis of Compound D-4
To the reaction vessel were added 37.5 g (100 mmol) of compound D-4-1, 27.3 g (100 mmol) of compound D-4-C, 23.1 g (240 mmol) of sodium t-butoxide, 575 mg (1 mmol) of bis-dibenzylideneacetone palladium, 953 mg (2 mmol%) of 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl and 1000mL of xylene (xylene) under an argon atmosphere, and the mixture was heated and stirred at 140℃for 20 hours. The reaction mixture was cooled to room temperature, 1000ml of water was added, filtered, the filter cake was washed with a large amount of water, dried in vacuo, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to give 45.6 g of compound D-4, 99.9% purity by HPLC, yield 80%. LC MS: M/Z569.31 (M+).
1 H NMR(400MHz,DMSO-d6)δ1.17(m,1H),1.28–1.41(m,2H),1.36–1.47(m,1H),1.47–1.72(m,4H),1.67(s,3H),1.71(s,3H),1.79–1.96(m,2H),2.04–2.15(m,2H),2.25–2.35(m,2H),6.95–7.04(m,3H),7.04–7.12(m,2H),7.19–7.29(m,2H),7.30–7.41(m,4H),7.46(m,2H),7.50–7.57(m,2H),7.82–7.92(m,4H)。
Example 2
Synthesis of Compound D-9
Figure BDA0003855463420000201
The procedure of example 1 was repeated except that the starting material was changed to D-9-C. LC MS: M/Z691.32 (M+).
HPLC purity: 99.9%, total yield: 55%.
1 H NMR(400MHz,DMSO-d6)δ1.17(m,1H),1.28–1.76(m,7H),1.79–1.96(m,2H),2.04–2.15(m,2H),2.25–2.35(m,2H),6.65–6.75(m,2H),6.80(m,1H),6.95–7.04(m,2H),7.04–7.12(m,2H),7.19–7.42(m,12H),7.46(m,1H),7.50–7.57(m,1H),7.82–7.94(m,6H)。
Example 3
Synthesis of Compound D-25
Figure BDA0003855463420000202
The procedure of example 1 was repeated except that the starting materials were changed to D-25-B and D-25-C. LC MS: M/Z609.25 (M+). Total synthesis yield: 53%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.17(m,1H),1.28–1.76(m,7H),1.79–1.96(m,2H),2.04–2.15(m,2H),2.25–2.35(m,2H),6.95–7.00(m,1H),7.03(m,1H),7.11(t,1H),7.30–7.40(m,2H),7.40–7.49(m,4H),7.44–7.55(m,2H),7.51–7.61(m,2H),7.61–7.67(m,1H),7.71(m,1H),7.73–7.82(m,1H),7.82–7.95(m,3H),7.99(m,1H),8.45(m,1H)。
Example 4
Synthesis of Compound D-32
Figure BDA0003855463420000211
The procedure of example 1 was repeated except that the starting materials were changed to D-32-B and D-32-C. LC MS: M/Z659.32 (M+). Total synthesis yield: 54%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.17(m,1H),1.28–1.74(m,13H),1.79–1.96(m,2H),2.04–2.15(m,2H),2.25–2.35(m,2H),6.91(m,1H),6.98(d,2H),7.26–7.36(m,2H),7.33–7.39(m,2H),7.36–7.41(m,1H),7.46(m,3H),7.50–7.58(m,3H),7.68(m,1H),7.82–7.92(m,4H),7.94–8.01(m,1H),8.01–8.06(m,1H)。
Example 5
Synthesis of Compound D-78
Figure BDA0003855463420000212
The procedure of example 1 was repeated except that the starting materials were changed to D-32-B and D-78-C. LC MS: M/Z677.27 (M+). Total synthesis yield: 52%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ3.42(d,2H),3.52(s,4H),3.67(d,2H),6.91(m,1H),7.19(m,1H),7.26–7.61(m,19H),7.68(m,1H),7.70–7.77(m,2H),7.84–7.92(m,1H),7.94–8.06(m,2H)。
Example 6
Synthesis of Compound D-85
Figure BDA0003855463420000221
The procedure of example 1 was repeated except that the starting materials were changed to D-85-B and D-78-C. LC MS: M/Z783.35 (M+). Total synthesis yield: 48%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.17(m,1H),1.28–1.76(m,7H),1.79–1.96(m,2H),2.04–2.15(m,2H),2.25–2.35(m,2H),6.95–7.05(m,4H),7.13–7.27(m,6H),7.27–7.57(m,16H),7.77(t,1H),7.82–7.94(m,4H)。
Example 7
Synthesis of Compound D-90
Figure BDA0003855463420000222
The procedure of example 1 was repeated except that the starting materials were changed to D-90-A, D-25-B and D-90-C. LC MS: M/Z668.32 (M+). Total synthesis yield: 50%; HPLC purity: 99.9%.
Example 8
Synthesis of Compound D-105
Figure BDA0003855463420000223
The procedure of example 1 was repeated except that the starting material was changed to D-105-A. LC MS: M/Z852.44 (M+). Total synthesis yield: 51%; HPLC purity: 99.9%.
Example 9
Synthesis of Compound D-109
Figure BDA0003855463420000224
The procedure of example 1 was repeated except that the starting materials were changed to D-105-A and D-109-C. LC MS: M/Z852.44 (M+). Total synthesis yield: 51%; HPLC purity: 99.9%.
Example 10
Synthesis of Compound D-115
Figure BDA0003855463420000231
The procedure of example 1 was repeated except that the starting material was changed to D-115-A. LC MS: M/Z695.36 (M+). Total synthesis yield: 51%; HPLC purity: 99.9%.
Example 11
Synthesis of Compound D-144
Figure BDA0003855463420000232
The procedure of example 1 was repeated except that the starting materials were changed to D-144-A, D-32-B and D-25-C. LC MS: M/Z751.33 (M+). Total synthesis yield: 54%; HPLC purity: 99.9%.
Example 12
Synthesis of Compound D-150
Figure BDA0003855463420000233
The procedure of example 1 was repeated except that the starting materials were changed to D-150-A and D-150-C. LC MS: M/Z924.44 (M+). Total synthesis yield: 51%; HPLC purity: 99.9%.
Example 13
Synthesis of Compound E-1
Figure BDA0003855463420000234
Under argon atmosphere, 33.0g (100 mmol) of E-1-A, 27.3g (100 mmol) of E-1-B, 1.16g (1.0 mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300 mmol) of 1.5M aqueous sodium carbonate solution and 800ml (DME) of ethylene glycol dimethyl ether were charged into the reactor, and heated and stirred at 80℃overnight. Cooling to room temperature, adding 500ml of water, separating out solid, filtering, washing the obtained solid with ethanol, refining the crude product by silica gel column chromatography (eluent: ethyl acetate/hexane) to obtain 31.1 g of compound E-1, HPLC purity 99.9%, yield 65%. LC MS: M/Z478.24 (M+).
1 H NMR(400MHz,DMSO-d6)δ1.17(m,1H),1.28–1.76(m,7H),1.79–1.96(m,2H),2.04–2.15(m,2H),2.25–2.35(m,2H),7.28(m,1H),7.31–7.40(m,3H),7.42–7.58(m,5H),7.54–7.66(m,2H),7.73–7.84(m,2H),7.84–7.92(m,1H),8.04–8.12(m,1H),8.56(m,1H)。
Example 14
Synthesis of Compound E-8
Figure BDA0003855463420000241
The procedure of example 13 was repeated except that the starting material was changed to E-8-B. LC MS: M/Z669.31 (M+). Total synthesis yield: 55%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.17(m,1H),1.28–1.41(m,2H),1.43(m,1H),1.47–1.76(m,4H),1.79–1.96(m,2H),2.04–2.15(m,2H),2.25–2.35(m,2H),7.30–7.43(m,3H),7.43–7.62(m,11H),7.69–7.81(m,5H),7.84–7.96(m,5H),8.08(m,1H)。
Example 15
Synthesis of Compound E-15
Figure BDA0003855463420000242
The procedure of example 13 was repeated except that the starting material was changed to E-15-B. LC MS: M/Z419.17 (M+). Total synthesis yield: 54%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.17(m,1H),1.28–1.76(m,7H),1.79–1.96(m,2H),2.04–2.15(m,2H),2.25–2.35(m,2H),7.35(m,2H),7.40–7.50(m,2H),7.50–7.60(m,2H),7.77(m,1H),7.84–7.92(m,2H),8.04–8.12(m,2H)。
Example 16
Synthesis of Compound E-21
Figure BDA0003855463420000243
The procedure of example 13 was repeated except that the starting material was changed to E-21-B. LC MS: M/Z1164.45 (M+). Total synthesis yield: 53%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.69(s,18H),3.52(s,4H),3.55(s,4H),6.93–7.00(m,4H),7.00–7.06(m,4H),7.09(d,2H),7.30–7.61(m,16H),7.61–7.67(m,2H),7.81–7.95(m,6H),7.99(m,2H),8.45(m,2H)。
Example 17
Synthesis of Compound E-42
Figure BDA0003855463420000251
The procedure of example 13 was repeated except that the starting material was changed to E-42-B. LC MS: M/Z530.24 (M+). Total synthesis yield: 55%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.17(m,1H),1.28–1.76(m,7H),1.79–1.96(m,2H),2.04–2.15(m,2H),2.25–2.35(m,2H),7.30–7.50(m,5H),7.50–7.59(m,2H),7.59–7.70(m,3H),7.73–7.84(m,3H),7.84–7.92(m,1H),7.96–8.08(m,1H),8.08(m,1H)。
Example 18
Synthesis of Compound E-58
Figure BDA0003855463420000252
The procedure of example 13 was repeated except that the starting material was changed to E-58-B. LC MS: M/Z637.26 (M+). Total synthesis yield: 55%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.17(m,1H),1.28–1.76(m,8H),1.79–1.96(m,2H),2.04–2.15(m,2H),2.25–2.35(m,2H),7.27–7.39(m,3H),7.39–7.57(m,7H),7.77(m,1H),7.84–7.92(m,1H),8.03–8.14(m,4H),8.14–8.25(m,4H)。
Example 19
Synthesis of Compound E-69
Figure BDA0003855463420000253
The procedure of example 13 was repeated except that the starting materials were changed to E-69-A and E-69-B. LC MS: M/Z616.229 (M+). Total synthesis yield: 56% of a glass fiber; HPLC purity: 99.9%.
Example 20
Synthesis of Compound E-76
Figure BDA0003855463420000261
The procedure of example 13 was repeated except that the starting materials were changed to E-69-A and E-76-B. LC MS: M/Z566.27 (M+). Total synthesis yield: 54%; HPLC purity: 99.9%.
Example 21
Synthesis of Compound E-89
Figure BDA0003855463420000262
The procedure of example 13 was repeated except that the starting materials were changed to E-89-A and E-89-B. LC MS: M/Z606.27 (M+). Total synthesis yield: 53%; HPLC purity: 99.9%.
Example 22
Synthesis of Compound E-107
Figure BDA0003855463420000263
The procedure of example 13 was repeated except that the starting materials were changed to E-107-A and E-107-B. LC MS: M/Z618.28 (M+). Total synthesis yield: 48%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.17(m,1H),1.28–1.76(m,7H),1.79–1.96(m,2H),2.04–2.15(m,2H),2.25–2.35(m,2H),7.29–7.35(m,1H),7.44–7.54(m,6H),7.54–7.62(m,2H),7.63(m,1H),7.73–7.83(m,2H),7.88–7.96(m,2H),8.08(m,2H),8.30–8.40(m,4H)。
Example 23
Synthesis of Compound E-111
Figure BDA0003855463420000264
The procedure of example 13 was repeated except that the starting materials were changed to E-111-A and E-107-. LC MS: M/Z643.27 (M+). Total synthesis yield: 48%; HPLC purity: 99.9%.
Example 24
Synthesis of Compound E-119
Figure BDA0003855463420000271
The procedure of example 13 was repeated except that the starting materials were changed to E-105-A and E-107-B. LC MS: M/Z748.33 (M+). Total synthesis yield: 49%; HPLC purity: 99.9%.
Example 25
Synthesis of Compound H-1
Figure BDA0003855463420000272
1) Synthesis of intermediate H-1-1
Under argon atmosphere, 36.5g (100 mmol) of D-4-A, 21.1g (100 mmol) of H-1-B, 1.16g (1.0 mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300 mmol) of 1.5M aqueous sodium carbonate solution and 800ml (DME) of ethylene glycol dimethyl ether were charged into the reactor, and heated and stirred at 80℃overnight. Cooled to room temperature, 500ml of water was added, the solid was precipitated, filtered, and the obtained solid was washed with ethanol to obtain 34.3g of Compound H-1-1, yield 76% and HPLC purity 98.8%. LC MS: M/Z451.23 (M+).
1 H NMR(400MHz,DMSO-d6)δ1.17(m,1H),1.28–1.76(m,8H),1.79–1.96(m,2H),2.04–2.15(m,2H),2.25–2.35(m,2H),7.24–7.39(m,3H),7.39(m,1H),7.42–7.50(m,3H),7.50–7.60(m,2H),7.73–7.81(m,2H),7.84–7.92(m,1H),8.08(m,1H),8.32–8.40(m,1H)。
2) Synthesis of H-1
To the reaction vessel were added 45.2 g (100 mmol) of compound H-1-1, 31.1 g (100 mmol) of compound H-1-C, 23.1 g (240 mmol) of sodium t-butoxide, 575 mg (1 mmol%) of bis-dibenzylideneacetone palladium, 953 mg (2 mmol%) of 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl, and 1000mL of xylene (xylene) under an argon atmosphere, and the mixture was heated and stirred at 140℃for 20 hours. The reaction mixture was cooled to room temperature, 1000ml of water was added, filtered, the filter cake was washed with a large amount of water, dried in vacuo, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to give 53.3 g of compound H-1, purity by HPLC was 99.9%, yield 78%. LC MS: M/Z682.31 (M+).
1 H NMR(400MHz,DMSO-d6)δ1.17(m,1H),1.28–1.76(m,8H),1.79–1.96(m,2H),2.04–2.15(m,2H),2.25–2.35(m,2H),7.19(m,1H),7.29–7.42(m,4H),7.42–7.52(m,2H),7.49(s,1H),7.47–7.57(m,4H),7.73–7.82(m,3H),7.84–7.92(m,1H),8.08(m,1H),8.21(m,2H),8.30–8.40(m,4H)。
Example 26
Synthesis of Compound H-7
Figure BDA0003855463420000281
The procedure of example 25 was repeated except that the starting materials were changed to D-90-A, H-7-B and H-7-C. LC MS: M/Z705.31 (M+). Total synthesis yield: 48%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.17(m,1H),1.28–1.76(m,7H),1.79–1.96(m,2H),2.04–2.15(m,2H),2.25–2.35(m,2H),7.12–7.24(m,2H),7.30–7.39(m,1H),7.46(m,1H),7.46–7.56(m,4H),7.59(m,1H),7.63–7.76(m,6H),7.79–7.97(m,3H),8.04–8.14(m,1H),8.15–8.25(m,2H),8.25–8.35(m,2H),8.51–8.64(m,2H)。
Example 27
Synthesis of Compound H-22
Figure BDA0003855463420000282
The procedure of example 25 was repeated except that the starting materials were changed to H-22-A and H-22-C. LC MS: M/Z594.28 (M+). Total synthesis yield: 45%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.17(m,1H),1.28–1.41(m,2H),1.43(m,1H),1.47–1.76(m,4H),1.79–1.96(m,2H),2.04–2.15(m,2H),2.25–2.35(m,2H),7.19(m,1H),7.30–7.41(m,2H),7.41–7.57(m,5H),7.54–7.65(m,2H),7.60–7.70(m,2H),7.74(m,1H),7.84–7.98(m,2H),7.95–8.03(m,1H),8.16–8.25(m,2H),8.30–8.37(m,1H),9.31(s,1H)。
Example 28
Synthesis of Compound H-32
Figure BDA0003855463420000283
1) Synthesis of H-32-1
To a reaction vessel were charged 36.5 g (100 mmol) of compound D-4-A, 21.1 g (100 mmol) of compound H-7-B, 23.1 g (240 mmol) of sodium t-butoxide, 575 mg (1 mmol) of bis-dibenzylideneacetone palladium, 953 mg (2 mmol%) of 2-dicyclohexylphosphine-2 ',4',6' -triisopropylbiphenyl and 1000mL of xylene (xylene) under an argon atmosphere, and the mixture was heated and stirred at 140℃for 20 hours. The reaction mixture was cooled to room temperature, 1000ml of water was added, filtered, the filter cake was washed with a large amount of water, dried in vacuo, and the crude product was purified by silica gel column chromatography (eluent: ethyl acetate/hexane) to give 37.2 g of compound H-32-1, hplc purity 98.8%, yield 75%. LC MS: M/Z495.24 (M+).
1 H NMR(400MHz,DMSO-d6)δ1.17(m,1H),1.28–1.76(m,7H),1.79–1.96(m,2H),2.04–2.15(m,2H),2.25–2.35(m,2H),7.00(m,1H),7.12–7.24(m,2H),7.30–7.44(m,2H),7.42–7.57(m,3H),7.58–7.70(m,3H),7.84–7.92(m,1H),7.97–8.06(m,3H),8.54–8.64(m,1H)。
2) Synthesis of intermediate H-32
Under argon atmosphere, the reactor was charged with 49.5g (100 mmol) of H-32-1, 33.5g (100 mmol) of H-32-C, 1.16g (1.0 mmol) of tetrakis (triphenylphosphine) palladium, 200ml (300 mmol) of 1.5M aqueous sodium carbonate solution and 800ml (DME) of ethylene glycol dimethyl ether, and heated and stirred at 80℃overnight. Cooling to room temperature, adding 500ml of water, separating out solid, filtering, washing the obtained solid with ethanol, refining the crude product by silica gel column chromatography (eluent: ethyl acetate/hexane) to obtain 49.4 g of compound H-32, HPLC purity 99.9%, yield 70%. LC MS: M/Z705.31 (M+).
1 H NMR(400MHz,DMSO-d6)δ1.17(m,1H),1.28–1.76(m,7H),1.79–1.96(m,2H),2.04–2.15(m,2H),2.25–2.35(m,2H),7.12–7.24(m,2H),7.30–7.70(m,12H),7.73(m,1H),7.78–7.85(m,1H),7.85–7.92(m,1H),8.00–8.06(m,1H),8.08–8.16(m,1H),8.24–8.32(m,2H),8.47(m,1H),8.54–8.64(m,1H),8.79(d,2H)。
Example 29
Synthesis of Compound H-38
Figure BDA0003855463420000291
The procedure of example 28 was repeated except that the starting materials were changed to H-38-B and H-7-C. LC MS: M/Z655.30 (M+). Synthesis yield: 75%; HPLC purity: 99.9%.
1 H NMR(400MHz,DMSO-d6)δ1.17(m,1H),1.28–1.76(m,7H),1.79–1.96(m,2H),2.04–2.15(m,2H),2.25–2.35(m,2H),7.19(m,1H),7.30–7.41(m,4H),7.42–7.57(m,4H),7.59–7.70(m,2H),7.78(m,2H),7.82–7.92(m,3H),8.00–8.06(m,1H),8.04–8.12(m,2H),8.16–8.24(m,1H),8.27–8.33(m,1H),8.33–8.41(m,1H),8.49(m,1H)。
Example 30
Synthesis of Compound H-53
Figure BDA0003855463420000301
The procedure of example 28 was repeated except that the starting material was changed to H-53-C. LC MS: M/Z695.29 (M+). Total synthesis yield: 48%; HPLC purity: 99.9%.
Example 31
Synthesis of Compound H-60
Figure BDA0003855463420000302
The procedure of example 25 was repeated except that the starting material was changed to H-60-B. LC MS: M/Z772.95 (M+). Total synthesis yield: 46%; HPLC purity: 99.9%.
Example 32
Synthesis of Compound H-74
Figure BDA0003855463420000303
The procedure of example 25 was repeated except that D-90-A, H-74-B and H-74-C were replaced with the starting materials. LC MS: M/Z721.35 (M+). Total synthesis yield: 46%; HPLC purity: 99.9%.
Example 33
Synthesis of Compound H-85
Figure BDA0003855463420000304
The procedure of example 25 was repeated except that the starting materials were changed to H-85-B and H-74-C. LC MS: M/Z779.33 (M+). Synthesis yield: 56% of a glass fiber; HPLC purity: 99.9%.
Example 34
Synthesis of Compound H-95
Figure BDA0003855463420000311
The procedure of example 25 was repeated except that the starting materials were changed to H-95-A, H-95-B and H-74-C. LC MS: M/Z870.37 (M+). Synthesis yield: 56% of a glass fiber; HPLC purity: 99.9%.
Device example 1: organic electroluminescent device
Figure BDA0003855463420000312
The preparation process is as follows:
1) A transparent anode ITO film layer (thickness 150 nm) was formed on a glass substrate to obtain a first electrode as an anode.
2) By vacuum evaporation, a mixed material of the compound T-1 and the compound T-2 was evaporated as a hole injection layer on the anode surface at a mixing ratio (mass ratio) of 3:97, thickness 10nm.
3) The compound T-2 having a thickness of 100nm was evaporated on the hole injection layer to obtain a first hole transport layer. Then, the compound D-4 of the present invention having a thickness of 10nm was evaporated on the first hole transport layer to obtain a second hole transport layer.
4) On the second hole transport layer, compound T-3 and compound T-4 were mixed in an amount of 95:5 mass ratio co-evaporation to form an organic light emitting layer with a thickness of 40 nm.
5) On the organic light-emitting layer, the compound T-5 was evaporated in order to form a hole blocking layer (thickness 10 nm) with a mixing ratio of 4: the compound T-6 of 6 (mass ratio) and LiQ form an electron transport layer (thickness 30 nm).
6) Magnesium (Mg) and silver (Ag) were mixed at 1:9, and evaporating the mixture on an electron injection layer serving as a second electrode in vacuum to complete the manufacture of the organic light-emitting device.
Device examples 2 to 12
An organic electroluminescent device was fabricated in the same manner as in device example 1, except that compounds D-9, D-25, D-32, D-78, D-85, D-90, D-105, D-109, D-115, D-144 and D-150 were used in place of compound D-4, respectively, in the formation of the second hole transport layer.
Device comparative examples 1 to 2
An organic electroluminescent device was fabricated in the same manner as in device example 1, except that compound HT-1 and compound HT-2 were used in place of compound D-4, respectively, in the formation of the second hole transport layer.
The operating voltage and efficiency of the organic electroluminescent device prepared above were calculated by a computer-controlled Keithley 2400 test system. The device lifetime in dark conditions was obtained using a polar onix (McScience co.) lifetime measurement system equipped with a power supply and a photodiode as detection units. Each of the above sets of device examples and device comparative example 1 were produced and tested in the same batch as the device of device comparative example 2, the operating voltage, efficiency and lifetime of the device of device comparative example 1 were each recorded as 1, and the ratios of the corresponding indices of device examples 1-12, device comparative example 2 and device comparative example 1 were calculated, respectively, as shown in table 1.
Table 1 test results for device examples 1 to 12 and device comparative examples 1 to 2
A second hole transport layer Relative operating voltage Relative efficiency Relative life span
Device comparative example 1 HT-1 1 1 1
Device comparative example 2 HT-2 1.071 1.032 1.430
Device example 1 Compound D-4 0.971 1.132 1.344
Device example 2 Compound D-9 0.962 1.131 1.322
Device example 3 Compound D-25 0.970 1.132 1.112
Device and method for manufacturing the sameExample 4 Compound D-32 0.952 1.173 1.234
Device example 5 Compound D-78 0.935 1.154 1.373
Device example 6 Compound D-85 0.923 1.133 1.285
Device example 7 Compound D-90 0.963 1.152 1.186
Device example 8 Compound D-105 0.956 1.191 1.294
Device example 9 Compound D-109 0.978 1.170 1.415
Device example 10 Compound D-115 0.952 1.163 1.278
Device example 11 Compound D-144 0.97 1.17 1.28
Device example 12 Compound D-150 0.98 1.16 1.26
As is clear from the results of table 1, when the second hole transport layer of the light-emitting device was formed, the compounds used in device examples 1 to 12 all had lower voltages, improved luminous efficiency (up to 19%) and improved lifetime by 40% or more, as compared with the devices formed from the compounds used in device comparative examples 1 to 2.
Device example 13: preparation of organic electroluminescent device
Figure BDA0003855463420000331
A glass substrate coated with Indium Tin Oxide (ITO) having a thickness of 100nm as a thin film was put into distilled water in which a cleaning agent was dissolved, and ultrasonic cleaning was performed. After washing the ITO for 20 minutes, the ultrasonic washing was repeated twice with distilled water for 10 minutes each. After washing with distilled water, the substrate was washed with isopropyl alcohol, acetone and methanol by ultrasonic waves, and then dried and transferred to a plasma cleaner. In addition, the substrate was cleaned with oxygen plasma for 5 minutes and then transferred to a in-vacuum depositor. On the transparent ITO electrode prepared as above, a hole injection layer was formed by thermally vacuum depositing a compound HI at a deposition rate of 0.04 to 0.09nm/s and a total film thickness of 60 nm.
1) And vacuum evaporating a compound HAT as a first hole transport layer on the hole injection layer, wherein the evaporation speed is 0.04-0.09 nm/s, and the total film thickness of the evaporation is 5nm.
2) Vacuum evaporation HT is carried out on the first hole transport layer as a second hole transport layer, the evaporation rate is 0.04-0.09 nm/s, and the total film thickness of the evaporation is 50nm.
3) A light-emitting layer was formed on the hole transport layer 2 by vacuum evaporation of the compound BH and the compound BD at a weight ratio of 25:1, the evaporation rate was 0.04 to 0.09nm/s, and the total film thickness of the evaporation was 20nm.
4) On the light-emitting layer, an electron transporting layer and an injection layer were formed by vacuum evaporation of the compound E-1 and the compound LiQ in a weight ratio of 1:1. The vapor deposition rate was 0.1nm/s, and the total vapor deposition film thickness was 35nm.
5) Lithium fluoride (LiF) was deposited on the electron injection and transport layer at a deposition rate of 0.03nm/s and a total film thickness of 1nm, and then aluminum was deposited at a deposition rate of 0.2nm/s and a total film thickness of 100nm to form a cathode.
The vacuum was maintained at 1 x 10 during this process -7 To 5 x 10 -5 And (5) a bracket.
Device examples 22 to 34
An organic electroluminescent device was fabricated in the same manner as in device example 13, except that the compounds E-1 were replaced with the compounds E-8, E-15, E-21, E-42, E-58, E-69, E-76, E-89, E-107, E-111 and E-119, respectively, in the formation of the electron transport layer.
Device comparative examples 3 to 4
Figure BDA0003855463420000332
An organic electroluminescent device was fabricated in the same manner as in device example 13, except that the compounds ET1 and ET2 were used instead of the compound E-2 in forming the electron transport layer.
The operating voltage and efficiency of the organic electroluminescent device prepared above were calculated by a computer-controlled Keithley 2400 test system. The device lifetime in dark conditions was obtained using a polar onix (McScience co.) lifetime measurement system equipped with a power supply and a photodiode as detection units. Each of the above sets of device examples and device comparative example 3 were produced and tested in the same batch as the device of device comparative example 4, the operating voltage, current efficiency and LT98 of the device of device comparative example 3 were each noted as 1, and the ratios of the corresponding indices of device examples 13-24, device comparative example 4 and device comparative example 3 were calculated, respectively, as shown in table 2.
Table 2 test results for device examples 13 to 24 and device comparative examples 3 to 4
Figure BDA0003855463420000341
As can be seen from the results of table 2, when the inventive series of compounds were used as electron transport layers of light emitting devices instead of the commercial electron transport materials ET1 and ET2 of device comparative examples 3 and 4, voltage reduction was achieved and current efficiency was improved. The result shows that the novel organic material of the invention is taken as an electron transport material of an organic electroluminescent device, is an organic luminescent functional material with good performance, and is expected to be popularized and applied commercially
Device example 25: preparation of organic electroluminescent device
Figure BDA0003855463420000351
The basic structural model of the organic photoelectric device is as follows: ITO/HAT-CN (10 nm)/TAPC (40 nm)/TCTA (10 nm)/EML (compound of the invention): RD (Ir complex) =94:6 (40 nm)/ETL (30 nm)/LiF (1 nm)/Al (80 nm).
The manufacturing method of the organic photoelectric device comprises the following steps:
(1) A transparent anodic Indium Tin Oxide (ITO) 20 (10Ω/sq) glass substrate was subjected to ultrasonic cleaning with acetone, ethanol and distilled water in this order, and then treated with ozone plasma for 15 minutes.
(2) After mounting the ITO substrate on the substrate holder of the vacuum vapor deposition equipment, the system pressure was controlled to 10 -6 A HAT-CN with a thickness of 10nm, TAPC with a thickness of 40nm and TCTA with a thickness of 10nm were sequentially deposited on the ITO substrate.
(3) A 40nm thick light emitting layer (EML) was evaporated on the TCTA described above, wherein the mass ratio of the compound H-1 of the present invention to RD was 94:6.
(4) An Electron Transport Layer (ETL) material having a thickness of 30nm was vapor deposited on the light emitting layer.
(5) LiF having a thickness of 1nm was vapor deposited as an electron injection layer on the electron transport layer.
(6) Finally, al with the thickness of 80nm is evaporated on the electron injection layer to be used as a cathode, and the device is packaged by utilizing a glass packaging cover.
Device examples 26 to 34
An organic electroluminescent device was fabricated in the same manner as in device example 25, except that the compounds H-7, H-22, H-32, H-38, H-53, H-60, H-74, H-85, and H-95 were used instead of the compound H-1, respectively, in forming the light-emitting layer.
Device comparative examples 5 to 6
An organic electroluminescent device was fabricated in the same manner as in device example 25, except that compound RH-01 and compound RH-02 were used in place of compound H-1, respectively, in the formation of the light-emitting layer.
The operating voltage and efficiency of the organic electroluminescent device prepared above were calculated by a computer-controlled Keithley 2400 test system. The device lifetime in dark conditions was obtained using a polar onix (McScience co.) lifetime measurement system equipped with a power supply and a photodiode as detection units. Each of the above sets of device examples and device comparative example 5 were produced and tested in the same batch as the device of device comparative example 6, the current, current efficiency and LT98 of the device of device comparative example 5 were each recorded as 1, and the ratios of the corresponding indices of device examples 25-34, device comparative example 6 and device comparative example 5 were calculated, respectively, as shown in table 3.
Table 3 test results for device examples 25 to 34 and device comparative examples 5 to 6
Figure BDA0003855463420000361
As is clear from the results of Table 3, when the compounds used in device examples 25 to 34 were used as the light-emitting layers of the light-emitting devices, the light-emitting efficiency was improved (up to 20%) and the lifetime was increased by 40% or more, as compared with the devices formed from the compounds used in device comparative examples 5 to 6.
Accordingly, the device structures in the above embodiment and the comparative example are identical except for the corresponding functional layers, the device performance based on the comparative material is used as a reference, the current efficiency of the device containing the compound of the present invention is remarkably improved, and the service life of the device is also improved.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art, who is within the scope of the present invention, should make equivalent substitutions or modifications according to the technical scheme of the present invention and the inventive concept thereof, and should be covered by the scope of the present invention.

Claims (13)

1. An organic compound, the chemical structure of which is shown in formula (I):
Figure FDA0003855463410000011
Wherein: r is R 1 -R 8 The groups are identical or different and are each independently selected from hydrogen, deuterium, cyano, fluorine atom-containing groups, substituted or unsubstituted linear or branched C1-C30 alkyl groups; substituted or unsubstituted C1-C30 heteroalkyl, substituted or unsubstituted C3-C30 cycloalkylA substituted or unsubstituted C3 to C30 heterocycloalkyl group, a substituted or unsubstituted C6 to C60 aryl group, or a substituted or unsubstituted C5 to C60 heteroaryl group, or a ring bonded to an adjacent atom.
2. The organic compound of claim 1, wherein R 1 -R 8 At least one selected from the following structures:
Figure FDA0003855463410000012
wherein:
R 9 -R 12 identical or different, each independently selected from hydrogen, deuterium, substituted or unsubstituted linear or branched C1-C30 alkyl; a substituted or unsubstituted C1-C30 heteroalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C3-C30 heterocycloalkyl group, a substituted or unsubstituted C6-C60 aryl group, or a substituted or unsubstituted C5-C60 heteroaryl group;
A. b is independently selected from substituted or unsubstituted C6-C60 aryl or substituted or unsubstituted C5-C60 heteroaryl;
Ar 1 -Ar 2 the same or different, each independently selected from substituted or unsubstituted C6-C60 aryl, or substituted or unsubstituted C5-C60 heteroaryl;
L 1 -L 9 The same or different, and are independently selected from single bond, substituted or unsubstituted straight-chain or branched-chain alkyl of C1-C30, substituted or unsubstituted heteroalkyl of C1-C30, substituted or unsubstituted cycloalkyl of C3-C30, substituted or unsubstituted heterocycloalkyl of C3-C30, substituted or unsubstituted aryl of C6-C60, or substituted or unsubstituted heteroaryl of C5-C60;
e is selected from an electron withdrawing group containing fluorine atoms, an electron withdrawing group containing nitrogen atoms or an electron withdrawing group containing oxygen;
* Is a junction site.
3. An organic compound according to claim 2, wherein a and B are independently selected from the group consisting of:
Figure FDA0003855463410000021
Ar 3 -Ar 8 the same or different, and are independently selected from substituted or unsubstituted C6-C60 aryl or substituted or unsubstituted C5-C60 heteroaryl;
X 1 -X 13 identical or different, independently selected from O, S, CR 13 R 14 、NR 15 Or SiR 16 R 17 ；R 13 -R 17 Identical or different, each independently selected from hydrogen, deuterium, substituted or unsubstituted linear or branched C1-C30 alkyl; a substituted or unsubstituted C1-C30 heteroalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C3-C30 heterocycloalkyl group, a substituted or unsubstituted C6-C60 aryl group, or a substituted or unsubstituted C5-C60 heteroaryl group.
4. The organic compound according to claim 2, wherein L 1 、L 2 、L 3 、L 5 、L 7 、L 8 And L 9 The groups are the same or different and are each independently selected from the following groups:
Figure FDA0003855463410000022
wherein is the site of attachment.
5. The organic compound of claim 2, wherein L 4 、R 11 、L 6 、R 12 E are identical or different and are each independently selected from the following groups:
Figure FDA0003855463410000023
Figure FDA0003855463410000031
wherein R is 11 ～R 14 The choices of (2) are the same or different; the R is 11 ～R 12 R as defined in claim 2 11 ～R 12 The method comprises the steps of carrying out a first treatment on the surface of the The R is 13 ～R 14 R as defined in claim 3 13 ～R 14 。
6. The organic compound of claim 1, wherein R 1 -R 8 At least one of which is selected from the following structures:
Figure FDA0003855463410000032
Figure FDA0003855463410000041
Figure FDA0003855463410000051
CN；
X 14 、X 15 independently selected from O, S, CR 15 R 16 、NR 17 Or SiR 18 R 19 ；R 15 ～R 19 Each independently selected from hydrogen, deuterium, substituted or unsubstituted straight or branched chain C1-C30 alkyl; a substituted or unsubstituted C1-C30 heteroalkyl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted C3-C30 heterocycloalkyl group, a substituted or unsubstituted C6-C60 aryl group, or a substituted or unsubstituted C5-C60 heteroaryl group; preferably, R 15 ～R 19 Independently selected from hydrogen, deuterium, methyl, ethyl, propyl, isopropylTertiary butyl, phenyl, biphenyl, or naphthyl;
* Is a junction site.
7. An organic compound according to any one of claims 1 to 6, wherein the organic compound is selected from one or more of the following chemical structures:
Figure FDA0003855463410000061
Figure FDA0003855463410000071
Figure FDA0003855463410000081
Figure FDA0003855463410000091
Figure FDA0003855463410000101
Figure FDA0003855463410000111
Figure FDA0003855463410000121
8. An organic layer comprising the organic compound according to any one of claims 1 to 7.
9. Use of an organic compound according to any one of claims 1 to 7 and/or an organic layer according to claim 8 in an organic optoelectronic device.
10. An organic optoelectronic device comprising a first electrode, a second electrode, and the organic layer of claim 8, wherein the organic layer is at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron injection layer, or an electron transport layer.
11. The organic optoelectronic device according to claim 10, wherein the light-emitting layer comprises one or more organic compounds according to claims 1 to 7;
and/or the hole transport layer comprises one or more organic compounds according to claims 1 to 7;
and/or the electron transport layer comprises one or more organic compounds according to claims 1 to 7.
12. The organic optoelectronic device according to claim 10, wherein the organic optoelectronic device is an organic photovoltaic device, an organic light emitting device, an organic solar cell, an electronic paper, an organic photoreceptor, an organic thin film transistor.
13. A display or lighting device comprising an organic optoelectronic device according to any one of claims 10 to 12.
CN202211146416.5A 2022-09-20 2022-09-20 Organic compound and application thereof in organic photoelectric device Pending CN116082167A (en)

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Inventor after: Wang Xiangcheng

Inventor after: He Mu

Inventor before: Wang Peng

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