CN110437103B - Cyclic compound, application thereof and electronic device - Google Patents

Cyclic compound, application thereof and electronic device Download PDF

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CN110437103B
CN110437103B CN201910707975.0A CN201910707975A CN110437103B CN 110437103 B CN110437103 B CN 110437103B CN 201910707975 A CN201910707975 A CN 201910707975A CN 110437103 B CN110437103 B CN 110437103B
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cyclic compound
ethyl acetate
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CN110437103A (en
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魏定纬
蔡烨
丁欢达
谢坤山
陈志宽
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Ningbo Lumilan New Material Co ltd
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Abstract

The invention relates to the technical field of display, in particular to a cyclic compound, application thereof and an electronic device. The cyclic compound at least comprises the compound represented by the formula 001-011, has good thermal stability, has a matched LUMO energy level with an adjacent layer, can promote hole generation when being applied to an OLED device as a p-doped material in a hole transport layer, enables electrons and holes to be more effectively recombined in the OLED device to form excitons, and enables the obtained OLED device to have lower driving voltage, higher carrier combination rate and luminous efficiency.

Description

Cyclic compound, application thereof and electronic device
Technical Field
The invention relates to the technical field of display, in particular to a cyclic compound, application thereof and an electronic device.
Background
Compared with inorganic electroluminescence, the organic electroluminescence device (OLED) has the advantages of high brightness, quick response, wide viewing angle, simple process, high color purity, capability of realizing full-color display from blue light to red light, flexibility and the like, is favored by a plurality of scientists, and has wide application prospect in the fields of display and illumination.
The current OLED devices include one or more layers of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, with appropriate electrodes, which are respectively composed of the following materials: hole injection materials, hole transport materials, light emitting materials, electron transport materials, and electron injection materials; for OLED devices, charge injection and transport are the first steps in converting electrical energy into light, and this process plays a crucial role in the turn-on voltage, the luminous efficiency, and the lifetime of the device. And the injection and transmission efficiency of charges can be effectively improved by improving the concentration and the mobility of carriers, so that the starting voltage of the device is reduced, the luminous efficiency is improved, and the luminous service life is prolonged. In the aspect of a hole transport layer, the concentration of holes can be effectively improved by adding a P doping material into the hole transport material, and further the transmission efficiency of the holes is improved.
The currently commercially used P-doped materials have a low LUMO level that can be matched to the HOMO level of common hole transport materials (e.g. NPB), but suffer from the following disadvantages: firstly, the synthesis and purification of the material are difficult, the stability of the material is poor, and the material is applied to an organic electroluminescent device, so that the service life of the device is short, and the price is high; secondly, some commercially used materials are extremely easy to diffuse into adjacent functional layers to cause luminescence quenching; thirdly, the P doping material used in the current commercial is easy to pollute the evaporation system, cross contamination is caused, the luminous efficiency of the device is reduced, and the repeatability and the thermal stability of the device are difficult to ensure.
Disclosure of Invention
The invention aims to solve the problems that the P doping material added into the hole transport material in the prior art has poor thermal stability and has limited improvement on the luminous efficiency and the service life of the organic electroluminescent device.
In order to achieve the purpose, the invention adopts the following technical scheme:
a cyclic compound consisting of n
Figure BDA0002152776090000011
With m Ar1Is formed in which
Figure BDA0002152776090000012
And Ar1The connection position is not fixed, and at least comprises the following structures:
Figure BDA0002152776090000021
wherein n is 1-4, m is 1-4, and at least one in the same structural formula
Figure BDA0002152776090000022
When it is, each
Figure BDA0002152776090000023
The radicals are the same or different, and at least one Ar is in the same structural formula1When each Ar is1The radicals are identical or different and are,
A1、A2identical or different and are each independently selected from CN, halogen, CF3Substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C1-C30Alkyl, substituted or unsubstituted C2-C30Alkenyl of (a), substituted or unsubstituted C3-C30Cycloalkyl, substituted or unsubstituted C3-C30Cycloalkenyl group of (1), substituted or unsubstituted C3-C30A heterocycle of,
Figure BDA0002152776090000024
Or A1、A2Are linked to each other to form a ring B selected from substituted or unsubstituted C3-C30Cycloalkyl, substituted or unsubstituted C3-C30Cycloalkenyl group of (1), substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C3-C30The heterocyclic ring of (a) is a heterocyclic ring,
X1independently selected from O, S, C (CN)2、C(CF3)2、C(CN)(CF3)、NCN，
Y1Is independently selected from the group consisting of C, SO,
R1independently selected from hydrogen, halogen, cyano, nitro, trifluoromethyl, substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C3-C30Heterocyclic, substituted or unsubstitutedC1-C30Alkyl, substituted or unsubstituted C1-C30The alkoxy group of (a) is (b),
Ar1is independently selected from C (R)18)C(R19) Substituted or unsubstituted C6-C30Arylene of (a), substituted or unsubstituted C3-C30The heterocyclic ring of (a) is a heterocyclic ring,
R18、R19each independently selected from CN, CF3，
Said substituted or unsubstituted C3-C30The heterocycle or heterocyclylene of (a) contains at least one heteroatom of N, B, O, P, S, Si.
Further, A is1、A2Are respectively and independently selected from CN and CF3Substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C3-C30A heterocycle of,
Figure BDA0002152776090000031
Or A1、A2Are linked to each other to form a ring B selected from substituted or unsubstituted C6-C30Aryl, substituted or unsubstituted C3-C30The heterocyclic ring of (1).
Further, said substituted or unsubstituted C6-C30The aryl group of (a) is selected from the following structures:
Figure BDA0002152776090000032
said substituted or unsubstituted C6-C30The arylene group of (a) is selected from the following structures:
Figure BDA0002152776090000041
said substituted or unsubstituted C3-C30The heterocycle of (a) is selected from the following structures:
Figure BDA0002152776090000042
Figure BDA0002152776090000051
said substituted or unsubstituted C3-C30The heterocyclylene of (a) is selected from the following structures:
Figure BDA0002152776090000061
Figure BDA0002152776090000071
wherein R is10-R16，R20-R44Each independently selected from hydrogen, cyano, nitro, halogen, trifluoromethyl, C (CN)2Or at least one adjacent group is linked to each other to form a saturated or unsaturated ring.
Further, the B ring is selected from the following structures:
Figure BDA0002152776090000081
wherein R is2-R9Each independently selected from hydrogen, halogen, trifluoromethyl, nitro, cyano, C (CN)2At least one adjacent group being linked to each other to form a saturated or unsaturated ring,
X2-X3is oxygen.
Further, said substituted or unsubstituted C3-C30The heterocycle of (a) is selected from the following structures:
Figure BDA0002152776090000082
Figure BDA0002152776090000091
said substituted or unsubstituted C3-C30The heterocyclylene of (a) is selected from the following structures:
Figure BDA0002152776090000101
the B ring is selected from the following structures:
Figure BDA0002152776090000111
further, said substituted or unsubstituted C1-C30Each alkyl group of (A) is independently selected from perfluoromethyl, perfluoroethyl, perfluoropropyl, said substituted or unsubstituted C2-C30Each alkenyl group of (a) is independently selected from perfluorovinyl, perfluoropropenyl, perfluoroisopropylidene, and/or,
said ring B is selected from substituted or unsubstituted heteroaryl, and/or,
said substituted or unsubstituted C3-C30Is N, and/or,
the halogen is fluorine, and/or,
the cyclic compound does not contain a hydrogen atom.
The invention also provides an application of the cyclic compound as an organic electroluminescent material.
The invention also provides an electronic device comprising at least one cyclic compound as described above, the electronic device comprising an organic electroluminescent device, an organic field effect transistor, an organic thin film transistor, an organic light emitting transistor, an organic integrated circuit, an organic solar cell, an organic field quenching device, a light emitting electrochemical cell, an organic laser diode or an organic photoreceptor.
The invention also provides a display device comprising the electronic device.
The invention also provides a lighting device comprising the electronic device.
The invention has the beneficial effects that:
1) the cyclic compound of the present invention comprises n
Figure BDA0002152776090000112
With m Ar1Is formed in which
Figure BDA0002152776090000113
And Ar1The binding position is not fixed, n is 1-4, m is 1-4, and the compound at least comprises a compound represented by formula 001-011, wherein the compound takes a ring as a core and provides free radicals; by using
Figure BDA0002152776090000121
The group ensures intramolecular conjugation, and simultaneously has a certain included angle between molecules, so that no interaction exists between the molecules, the cyclic compound is effectively ensured to have good thermal stability, and the group has a matched LUMO energy level with an adjacent layer, and the group can be applied to an OLED device as a p-doped material in a hole transport layer, so that hole generation can be promoted, electrons and holes can be more effectively recombined in the OLED device to form excitons, the obtained OLED device has lower driving voltage, higher carrier combination rate, luminous efficiency and longer device life, and meanwhile, a strong electron-withdrawing group is introduced, so that the deeper LUMO energy level can be ensured, and the group has a better matched LUMO energy level with the adjacent layer.
2) The cyclic compound provided by the invention further does not contain hydrogen atoms, single bonds and double bonds in the structural formula of the cyclic compound are alternately arranged, and when the cyclic compound is used as a doping material in a hole transport layer and applied to an OLED device, the current efficiency of the device is higher, and the service life of the device is longer.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
Fig. 1 is a graph comparing theoretical calculation results of HOMO level, LUMO level, and single-triplet energy gap Eg of the compound represented by C4 provided in example 5 of the present invention.
Detailed Description
The following examples are provided to further understand the present invention, not to limit the scope of the present invention, but to provide the best mode, not to limit the content and the protection scope of the present invention, and any product similar or similar to the present invention, which is obtained by combining the present invention with other prior art features, falls within the protection scope of the present invention.
The examples do not show the specific experimental steps or conditions, and can be performed according to the conventional experimental steps described in the literature in the field. The reagents or instruments used are not indicated by manufacturers, and are all conventional reagent products which can be obtained commercially.
The following are explanations of some of the terms and symbols appearing in the present invention, and are specifically as follows:
alkyl groups: the saturated hydrocarbon group is a hydrocarbon group having one hydrogen atom less in the alkyl molecule, and includes branched and straight chain hydrocarbon groups. For example: methyl, ethyl, propyl, isopropyl, and the like.
Alkenyl: the hydrocarbon group formed by removing one or more hydrogen atoms from an olefin molecule includes branched and straight chain. For example, vinyl, propenyl, isopropenyl, and the like.
Aryl: any functional group or substituent derived from a simple aromatic ring, wherein one atom is attached to the main ring.
Arylene group: any functional group or substituent derived from a simple aromatic ring in which two atoms are attached to the main ring.
Heterocyclic ring: the atoms constituting the ring include other atoms in addition to carbon atoms, one of which is bonded to the main ring, and the hetero atom may be one atom or a plurality of different atoms; the ring may be a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, or the like; the rings may also be monocyclic, spiro or fused; heterocycles also include saturated and partially unsaturated aliphatic and aromatic heterocycles. For example: ethylene oxide, thiirane, caprolactam, furan, thiophene, pyridine, quinoline, pyrimidine, tetrahydropyran, and the like.
Heterocyclic ring (II): the atoms constituting the ring are other than carbon atoms, two of which are bonded to the main ring, and the hetero atom may be one atom or a plurality of different atoms; the ring may be a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, or the like; the rings may also be monocyclic, spiro or fused; heterocycles also include saturated and partially unsaturated aliphatic and aromatic heterocycles.
A main ring: the main ring of the invention is m (Ar)1) The upper two atoms and n (C).
Alkoxy groups: and groups in which an alkyl group is directly bonded to an oxygen atom, such as methoxy, ethoxy, propoxy, and the like.
Cycloalkyl groups: saturated cyclic carbon chains such as cyclopropane, cyclobutane, cyclopentane, cyclohexane, and the like.
Cycloalkenyl group: unsaturated cyclic carbon chains such as cyclopropene, cyclobutene, cyclobutadiene, cyclopentene, cyclohexene, and the like.
Full conjugated structure: the single bond and the double bond are arranged alternately.
Figure BDA0002152776090000131
Represents a connecting bond; "·" denotes a connection site on ring B, wherein A is connected to1、A2The carbon atom connected is the carbon atom at the position of "·";
Figure BDA0002152776090000132
denotes a linking site wherein
Figure BDA0002152776090000133
Two carbon atoms are represented by formula 001-Asca 011 with Ar1Two carbon atoms attached.
Example 1
This example provides a cyclic compound having the structure shown in formula C1 below:
Figure BDA0002152776090000134
the synthetic route for the compound of formula C1 is shown below:
Figure BDA0002152776090000141
the preparation method of the compound shown as the formula C1 specifically comprises the following steps:
1) synthesis of intermediate 1-1: compound N1(19.00 g, 1 eq) was dissolved in 50 ml of absolute ethanol in a 250 ml single-neck flask under nitrogen, and potassium carbonate (14.49 g, 1.05 eq) and compound M1 (8.80 g, 1 eq) were added and stirred at room temperature for 4 hours. Quenching with 50 ml of water, spin-drying the solvent, extraction with ethyl acetate (100 ml. times.3), and spin-drying the organic solvent gave the crude product, which was purified by chromatography (ethyl acetate/hexane ratio by volume 1/20) to give intermediate 1-1(21.32 g, 82% yield).
2) Synthesis of intermediate 2-1: in a 250 ml three-necked flask, the intermediate 1-1(26.00 g, 1 eq) and 50 ml of nitric acid were added under nitrogen protection and reacted at room temperature for 2 hours. After completion of the reaction, 50 ml of water was added to quench, and extraction was performed with ethyl acetate (100 ml. times.3), and the organic phase was dried over anhydrous sodium sulfate and dried by spin-drying to obtain a crude product. The crude product was purified by chromatography (volume ratio of ethyl acetate/hexane 1/15) to afford intermediate 2-1(21.76 g, 85% yield).
3) Synthesis of compound C1: in a 250 ml three-neck flask, adding the intermediate 2-1(25.60 g, 1 eq), compound N2(10.80 g, 1 eq) and acetic acid (100 ml) under the protection of nitrogen, reacting at 40 ℃ for 4 hours, cooling to room temperature, adding 150 ml of water to quench, extracting with ethyl acetate (150 ml. times.3), drying the organic phase with anhydrous sodium sulfate, and spin-drying the organic phase to obtain the crude product. The crude product was purified by chromatography (volume ratio of ethyl acetate/hexane 1/10) to yield compound C1(21.32 g, 65% yield).
Elemental analysis: c14N6F4Theoretical value: c, 51.24; n, 25.61; measured value: c, 51.26; n, 25.60; HRMS (ESI) M/z (M +): theoretical value: 328.0121, respectively; measured value: 328.0120.
example 2
This example provides a cyclic compound having the structure shown in formula C2 below:
Figure BDA0002152776090000151
the synthetic route for the compound of formula C2 is shown below:
Figure BDA0002152776090000152
the preparation method of the compound shown as the formula C2 specifically comprises the following steps:
1) synthesis of intermediates 1-2: compound N2(10.80 g, 1 eq) was dissolved in 50 ml of absolute ethanol in a 250 ml single-neck flask under nitrogen, potassium carbonate (14.49 g, 1.05 eq) and compound M2 (11.60 g, 1 eq) were added and stirred at room temperature for 4 hours. Quenching with 50 ml of water, spin-drying the solvent, extraction with ethyl acetate (100 ml. times.3), and spin-drying the organic solvent gave the crude product, which was purified by chromatography (ethyl acetate/hexane ratio by volume 1/20) to give intermediate 1-2(14.85 g, 79% yield).
2) Synthesis of intermediate 2-2: the intermediate 1-2(18.80 g, 1 eq) and 50 ml of nitric acid were added to a 250 ml three-necked flask under nitrogen protection and reacted at room temperature for 2 hours. After the reaction was completed, 50 ml of water was added to quench, ethyl acetate (100 ml. times.3) was extracted, the organic phase was dried over anhydrous sodium sulfate, and the organic solvent was spin-dried to obtain a crude product. The crude product was purified by chromatography (ethyl acetate/hexane ratio by volume 1/15) to afford intermediate 2-2(13.80 g, 75% yield).
3) Synthesis of compound C2: in a 250 ml three-neck flask, adding the intermediate 2-2(18.40 g, 1 eq), the compound N3(42.80 g, 2 eq) and acetic acid (120 ml) under the protection of nitrogen, reacting at 40 ℃ for 5 hours, cooling to room temperature, adding 150 ml of water to quench, extracting with ethyl acetate (150 ml. times.3), drying the organic phase with anhydrous sodium sulfate, and spin-drying the organic solvent to obtain the crude product. The crude product was purified by chromatography (etoac/hexanes vol 1/10) to provide compound C2(35.71 g, 62% yield).
Elemental analysis: c26N8F8Theoretical value: c, 54.18; n, 19.44; measured value: c, 54.15; n, 19.47; HRMS (ESI) M/z (M +): theoretical value: 576.0118, respectively; measured value: 576.0120.
example 3
This example provides an intermediate compound, the synthetic route of which is shown below:
Figure BDA0002152776090000161
1) synthesis of intermediate 1': in a 250 ml three-necked flask, 4, 5-dihydroxycyclopent-4-ene-1, 2, 3-trione (14.21 g, 1 eq), 2, 3-diamino-2-butenedionitrile (10.80 g, 1 eq), acetic acid (100 ml) were added under nitrogen protection, reacted at 40 ℃ for 4 hours, cooled to room temperature, quenched with 150 ml of water, extracted with ethyl acetate (150 ml. times.3), the organic phase was dried over anhydrous sodium sulfate, and the organic solvent was spin-dried to give the crude product. The crude product was purified by chromatography (ethyl acetate/hexane ratio by volume 1/10) to afford intermediate 1' (14.98 g, 70% yield).
2) Synthesis of intermediate 2': intermediate 1' (21.40 g, 1 eq) and 50 ml nitric acid were added under nitrogen protection in a 250 ml three-necked flask and reacted at room temperature for 2 hours. After the reaction was completed, 50 ml of water was added to quench, ethyl acetate (100 ml. times.3) was extracted, the organic phase was dried over anhydrous sodium sulfate, and the organic solvent was spin-dried to obtain a crude product. The crude product was purified by chromatography (etoac/hexanes volume ratio 1/10) to afford intermediate 2' (12.30 g, 58% yield).
3) Synthesis of intermediate 3': in a 250 ml three-necked flask, adding the intermediate 2' (21.20 g, 1 eq), 2, 3-diamino-2-butenedionitrile (10.80 g, 1 eq) and acetic acid (100 ml) under nitrogen protection, reacting at 40 ℃ for 4 hours, cooling to room temperature, adding 50 ml of water to quench, extracting with ethyl acetate (150 ml. times.3), drying the organic phase with anhydrous sodium sulfate, and spin-drying the organic solvent to obtain a crude product. The crude product was purified by chromatography (ethyl acetate/hexane, 1/10 vol%) to give compound 3' (20.45 g, 78%).
Example 4
This example provides a cyclic compound having the structure shown in formula C3 below:
Figure BDA0002152776090000171
the synthetic route for the compound of formula C3 is shown below:
Figure BDA0002152776090000172
the preparation method of the compound shown as the formula C3 specifically comprises the following steps:
synthesis of compound C3: compound N1(20.70 g, 1 eq) was dissolved in 100 ml of absolute ethanol in a 250 ml single-neck flask under nitrogen, potassium carbonate (14.49 g, 1.05 eq), intermediate 3' (28.40 g, 1 eq) were added and stirred at room temperature for 4 hours. Quenching with 50 ml of water, drying the organic solvent, extraction with ethyl acetate (100 ml. times.3), drying the organic solvent and chromatography of the crude product (1/8 volume ratio of ethyl acetate/hexane) gave compound C3(35.57 g, 78% yield).
Elemental analysis: c20N10F4Theoretical value: c, 52.65; n, 30.70; measured value: c, 52.67; n, 30.71; HRMS (ESI) M/z (M +): theoretical value: 456.0244, respectively; measured value: 456.0245.
example 5
This example provides a cyclic compound having the structure shown in formula C4 below:
Figure BDA0002152776090000181
the synthetic route for the compound of formula C4 is shown below:
Figure BDA0002152776090000182
the preparation method of the compound shown as the formula C4 specifically comprises the following steps:
synthesis of compound C4: compound N4(36.20 g, 1 eq) was dissolved in 100 ml of absolute ethanol in a 250 ml single-neck flask under nitrogen, potassium carbonate (14.49 g, 1.05 eq), intermediate 3' (28.40 g, 1 eq) were added and stirred at room temperature for 4 hours. Quenching was performed by adding 50 ml of water, followed by rotary drying of the organic solvent, extraction with ethyl acetate (100 ml. times.3), and rotary drying of the organic solvent to obtain a crude product, which was purified by chromatography (ethyl acetate/hexane volume ratio 1/7) to obtain compound C4(42.70 g, yield 68%).
Elemental analysis: c25N10F8Theoretical value: c, 53.52; n, 22.29; measured value: c, 53.50; n, 22.30; HRMS (ESI) M/z (M +): theoretical value: 628.0180, respectively; measured value: 628.0184.
example 6
This example provides a cyclic compound having the structure shown in formula C5 below:
Figure BDA0002152776090000191
the synthetic route for the compound of formula C5 is shown below:
Figure BDA0002152776090000192
the preparation method of the compound shown as the formula C5 specifically comprises the following steps:
synthesis of intermediates 1 to 5: 4, 5-dinitrile cyclopent-4-ene-1, 2, 3-trione (16.00 g, 1 equiv.), 2, 3-diamino-2-butenedionitrile (10.80 g, 1 equiv.), and acetic acid (100 ml) were added into a 250 ml three-necked flask under the protection of nitrogen, reacted at 40 ℃ for 4 hours, cooled to room temperature, quenched with 150 ml of water, extracted with ethyl acetate (150 ml. times.3), the organic phase was dried over anhydrous sodium sulfate, and the organic solvent was spin-dried to obtain a crude product. The crude product was purified by chromatography (ethyl acetate/hexane ratio by volume 1/10) to afford intermediates 1-5(15.08 g, 65% yield).
Synthesis of compound C5: compound N1(19.00 g, 1 eq) was dissolved in 100 ml of absolute ethanol in a 250 ml single-neck flask under nitrogen, potassium carbonate (14.49 g, 1.05 eq), intermediate 1-5 (23.20 g, 1 eq) were added and stirred at room temperature for 4 hours. Quenching with 50 ml of water, drying the organic solvent, extraction with ethyl acetate (100 ml. times.3) and drying the organic solvent to give the crude product, which is purified by chromatography (ethyl acetate/hexane ratio 1/8 by volume) to give compound C5(33.13 g, 82% yield).
Elemental analysis: c18N8F4Theoretical value: c, 53.48; n, 27.72; measured value: c, 53.47; n, 27.73; HRMS (ESI) M/z (M +): theoretical value: 404.0182, respectively; measured value: 404.0185.
example 7
This example provides a cyclic compound having the structure shown in formula C6 below:
Figure BDA0002152776090000201
the synthetic route for the compound of formula C6 is shown below:
Figure BDA0002152776090000202
the preparation method of the compound shown as the formula C6 specifically comprises the following steps:
synthesis of compound C6: tetrahydrofuran (20 ml), mercury dichloride (0.55 g, 1 eq), magnesium turnings (1.8 g, 4 eq) were added under nitrogen in a 250 ml three-necked flask, the mixture was stirred at room temperature for 30 minutes, the supernatant liquid was removed by syringe, the remaining amalgam was washed with tetrahydrofuran (10 ml x 3 times), then covered with tetrahydrofuran (50 ml), cooled to-10 ℃ and then titanium tetrachloride (4.4 ml, 20 eq) was added dropwise to give a yellow-green mixture. Intermediate 3' (2.84 g, 5 equivalents) dissolved in tetrahydrofuran (25 ml) was added to the above yellow-green mixture and the mixture was stirred at 0 ℃ for 2 hours in the dark. The reaction system was heated to room temperature and then heated under reflux for 24 hours. After the reaction was completed, the temperature was decreased to room temperature, and the reaction was quenched with saturated potassium carbonate (5 ml), stirred for 30 minutes, diluted with ether (5 ml) and filtered. The filtrate was concentrated, the residue was dissolved in ether, washed with brine, dried over anhydrous magnesium sulfate and concentrated, and the concentrated filtrate was separated by silica gel column chromatography (ethyl acetate/hexane in a volume ratio of 1/8) to obtain compound C6 (yield 4.45 g, 83%).
Elemental analysis: c26N16Theoretical value: c, 58.22; n, 41.78; measured value: c, 58.25; n, 41.75; HRMS (ESI) M/z (M +): theoretical value: 536.0492, respectively; measured value: 536.0490.
example 8
This example provides a cyclic compound having the structure shown in formula C7 below:
Figure BDA0002152776090000211
the synthetic route for the compound of formula C7 is shown below:
Figure BDA0002152776090000212
1) synthesis of intermediates 1 to 7: compound M8(14.20 g, 1 eq) was dissolved in 50 ml of absolute ethanol in a 250 ml single-neck flask under nitrogen, potassium carbonate (14.49 g, 1.05 eq) and compound N2(10.80 g, 1 eq) were added and stirred at room temperature for 4 hours. Quenching with 50 ml of water, drying the organic solvent, extraction with ethyl acetate (100 ml. times.3), drying the organic solvent to give the crude product, which is purified by chromatography (ethyl acetate/hexane ratio 1/20 by volume) to give intermediates 1-7(13.05 g, 61% yield).
2) Synthesis of intermediates 2 to 7: the intermediates 1 to 7(21.40 g, 1 eq) and 50 ml of nitric acid were added to a 250 ml three-necked flask under nitrogen protection and reacted at room temperature for 2 hours. After the reaction was completed, 50 ml of water was added to quench, ethyl acetate (100 ml. times.3) was extracted, the organic phase was dried over anhydrous sodium sulfate, and the organic solvent was spin-dried to obtain a crude product. The crude product was purified by chromatography (ethyl acetate/hexane ratio by volume 1/15) to afford intermediates 2-7(16.54 g, 78% yield).
3) Synthesis of compound C7: in a 250 ml three-neck flask, adding the intermediate 2-7(21.20 g, 1 eq), the compound N13(64.80 g, 3 eq) and acetic acid (180 ml) under the protection of nitrogen, reacting at 40 ℃ for 5 hours, cooling to room temperature, adding 150 ml of water to quench, extracting with ethyl acetate (150 ml. times.3), drying the organic phase with anhydrous sodium sulfate, and spin-drying the organic solvent to obtain the crude product. The crude product was purified by chromatography (ethyl acetate/hexane, vol 1/10) to yield compound C7(33.30 g, 45% yield).
Elemental analysis: c36N22Theoretical value: c, 58.39; n, 41.61; measured value: c, 58.42; n, 41.58; HRMS (ESI) M/z (M +): theoretical value: 740.0676, respectively; measured value: 740.0612.
example 9
This example provides a cyclic compound having the structure shown in formula C8 below:
Figure BDA0002152776090000221
the synthetic route for the compound of formula C8 is shown below:
Figure BDA0002152776090000222
the preparation method of the compound shown as the formula C8 specifically comprises the following steps:
1) synthesis of intermediates 1 to 8: compound M5(42.77 g, 1 eq), compound N1(38.00 g, 2 eq), potassium carbonate (28.98 g, 2.1 eq), and 100 ml of tetrahydrofuran were added to a 250 ml single-neck flask, and after stirring at room temperature for 3 hours, the solvent was dried by spinning to give a crude product, which was purified by chromatography (ethyl acetate/hexane volume ratio 1/8) to give compounds 1-8(57.88 g, 75%).
2) Synthesis of intermediates 2 to 8: intermediate 1-8(1 eq), acetonitrile (100 ml) were added to a 250 ml single-neck flask, an ice-water bath was maintained at 0-5 ℃, and aqueous solutions (10 ml) of RuCl 3. H2O (0.07 eq) and sodium periodate (1.5 eq) were added, stirred for 5 hours, and the solvent was spun dry to give the crude product, which was purified by chromatography (ethyl acetate/hexane ratio by volume 1/15) to give intermediate 2-8(35.84 g, 70%).
3) Synthesis of compound C8: to a 250 ml single-neck flask were added intermediate 2-8(51.20 g, 1 eq), compound N2(21.60 g, 2 eq), potassium carbonate (28.98 g, 2.1 eq), and 100 ml of tetrahydrofuran, and stirred at room temperature for 5 hours. The solvent was spun dry to give the crude product, which was purified by chromatography (etoac/hexanes volume ratio 1/8) to give compound C8(45.92 g, 70%).
Elemental analysis: c24N6F4Theoretical value: c, 51.24; n, 25.61; measured value: c, 51.26; n, 25.60; HRMS (ESI) M/z (M +): theoretical value: 656.0241, respectively; measured value: 656.0245.
example 10
This example provides a cyclic compound having the structure shown in formula C9 below:
Figure BDA0002152776090000231
the synthetic route for the compound of formula C9 is shown below:
Figure BDA0002152776090000241
the preparation method of the compound shown as the formula C9 specifically comprises the following steps:
1) synthesis of intermediates 1 to 9: in a 250 ml three-necked flask, 4, 5-dihydroxycyclopent-4-ene-1, 2, 3-trione (14.21 g, 1 eq), compound N6(10.81 g, 1 eq), and acetic acid (100 ml) were added under nitrogen protection, reacted at 40 ℃ for 2 hours, cooled to room temperature, quenched with 150 ml of water, extracted with ethyl acetate (150 ml × 3), the organic phase was dried over anhydrous sodium sulfate, and the organic solvent was spin-dried to give the crude product. The crude product was purified by chromatography (ethyl acetate/hexane ratio by volume 1/10) to afford intermediates 1-9(16.71 g, 78% yield).
2) Synthesis of intermediates 2 to 9: the intermediates 1 to 9(21.42 g, 1 eq) and 50 ml of nitric acid were added to a 250 ml three-necked flask under nitrogen protection and reacted at room temperature for 2 hours. After the reaction was completed, 50 ml of water was added to quench, ethyl acetate (100 ml. times.3) was extracted, the organic phase was dried over anhydrous sodium sulfate, and the organic solvent was spin-dried to obtain a crude product. The crude product was purified by chromatography (ethyl acetate/hexane ratio by volume 1/10) to afford intermediates 2-9(13.16 g, 62% yield).
3) Synthesis of intermediates 3 to 9: in a 250 ml three-neck flask, 2-9(21.22 g, 1 eq), compound N6(10.81 g, 1 eq), and acetic acid (100 ml) were added under nitrogen protection, reacted at 40 ℃ for 2 hours, cooled to room temperature, quenched by adding 50 ml of water, extracted with ethyl acetate (150 ml × 3), the organic phase was dried over anhydrous sodium sulfate, and the organic solvent was spin-dried to give the crude product. The crude product was purified by chromatography (ethyl acetate/hexane, 1/10 vol.) to afford compounds 3-9(22.73 g, 80%).
4) Synthesis of compound C9: to a 250 ml single-neck flask were added intermediate 3-9(28.41 g, 1 eq), compound N1(19.00 g, 1 eq), potassium carbonate (14.49 g, 1.05 eq), and 100 ml of tetrahydrofuran, and stirred at room temperature for 3 hours. The solvent was spun dry to give the crude product, which was purified by chromatography (etoac/hexanes volume ratio 1/8) to give compound C9(32.86 g, 72%).
Elemental analysis: c24H8N6F4Theoretical value: c, 63.17; n, 18.42; h, 1.77; measured value: c, 63.20; n, 18.43; h, 1.74; HRMS (ESI) M/z (M +): theoretical value: 456.0747, respectively; measured value: 456.0750.
example 11
This example provides a cyclic compound having the structure shown in formula C10 below:
Figure BDA0002152776090000251
the synthetic route for the compound of formula C10 is shown below:
Figure BDA0002152776090000252
the preparation method of the compound shown as the formula C10 specifically comprises the following steps:
synthesis of compound C10: to a 250 ml single-neck flask were added intermediate 3' (28.41 g, 1 eq), compound N7(10.00 g, 1 eq), potassium carbonate (14.49 g, 1.05 eq), and 100 ml of tetrahydrofuran, and stirred at room temperature for 6 hours. The solvent was spun dry to give the crude product, which was purified by chromatography (etoac/hexanes volume ratio 1/8) to give compound C10(23.06 g, 63%).
Elemental analysis: c17H2N8Theoretical value of OS: c, 55.74; n, 30.59; h, 0.55; s, 8.75; measured value: c, 55.75; n, 30.62; h, 0.54; s, 8.73; HRMS (ESI) M/z (M +): theoretical value: 366.0072, respectively; measured value: 366.0070.
example 12
This example provides a cyclic compound having the structure shown in formula C11 below:
Figure BDA0002152776090000253
the synthetic route for the compound of formula C11 is shown below:
Figure BDA0002152776090000261
the preparation method of the compound shown as the formula C11 specifically comprises the following steps:
synthesis of compound C11: m5(35.20 g, 1 eq), compound N8 (20.70 g, 1 eq), potassium carbonate (28.98 g, 2.10 eq), and tetrahydrofuran 150 ml were added to a 250 ml single-neck flask and stirred at room temperature for 4 hours. The solvent was spun dry to give the crude product, which was purified by chromatography (ethyl acetate/hexane ratio by volume 1/8) to give compound C11(45.26 g, 62%).
Elemental analysis: c24N6Theoretical value: c, 49.34; n, 3.84; measured value: c, 49.31; n, 3.84; HRMS (ESI) M/z (M +): theoretical value: 729.9774, respectively; measured value: 729.9716.
example 13
This example provides a cyclic compound having the structure shown in formula C12 below:
Figure BDA0002152776090000262
the synthetic route for the compound of formula C12 is shown below:
Figure BDA0002152776090000271
the preparation method of the compound shown as the formula C12 specifically comprises the following steps:
1) synthesis of intermediates 1 to 12: compound N6(17.60 g, 1 eq) was dissolved in 50 ml of absolute ethanol in a 250 ml single-neck flask under nitrogen, potassium carbonate (14.49 g, 1.05 eq) and compound M9(31.20 g, 1 eq) were added and stirred at room temperature for 4 hours. Quenching with 50 ml of water, spin-drying the solvent, extraction with ethyl acetate (100 ml. times.3), spin-drying the solvent to give the crude product, which was purified by chromatography (ethyl acetate/hexane ratio by volume 1/20) to give intermediates 1-12(30.29 g, 67% yield).
2) Synthesis of intermediates 2 to 12: the intermediates 1 to 12(45.21 g, 1 eq) and 50 ml of nitric acid were added under nitrogen protection in a 250 ml three-necked flask and reacted at room temperature for 2 hours. After the reaction was completed, 50 ml of water was added to quench, ethyl acetate (100 ml. times.3) was extracted, the organic phase was dried over anhydrous sodium sulfate, and the organic solvent was spin-dried to obtain a crude product. The crude product was purified by chromatography (ethyl acetate/hexane ratio by volume 1/15) to afford intermediate 2-12(32.86 g, 74% yield).
3) Synthesis of compound C12: in a 250 ml three-neck flask, adding the intermediate 2-12(44.40 g, 1 eq), the compound N10(30.40 g, 2 eq) and acetic acid (120 ml) under the protection of nitrogen, reacting at 40 ℃ for 5 hours, cooling to room temperature, adding 150 ml of water to quench, extracting with ethyl acetate (150 ml. times.3), drying the organic phase with anhydrous sodium sulfate, and spin-drying the organic solvent to obtain the crude product. The crude product was purified by chromatography (ethyl acetate/hexane, 1/10 vol%) to give compound C12(55.86 g, 57% yield).
Elemental analysis: c32N10F24Theoretical value: c, 39.20; n, 14.29; measured value: c, 39.23; n, 14.28; HRMS (ESI) M/z (M +): theoretical value: 979.9924, respectively; measured value: 979.9989.
example 14
This example provides a cyclic compound having the structure shown in formula C13 below:
Figure BDA0002152776090000281
the synthetic route for the compound of formula C13 is shown below:
Figure BDA0002152776090000282
the preparation method of the compound shown as the formula C13 specifically comprises the following steps:
1) synthesis of intermediates 1 to 13: in a 250 ml three-neck flask, compound M9(17.60 g, 1 eq), compound N14(32.10 g, 1 eq), and acetic acid (180 ml) were added under nitrogen protection, reacted at 40 ℃ for 5 hours, cooled to room temperature, quenched by addition of 150 ml of water, extracted with ethyl acetate (150 ml × 3), the organic phase was dried over anhydrous sodium sulfate, and the organic solvent was spin-dried to give the crude product. The crude product was purified by chromatography (ethyl acetate/hexane ratio by volume 1/10) to afford intermediates 1-13(50.83 g, 65% yield).
2) Synthesis of intermediates 2 to 13: the intermediates 1 to 13(78.20 g, 1 eq) and 100 ml of nitric acid were added to a 250 ml three-necked flask under nitrogen protection and reacted at room temperature for 2 hours. After the reaction was completed, 150 ml of water was added to quench, ethyl acetate (200 ml. times.3) was extracted, the organic phase was dried over anhydrous sodium sulfate, and the organic solvent was spin-dried to obtain a crude product. The crude product was purified by chromatography (ethyl acetate/hexane ratio by volume 1/15) to afford intermediates 2-13(59.60 g, 77% yield).
3) Synthesis of compound C13: intermediate 2-13(77.40 g, 1 eq) was dissolved in 50 ml of absolute ethanol in a 250 ml single-neck flask under nitrogen, potassium carbonate (28.98 g, 2.10 eq), compound N2(21.60 g, 2 eq) were added and stirred at room temperature for 4 hours. Quenching with 50 ml of water, spin-drying the solvent, extraction with ethyl acetate (100 ml. times.3) and spin-drying the solvent gave the crude product, which was purified by chromatography (ethyl acetate/hexane ratio by volume 1/20), compound C13(42.23 g, 46% yield).
Elemental analysis: c40N10F14O2Theoretical value: c, 55.31; n, 15.25; measured value: c, 55.29; n, 15.26; HRMS (ESI) M/z (M +): theoretical value: 917.9982, respectively; measured value: 917.9876.
example 15
This example provides a cyclic compound having the structure shown in formula C14 below:
Figure BDA0002152776090000291
the synthetic route for the compound of formula C14 is shown below:
Figure BDA0002152776090000301
the preparation method of the compound shown as the formula C14 specifically comprises the following steps:
1) synthesis of intermediates 1 to 14: compound M7(19.80 g, 1 eq) was dissolved in 50 ml of absolute ethanol in a 250 ml single-neck flask under nitrogen, potassium carbonate (43.47 g, 3.15 eq), compound N11 (48.00 g, 3 eq) were added and stirred at room temperature for 4 hours. Quenching with 50 ml of water, spin-drying the solvent, extraction with ethyl acetate (100 ml. times.3), spin-drying the solvent to give the crude product, which was purified by chromatography (ethyl acetate/hexane ratio by volume 1/20) to give intermediates 1-14(30.79 g, 54% yield).
2) Synthesis of intermediates 2 to 14: intermediates 1 to 14(57.01 g, 1 eq.) and 50 ml of nitric acid were added under nitrogen in a 250 ml three-necked flask and reacted at room temperature for 2 hours. After the reaction was completed, 50 ml of water was added to quench, ethyl acetate (100 ml. times.3) was extracted, the organic phase was dried over anhydrous sodium sulfate, and the organic solvent was spin-dried to obtain a crude product. The crude product was purified by chromatography (ethyl acetate/hexane ratio by volume 1/15) to afford intermediates 2-14(42.04 g, 74% yield).
3) Synthesis of compound C14: in a 250 ml three-neck flask, adding the intermediate 2-14(56.81 g, 1 eq), compound N12(14.20 g, 1 eq) and acetic acid (120 ml) under the protection of nitrogen, reacting at 40 ℃ for 5 hours, cooling to room temperature, adding 150 ml of water to quench, extracting with ethyl acetate (150 ml. times.3), drying the organic phase with anhydrous sodium sulfate, and spin-drying the organic solvent to obtain a crude product. The crude product was purified by chromatography (etoac/hexanes volume ratio 1/10) to provide compound C14(35.30 g, 51% yield).
Elemental analysis: c32N22Theoretical value: c, 55.50; n, 45.50; measured value: c, 55.48; n, 45.52; HRMS (ESI) M/z (M +): theoretical value: 692.0676, respectively; measured value: 692.0697.
example 16
The embodiment provides an organic electroluminescent device, which includes an anode (ITO)/a Hole Transport Layer (HTL)/an organic light emitting layer (EML)/an Electron Transport Layer (ETL)/an Electron Injection Layer (EIL)/a cathode (Al) that are sequentially stacked from bottom to top.
Wherein the material of the Hole Transport Layer (HTL) is formed by co-doping a compound shown by NPB and a compound shown by C1, and the doping mass ratio of the NPB to the C1 is 100: 5;
Figure BDA0002152776090000311
the organic light emitting layer (EML) material is 1, 4-bis (2, 2-diphenylvinyl) benzene;
Figure BDA0002152776090000312
the Electron Transport Layer (ETL) material is selected from a compound TPBI with the structure as follows:
Figure BDA0002152776090000313
LiF is selected as the material of the Electron Injection Layer (EIL);
the preparation of the organic electroluminescent device comprises the following steps:
1) substrate cleaning:
sequentially carrying out ultrasonic treatment on a transparent glass substrate coated with an ITO transparent conductive film in an aqueous cleaning agent (the components and concentration of the aqueous cleaning agent are that a glycol solvent is less than or equal to 10 wt% and triethanolamine is less than or equal to 1 wt%), washing in deionized water, ultrasonically removing oil in a mixed solvent of acetone and ethanol (the volume ratio is 1: 1), baking in a clean environment to completely remove water, and finally cleaning by using ultraviolet light and ozone;
2) preparation of organic layer and cathode:
placing the ITO transparent glass substrate treated in the step 1) in evaporation equipment, and sequentially evaporating a 40nm HTL layer, a 40nm EML layer, a 40nm ETL layer, a 1nm EIL layer and 150nm aluminum as a cathode, wherein the HTL layer is formed by co-doping NPB and C1, and the doping mass ratio of the NPB to the C1 is 100: 5.
Example 17
This example provides an organic electroluminescent device, which differs from that provided in example 16 only in that: the Hole Transport Layer (HTL) material is formed by co-doping a compound shown as NPB and a compound shown as C2, wherein the NPB and C2 are doped in a mass ratio of 100: 5.
Example 18
This example provides an organic electroluminescent device, which differs from that provided in example 16 only in that: the Hole Transport Layer (HTL) material is formed by co-doping a compound shown as NPB and a compound shown as C3, wherein the NPB and C3 are doped in a mass ratio of 100: 5.
Example 19
This example provides an organic electroluminescent device, which differs from that provided in example 16 only in that: the Hole Transport Layer (HTL) material is formed by co-doping a compound shown as NPB and a compound shown as C4, wherein the NPB and C4 are doped in a mass ratio of 100: 5.
Example 20
This example provides an organic electroluminescent device, which differs from that provided in example 16 only in that: the Hole Transport Layer (HTL) material is formed by co-doping a compound shown as NPB and a compound shown as C5, wherein the NPB and C5 are doped in a mass ratio of 100: 5.
Example 21
This example provides an organic electroluminescent device, which differs from that provided in example 16 only in that: the Hole Transport Layer (HTL) material is formed by co-doping a compound shown as NPB and a compound shown as C6, wherein the NPB and C6 are doped in a mass ratio of 100: 5.
Example 22
This example provides an organic electroluminescent device, which differs from that provided in example 16 only in that: the Hole Transport Layer (HTL) material is formed by co-doping a compound shown as NPB and a compound shown as C7, wherein the NPB and C7 are doped in a mass ratio of 100: 5.
Example 23
This example provides an organic electroluminescent device, which differs from that provided in example 16 only in that: the Hole Transport Layer (HTL) material is formed by co-doping a compound shown as NPB and a compound shown as C8, wherein the NPB and C8 are doped in a mass ratio of 100: 5.
Example 24
This example provides an organic electroluminescent device, which differs from that provided in example 16 only in that: the Hole Transport Layer (HTL) material is formed by co-doping a compound shown as NPB and a compound shown as C9, wherein the NPB and C9 are doped in a mass ratio of 100: 5.
Example 25
This example provides an organic electroluminescent device, which differs from that provided in example 16 only in that: the Hole Transport Layer (HTL) material is formed by co-doping a compound shown as NPB and a compound shown as C10, wherein the NPB and C10 are doped in a mass ratio of 100: 5.
Example 26
This example provides an organic electroluminescent device, which differs from that provided in example 16 only in that: the Hole Transport Layer (HTL) material is formed by co-doping a compound shown as NPB and a compound shown as C11, wherein the NPB and C11 are doped in a mass ratio of 100: 5.
Example 27
This example provides an organic electroluminescent device, which differs from that provided in example 16 only in that: the Hole Transport Layer (HTL) material is formed by co-doping a compound shown as NPB and a compound shown as C12, wherein the NPB and C12 are doped in a mass ratio of 100: 5.
Example 28
This example provides an organic electroluminescent device, which differs from that provided in example 16 only in that: the Hole Transport Layer (HTL) material is formed by co-doping a compound shown as NPB and a compound shown as C13, wherein the NPB and C13 are doped in a mass ratio of 100: 5.
Example 29
This example provides an organic electroluminescent device, which differs from that provided in example 16 only in that: the Hole Transport Layer (HTL) material is formed by co-doping a compound shown as NPB and a compound shown as C14, wherein the NPB and C14 are doped in a mass ratio of 100: 5.
Comparative example 1
This comparative example provides an organic electroluminescent device, which differs from that provided in example 16 only in that: the Hole Transport Layer (HTL) material is formed by co-doping a compound shown by NPB and a compound shown by NDP-9, and the doping mass ratio of the NPB to the NDP-9 is 100: 5.
Figure BDA0002152776090000341
Test example 1
1. Measurement of thermal decomposition temperature
Thermal decomposition temperature test is carried out on the material by using a thermogravimetric analyzer (TGA), the test range is from room temperature to 600 ℃, the heating rate is 10 ℃/min, and the temperature of 5% weight loss under nitrogen atmosphere is defined as the decomposition temperature.
2. LUMO energy level test
The LUMO energy level of the material is tested by Cyclic Voltammetry (CV) by using an electrochemical workstation, and platinum wires (Pt) are used as a counter electrode, and silver/silver chloride (Ag/AgCl) is used as a reference electrode. Under the nitrogen atmosphere, the test is carried out in methylene chloride electrolyte containing 0.1M tetrabutylammonium hexafluorophosphate at the scanning rate of 100mV/s, the potential calibration is carried out by ferrocene, and the absolute energy level of the potential of the ferrocene in the vacuum state is set as-4.8 eV:
Figure BDA0002152776090000342
the test results are shown in Table 1.
TABLE 1
Figure BDA0002152776090000343
Figure BDA0002152776090000351
The results in table 1 show that the cyclic compound provided by the invention has a high thermal decomposition temperature, and can ensure that the material maintains excellent thermal stability in a device, so that the cyclic compound is not easy to decompose and deteriorate in the device preparation process; the low LUMO energy level of the cyclic compound provided by the invention can promote the hole transport layer to generate holes more effectively, improve the carrier combination rate, reduce the working voltage of the device and improve the luminous efficiency of the device.
Test example 2
The current, voltage, brightness, luminescence spectrum and other characteristics of the device are synchronously tested by adopting a PR 650 spectrum scanning luminance meter and a Keithley K2400 digital source meter system, and the service life of the device is tested at 20mA/cm2The device life T95 was tested at current density (life testing instrument commercially available from Fushida scientific instruments, Inc.).
The organic electroluminescent devices provided in examples 16 to 29 and comparative example 1 were tested, and the results are shown in table 2:
TABLE 2
Figure BDA0002152776090000352
Figure BDA0002152776090000361
As shown in table 2, when the cyclic compound provided in the present invention is applied to an OLED device as a doping material in a hole transport layer, the operating voltage of the device can be effectively reduced, the light emitting efficiency of the device can be improved, and the service life of the device can be prolonged.
It is worth noting that in the research process, the inventor finds that when the cyclic compound provided by the invention does not contain hydrogen atoms in the structure and is in a fully conjugated structure (single bonds and double bonds are alternately arranged), and the cyclic compound is used as a doping material in a hole transport layer and applied to an OLED device, the current efficiency of the device is higher, and the service life is longer. When the structure of the cyclic compound provided by the invention contains active hydrogen (hydrogen atoms), hydrogen bonds are easily generated among molecules, which is not beneficial to improving the current efficiency of a device and prolonging the service life of the device; when the cyclic compound provided by the invention is not in a full-conjugated structure and the structure of the molecule cannot realize the alternate arrangement of single bonds and double bonds, the conjugation of the molecular structure is reduced, the stability of a device film is not facilitated, and the stability of the device is relatively poor, so that the improvement of the current efficiency and the prolonging of the service life of the device are influenced. According to the invention, the compound shown as C9 contains active hydrogen, and the compound shown as C10 cannot completely realize the alternating arrangement of single bonds and double bonds due to the existence of S atoms in the compound shown as C10. As can be seen from the data in tables 1 and 2, the LUMO level of the compound represented by C9 and the compound represented by C10 was higher than that of the other examples, and when they were applied to an OLED device as a doping material in a hole transport layer, the driving voltage of the device was relatively high, and the current efficiency and the lifetime of the device were relatively low.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.

Claims (9)

1. A cyclic compound having the structure shown below:
Figure FDA0002808104700000011
wherein A is1、A2Identical or different and each independently selected from CF3CN, halogen;
Ar1is independently selected from
Figure FDA0002808104700000012
R37、R38、R39And R40Selected from cyano groups.
2. A cyclic compound having the structure shown below:
Figure FDA0002808104700000013
ar1 is independently selected from
Figure FDA0002808104700000014
R37、R38Each independently selected from cyano, halogen, trifluoromethyl, C (CN)2；
A1 and A2 are independently selected from cyano,
Figure FDA0002808104700000015
R10-R13、R20-R24Each independently selected from cyano, halogen, trifluoromethyl,
or A1、A2Are linked to each other to form a ring B selected from
Figure FDA0002808104700000021
R3-R4、R7-R8Each independently selected from cyano, halogen, trifluoromethyl.
3. The cyclic compound of claim 1, having the structure shown below:
Figure FDA0002808104700000022
4. the cyclic compound of claim 2, having the structure shown below:
Figure FDA0002808104700000023
5. the cyclic compound of claim 1 or 2, wherein the halogen is fluorine.
6. Use of a cyclic compound according to any one of claims 1 to 5 as an organic electroluminescent material.
7. An electronic device comprising at least one cyclic compound of any one of claims 1-5, the electronic device comprising an organic electroluminescent device, an organic thin film transistor, an organic light emitting transistor, an organic integrated circuit, an organic solar cell, an organic field quenching device, a light emitting electrochemical cell, an organic laser diode, or an organic photoreceptor.
8. A display device comprising the electronic device according to claim 7.
9. A lighting device comprising the electronic device of claim 7.
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KR20170003471A (en) * 2015-06-30 2017-01-09 (주)피엔에이치테크 An electroluminescent compound and an electroluminescent device comprising the same
KR102192692B1 (en) * 2015-06-30 2020-12-17 (주)피엔에이치테크 An electroluminescent compound and an electroluminescent device comprising the same
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TW201900623A (en) * 2017-05-12 2019-01-01 傑秀有限公司 Quinoxaline-fused dibenzosuberane based helicenes and organic light-emitting diodes using the same
US11839147B2 (en) * 2017-09-04 2023-12-05 Beijing Summer Sprout Technology Co., Ltd. Hole injection layer and charge generation layer containing a truxene based compound
CN108586289B (en) * 2018-05-04 2020-12-29 西北大学 Malononitrile substituted aryl anthracene phenanthrene organic electroluminescent material and preparation method and application thereof
CN108947925B (en) * 2018-08-22 2020-12-01 石家庄诚志永华显示材料有限公司 1,3, 4-oxadiazole derivative, material and organic electroluminescent device
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