CN113845430B - Organic compound and application thereof - Google Patents

Organic compound and application thereof Download PDF

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CN113845430B
CN113845430B CN202111129171.0A CN202111129171A CN113845430B CN 113845430 B CN113845430 B CN 113845430B CN 202111129171 A CN202111129171 A CN 202111129171A CN 113845430 B CN113845430 B CN 113845430B
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organic compound
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CN113845430A (en
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陈婷
呼建军
向陆军
张小玲
杭德余
程丹丹
段陆萌
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Xiamen Hangchuang Technology Co.,Ltd.
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Beijing Yanhua Jilian Optoelectronic Technology Co ltd
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Abstract

The invention relates to the technical field of materials for organic electroluminescent display, and particularly discloses an organic compound and application of the organic compound in an organic electroluminescent device. The invention provides an organic compound, which has a structure shown in a general formula (I). Meanwhile, an organic electroluminescent device is provided, wherein the luminescent layer comprises an organic compound shown as a formula (I) as a fluorescent luminescent material, and the device provided by the invention has the advantages of high purity, high brightness and high efficiency.

Description

Organic compound and application thereof
Technical Field
The invention relates to the technical field of materials for organic electroluminescent display, and particularly discloses an organic compound and application of the organic compound in an organic electroluminescent device.
Background
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. Currently the main display technologies are plasma display devices, field emission display devices and organic electroluminescent display devices (OLEDs). Compared with a liquid crystal display device, the OLEDs do not need a backlight source, have wider visual angles and low power consumption, and have response speed which is 1000 times that of the liquid crystal display device, so that the OLEDs have wider application prospect.
Organic electroluminescence was studied starting in the 60 s of the 19 th century, pope achieved electroluminescence for the first time on anthracene single crystals, but when the driving voltage was as high as 100V, the quantum efficiency was very low. In 1987, tang and VanSlyke adopted a double-layer film structure with 8-hydroxyquinoline aluminum complex (Alq 3) as the light-emitting layer and electron transport layer, TAPC as the hole transport layer, and ITO electrode and Mg: ag electrode respectively as anode and cathode, to obtain high brightness [ (]>1000cd/m 2 ) The driving voltage of the green light organic electroluminescent film device with high efficiency (1.5 lm/W) is reduced to below 10V. In 1990, the polymeric thin film electroluminescent device of Burroughes et al, prepared with poly-p-styrene (PPV), gave a blue-green light output with a quantum efficiency of 0.05% and a driving voltage of less than 14V. In 1991, braun et al produced green and orange light outputs with 1% quantum efficiency using PPV derivatives, with a driving voltage of about 3V. These developments immediately bring great importance to the scientists of all countries, and organic electroluminescence research is widely carried out worldwide and gradually starts to market.
Generally, OLEDs are constructed to include an anode formed on a substrate, and a hole transport layer, a light emitting layer, an electron transport layer, and a cathode sequentially formed on the anode. The hole transport layer, the light emitting layer, and the electron transport layer are organic thin films composed of organic compounds. The driving principle of the organic electroluminescent display device having the above structure is as follows: holes are injected from the anode into the light emitting layer through the hole transporting layer whenever a voltage is applied between the anode and the cathode; meanwhile, electrons are injected from the cathode into the light emitting layer through the electron transport layer; in the light-emitting layer region, carriers are rearranged to form excitons, and the excitons in an excited state are converted to a ground state, causing the light-emitting layer molecules to emit light.
Conventional OLEDs have problems such as high driving voltage, low light emission luminance, low light emission efficiency, and the like, as compared with inorganic light emitting diodes, but in recent years, performance of OLEDs has been improved by improvement of organic electroluminescent materials. However, the blue light-emitting machine electroluminescent display device has the defects of low color saturation, low light-emitting brightness, low light-emitting efficiency, short service life and the like. A light emitting material having dibenzofuran and dibenzothiophene is disclosed in japanese patent CN102232068B, but there are still problems of high driving voltage, low light emitting efficiency, and the like. Therefore, the compound is structurally improved to develop a new blue luminescent material with better performance and promote commercial application, which has important significance.
Disclosure of Invention
The invention aims to provide an organic compound, particularly a fluorescent luminescent material, which is preferably applicable to an organic electroluminescent device.
Specifically, in a first aspect, the present invention provides an organic compound having a structure represented by the general formula (i):
in formula (I): r is R 1 ～R 8 Each independently selected from one of hydrogen, halogen, substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 alkoxy, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, R 1 ～R 8 Two adjacent to each other are connected in a ring or not connected in a ring;
r is as described above 1 ～R 8 The substitution in the middle or unsubstituted is selected from deuterium, halogen, C1-C10 alkyl, C1-C10 alkoxy, cyano, amino, C6-C30 arylamino, C3-C30 heteroarylamino,Substituted by one or a combination of at least two of C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C30 aryl and C3-C30 heteroaryl;
as a preferred embodiment, the R 1 ～R 8 The substituent in the middle or unsubstituted is substituted by one or a combination of at least two selected from deuterium, halogen, C1-C10 straight-chain alkyl, C1-C10 cycloalkyl, C1-C6 alkoxy, C6-C20 arylamino, C3-C20 heteroarylamino, C6-C20 aryloxy, C3-C20 heteroaryloxy, C6-C20 aryl and C3-C20 heteroaryl;
in formula (I): a is that 1 And A 2 Is of the structure shown in formula (1), A 1 And A 2 Identical to or different from each other:
in the formula (1), ar 1 、Ar 2 Each independently represents one of a substituted or unsubstituted C6-C60 monocyclic aromatic hydrocarbon, a substituted or unsubstituted C6-C60 polycyclic aromatic hydrocarbon, a substituted or unsubstituted C6-C60 monocyclic heteroaromatic hydrocarbon, a substituted or unsubstituted C6-C60 polycyclic heteroaromatic hydrocarbon, a substituted or unsubstituted C6-C60 polyphenylarene, and a substituted or unsubstituted C3-C20 cycloalkyl group, the Ar 1 、Ar 2 Identical or different from each other, and Ar 1 With Ar 2 Is connected or disconnected;
ar as described above 1 、Ar 2 The substituent(s) in the substituent(s) or the unsubstituted substituent(s) means a substituent(s) substituted by one or a combination of at least two selected from deuterium, halogen, C1-C10 straight-chain alkyl, C1-C10 cycloalkyl, C1-C10 alkoxy, cyano, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C30 aryl and C3-C30 heteroaryl, wherein the substituent(s) are independently connected with or not connected with an attached aromatic ring or heteroaromatic ring.
As a further preferred embodiment, in formula (I), the R 2 And R is 6 Is not hydrogen;
preferably, said R 2 And R is 6 Each independently selected from one of substituted or unsubstituted C1-C20 chain alkyl, substituted or unsubstituted C3-C20 cycloalkyl, substituted or unsubstituted C3-C20 alkoxy, wherein the substitution in the substitution is substituted by one or a combination of at least two selected from deuterium, halogen, C1-C10 alkyl, C1-C10 alkoxy, cyano, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C30 aryl, C3-C30 heteroaryl.
As a further preferred embodiment, the organic compound of the present invention is preferably of the structure represented by the general formula (II):
in formula (II): r is R 2 、R 6 、A 1 And A 2 All have the same meaning as in formula (I);
further preferably, said R 2 And R is 6 Each independently selected from one of a substituted or unsubstituted C1-C20 chain alkyl, a substituted or unsubstituted C3-C20 cycloalkyl, a substituted or unsubstituted C6-C60 aryl, a substituted or unsubstituted C3-C60 heteroaryl, wherein the substitution in the substitution refers to substitution by one or a combination of at least two selected from deuterium, halogen, C1-C10 alkyl, C1-C10 alkoxy, cyano, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C30 aryl, C3-C30 heteroaryl;
still further, the R 2 And R is 6 Each independently selected from one of substituted or unsubstituted C3-C20 cycloalkyl, and heteroaryl in which the heteroatom of substituted or unsubstituted C3-C60 is oxygen or sulfur, wherein the substituent is selected from one of deuterium, C1-C10 alkyl, and C3-C30 heteroaryl;
still further, each of R2 and R6 is independently selected from the group consisting of:
as a further preferred embodiment of the present invention, the Ar 1 、Ar 2 Each independently selected from the group consisting of substituted or unsubstituted:
phenyl, biphenyl, indenyl, naphthyl, acenaphthylenyl, fluorenyl, spirobifluorenyl, phenanthryl, anthracenyl, fluoranthenyl, pyrenyl, triphenylenyl, benzo (a) anthracenyl, benzo (b) fluoranthenyl, benzo (k) fluoranthenyl, benzo (a) pyrenyl, xanthenyl, acridinyl, carbazolyl, dibenzofuranyl or dibenzothienyl, ar 1 、Ar 2 The substituent(s) in the substituent(s) or the unsubstituted substituent(s) means a substituent(s) substituted by one or a combination of at least two selected from deuterium, halogen, C1-C10 straight-chain alkyl, C1-C10 cycloalkyl, C1-C10 alkoxy, cyano, amino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C3-C30 heteroaryloxy, C6-C30 aryl and C3-C30 heteroaryl, wherein the substituent(s) are independently connected with or not connected with an attached aromatic ring or heteroaromatic ring.
As a still further preferred embodiment, the A 1 And A 2 Each independently selected from one of the following groups, wherein the dotted line represents the site of attachment to the parent nucleus:
as a more preferred embodiment, the A 1 And A 2 Each independently selected from one of the following groups, wherein the dotted line represents the site of attachment to the parent nucleus:
in the present specification, the expression of Ca to Cb means that the group has a carbon number of a to b, and unless otherwise specified, the carbon number generally does not include the carbon number of a substituent. In the present invention, unless otherwise specified, the expression of chemical elements generally includes the concept of isotopes having the same chemical properties, for example, the expression of "hydrogen" includes the concept of "deuterium", "tritium" having the same chemical properties, and carbon (C) includes 12 C、 13 C, etc., and are not described in detail.
Heteroaryl in the present specification refers to an aromatic cyclic group comprising heteroatoms, typically selected from N, O, S, P, si and Se, preferably from N, O, S.
In the present specification, the C6-C60 aryl group and the C3-C60 heteroaryl group are aromatic groups satisfying pi conjugated system, and include both monocyclic and condensed ring cases unless otherwise specified. By monocyclic is meant that the molecule contains at least one phenyl group, and when the molecule contains at least two phenyl groups, the phenyl groups are independent of each other and are linked by a single bond, such as phenyl, biphenyl, terphenyl, and the like; condensed rings refer to molecules containing at least two benzene rings, but the benzene rings are not independent, but the common ring edges are condensed with each other, such as naphthyl, anthryl, phenanthryl and the like; monocyclic heteroaryl means that the molecule contains at least one heteroaryl group, and when the molecule contains one heteroaryl group and other groups (such as aryl, heteroaryl, alkyl, etc.), the heteroaryl group and the other groups are independent of each other and are connected by a single bond, such as pyridine, furan, thiophene, etc.; condensed ring heteroaryl means fused from at least one phenyl group and at least one heteroaryl group, or fused from at least two heteroaryl groups, such as, for example, quinoline, isoquinoline, benzofuran, dibenzofuran, benzothiophene, dibenzothiophene, and the like
In the present specification, the substituted or unsubstituted C6 to C60 aryl group is preferably a C6 to C30 aryl group, and exemplary preferred is an aryl group of the group consisting of phenyl, naphthyl, anthryl, benzanthrenyl, phenanthryl, benzophenanthryl, pyrenyl, hole, perylene, fluoranthenyl, naphthacene, pentacenyl, benzopyrene, biphenyl, terphenyl, tetraphenyl, fluorenyl, spirobifluorenyl, dihydrophenanthryl, dihydropyrenyl, tetrahydropyrenyl, cis or trans indenofluorenyl, trimeric indenyl, heterotrimeric indenyl, spirotrimeric indenyl, spiroheterotrimeric indenyl. The C6-C60 aryl group of the present invention may be a group in which the above groups are bonded by single bonds or/and condensed.
In the present specification, the substituted or unsubstituted C3-C60 heteroaryl group is preferably a C3-C30 heteroaryl group, and may be a nitrogen-containing heteroaryl group, an oxygen-containing heteroaryl group, a sulfur-containing heteroaryl group, or the like. As preferable examples of the heterocyclic ring in the present invention, for example, furyl, thienyl, pyrrolyl, benzofuryl, benzothienyl, isobenzofuryl, indolyl, dibenzofuryl, dibenzothienyl, carbazolyl and derivatives thereof are mentioned, wherein the carbazolyl derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazole benzocarbazole, dibenzocarbazole or indolocarbazole. The C3-C60 heteroaryl groups of the present invention may also be those wherein the above groups are joined singly or in combination by fusion.
In the present specification, alkyl groups are not particularly specified, and include the concept of straight-chain alkyl groups and branched-chain alkyl groups as well as cycloalkyl groups. Examples are: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, adamantyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, pentafluoroethyl, 2-trifluoroethyl and the like.
In the present specification, cycloalkyl includes monocycloalkyl and multicycloalkyl, and examples thereof include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and the like.
In the present specification, examples of the C1 to C20 alkoxy group include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentyloxy, isopentyloxy, hexyloxy, heptyloxy, octyloxy, nonyloxy, decyloxy, undecyloxy, dodecyloxy and the like are preferred, methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, sec-butoxy, isobutoxy, isopentyloxy are more preferred.
In the present specification, examples of the aryloxy group of C6 to C60 include those in which each group of the substituted or unsubstituted C6 to C60 aryl group is bonded to oxygen, and specific examples thereof are described with reference to the above examples and are not described here.
In the present specification, examples of halogen include: fluorine, chlorine, bromine, iodine, and the like.
In the present specification, C6-C60 arylamino and C3-C60 heteroarylamino refer to amino-NH 2 One or two H's are substituted by the above-exemplified C6-C60 aryl or C3-C60 heteroaryl groups.
Further, the organic compound of the present invention may preferably be a compound of the specific structure shown below, which is merely representative and does not limit the scope of the present invention:
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the luminescent material with dibenzofuran and dibenzothiophene reported in patent document CN102232068B, both the parent nucleus and the substituent group do not contain deuterium atoms.
The molecular structure of the compound of the invention designs A1 and A2 groups with specific sites, and simultaneously, R of the sites with specific substituents in the parent nucleus is further optimized 2 And R is 6 A group, preferably R 2 And R is 6 Is a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted thienyl group, and the most preferred scheme is R 2 And R is 6 Deuterium atom substitution is designed on cycloalkyl, furyl and thienyl, which are selected from deuterium atom substituted cycloalkyl, deuterium atom substituted furyl or deuterium atom substituted thienyl, because after deuterium atom is introduced, the bond length of a carbon-deuterium bond is shorter than that of a carbon-hydrogen bond, the bond energy becomes larger, the energy of the compound is reduced, and the more stable the compound is, so that the efficiency and the service life of the light-emitting device are both remarkably enhanced.
The organic compound of the invention is used as a luminescent material of a luminescent layer of an organic electroluminescent device, and has the following beneficial effects compared with the prior art: the thermal stability of the compound can be increased, the purity can be improved, and the efficiency and the service life of the device can be improved.
As a second aspect of the present invention, there is provided the use of an organic compound having a structure represented by the above general formula (I). In particular, the organic compound is applied to an organic electronic device, and the organic electronic device comprises an organic electroluminescent device, an optical sensor, a solar cell, a lighting element, an organic thin film transistor, an organic field effect transistor, an organic thin film solar cell, an information tag, an electronic artificial skin sheet, a sheet scanner or electronic paper.
Preferably, the organic compound of the present invention is applied to an organic electroluminescent device, preferably to a light emitting layer of the organic electroluminescent device, used as a dye material doped in a host material, and the electroluminescent device prepared using the fluorescent material of the present invention exhibits superior properties of high purity, high brightness, and high efficiency.
In a third aspect, the present invention provides an organic electroluminescent device comprising a light-emitting layer comprising the above-mentioned organic compound as a fluorescent light-emitting material, which exhibits superior properties of high purity, high luminance, and high efficiency.
Further, the organic electroluminescent device provided by the invention comprises a substrate, and an anode layer, a plurality of light-emitting unit layers and a cathode layer which are sequentially formed on the substrate; the light-emitting unit layer comprises a light-emitting layer and one or more of a hole injection layer, a hole transmission layer, an electron blocking layer and the like, wherein the hole injection layer is formed on the anode layer, the hole transmission layer is formed on the hole injection layer, the cathode layer is formed on the electron transmission layer, and a plurality of light-emitting layers are arranged between the hole transmission layer and the electron transmission layer. Preferably, the luminescent dye in the luminescent layer is the luminescent material of the invention.
Specifically, the light-emitting layer of the device comprises a host material and a dye material, wherein the dye material comprises the organic compound provided by the invention. The doping concentration of the organic compound of the present invention in the host material of the light-emitting layer is 3 to 12%, preferably 5 to 10%, more preferably 7 to 9%. When the doping concentration of the fluorescent light-emitting material in the main material is about 8%, the performance of the device is optimal, and the doping concentration is the mass percentage concentration.
In a fourth aspect, the present invention provides a display apparatus comprising the organic electroluminescent device.
In a fifth aspect, the present invention provides a lighting apparatus comprising the organic electroluminescent device.
Detailed Description
The technical scheme of the invention is described in detail through specific examples. The following examples are illustrative of the invention and are not intended to limit the scope of the invention. According to the preparation method provided by the invention, the preparation method can be realized by adopting known common means by a person skilled in the art, such as further selecting a proper catalyst, a solvent, a halogenated compound, determining a proper reaction temperature, a proper time, a proper material ratio and the like, and the invention is not particularly limited. Unless otherwise indicated, starting materials for solvents, catalysts, bases, etc. used in the preparation process may be synthesized by published commercial routes or by methods known in the art.
The specific synthetic method of a representative compound among the organic compounds of the present invention will be briefly described below.
Synthesis of intermediate M1
The synthetic route is as follows:
the specific operation steps are as follows:
(1) 1, 6-dibromopyrene (36 g,0.1 mol) is added into a clean and dry 2L three-neck flask, 400mL of toluene is used for stirring and dissolving, further (cyclopropyl-2, 3-d 4) boric acid (18 g,0.2 mol), potassium carbonate (55.2 g,0.4 mol), 100mL of absolute ethyl alcohol and 100mL of deionized water are added, finally tetraphenylphosphine palladium (1.5 g,1 mmol) is added, stirring is started, heating is carried out under the protection of nitrogen to reflux (80-90 ℃) for 6 hours, the reaction is finished, the temperature is reduced to room temperature, ethyl acetate is used for extraction, liquid separation is carried out, the aqueous phase is extracted twice with 50mL of ethyl acetate, the organic phase is combined, 300mL of water is washed three times to be neutral, then anhydrous sodium sulfate is used for drying, suction filtration is carried out, the solvent is removed by rotary evaporation, column chromatography is carried out, the eluting agent is heptane and ethyl acetate (volume ratio is 20:1), column liquid is concentrated to obtain yellow solid, and then 15.2g of light yellow solid M1-01 is recrystallized from toluene heptane, and the yield is 52%.
(2) To a clean and dry 1L three-neck flask, adding a compound M1-01 (29.2 g,0.1 mol), stirring and dissolving with 100mLN and N dimethylformamide, cooling to-40 to-30 ℃ under the protection of nitrogen, dropwise adding 200mL of N, N dimethylformamide solution of NBS (35.6 g,0.2 mol), dropwise adding the solution for 1.5 hours, carrying out heat preservation reaction for 1 hour, naturally heating to room temperature, reacting for 1 hour, ending the reaction, adding 500mL of water into the flask, quenching, stirring, precipitating with solid, leaching to obtain an off-white solid, drying, dissolving with heptane, passing through a silica gel column, concentrating the column liquid, and recrystallizing with ethanol heptane to obtain 27.2g of off-white solid M1, wherein the yield is 61.0%.
Product MS (m/e): 446.0; elemental analysis (C) 22 H 8 D 8 Br 2 ): theoretical value C:58.95%, H:5.39%; measured value C:58.97%, H:5.42%.
Synthesis of intermediate M2
Reference to the synthesis of intermediate M1, byReplace->And selecting a proper material ratio, and obtaining an intermediate M2 by using other raw materials and steps which are the same as those of the intermediate M1.
Product MS (m/e): 480.1; elemental analysis (C) 24 H 6 D 14 Br 2 ): theoretical value C:59.77%, H:7.10%; measured value C:59.81%, H:7.14%.
Synthesis of intermediate M3
Reference to the synthesis of intermediate M1, byReplace->And selecting a proper material ratio, and obtaining an intermediate M3 by using other raw materials and steps which are the same as those of the intermediate M1.
Product MS (m/e): 512.1; elemental analysis (C) 26 H 6 D 18 Br 2 ): theoretical value C:60.71%, H:8.22%; measured value C:60.73%, H:8.19%.
Synthesis of intermediate M4
Reference to the synthesis of intermediate M1, byReplace->And selecting a proper material ratio, and obtaining an intermediate M4 by using other raw materials and steps which are the same as those of the intermediate M1. />
Product MS (m/e): 544.2; elemental analysis (C) 28 H 6 D 22 Br 2 ): theoretical value C:61.54%, H:9.22%; measured value C:61.56%, H:9.25%.
Synthesis of intermediate M5
In reference toSynthesis of intermediate M1 byReplace->And selecting a proper material ratio, and obtaining an intermediate M5 by using other raw materials and steps which are the same as those of the intermediate M1.
Product MS (m/e): 576.3; elemental analysis (C) 30 H 6 D 26 Br 2 ): theoretical value C:62.28%, H:10.10%; measured value C:62.24%, H:10.16%.
Synthesis of intermediate M6
Reference to the synthesis of intermediate M1, byReplace->And selecting a proper material ratio, and obtaining an intermediate M6 by using other raw materials and steps which are the same as those of the intermediate M1.
Product MS (m/e): 608.3; elemental analysis (C) 32 H 6 D 30 Br 2 ): theoretical value C:62.94%, H:10.89%; measured value C:62.88%, H:10.96%.
Synthesis of intermediate M7
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Reference to the synthesis of intermediate M1, byReplace->And selecting a proper material ratio, and obtaining an intermediate M7 by using other raw materials and steps which are the same as those of the intermediate M1.
Product MS (m/e): 496.0; elemental analysis (C) 24 H 6 D 6 Br 2 O 2 ): theoretical value C:57.86%, H:3.64%; measured value C:57.89%, H:3.68%.
Synthesis of intermediate M8
Reference to the synthesis of intermediate M1, byReplace->And selecting a proper material ratio, and obtaining an intermediate M8 by using other raw materials and steps which are the same as those of the intermediate M1.
Product MS (m/e): 527.9; elemental analysis (C) 24 H 6 D 6 Br 2 S 2 ): theoretical value C:54.36%, H:3.42%; measured value C:54.41%, H:3.45%.
Synthesis of intermediate M9
Reference to the synthesis of intermediate M1, byReplace->And selecting a proper material ratio, and obtaining an intermediate M9 by using other raw materials and steps which are the same as those of the intermediate M1.
Product MS (m/e): 704.1; elemental analysis (C) 40 H 6 D 14 Br 2 O 2 ): theoretical value C:68.00%, H:4.85%; measured value C:68.04%, H:4.91%.
Synthesis of intermediate M10
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Reference to the synthesis of intermediate M1, byReplace->And selecting a proper material ratio, and obtaining an intermediate M10 by using other raw materials and steps which are the same as those of the intermediate M1.
Product MS (m/e): 736.0; elemental analysis (C) 40 H 6 D 14 Br 2 S 2 ): theoretical value C:65.05%, H:4.64%; measured value C:65.09%, H:4.67%.
EXAMPLE 1 Synthesis of Compound I-1
The synthetic route is as follows:
A2L three-necked flask was stirred magnetically, and after nitrogen substitution, sodium tert-butoxide (28.8 g,0.3 mol), diphenylamine (33.8 g,0.2 mol) and 400ml of toluene were added in this order. After nitrogen substitution again, (0.4 g,2 mmol) tri-tert-butylphosphine and (0.92 g,1 mmol) dibenzyl acetone dipalladium were added sequentially. After the addition, the temperature was raised to 85 ℃. A solution of (44.6 g,0.1 mol) M1 and 100ml toluene was started to be added dropwise, and the mixture was heated to reflux (110-120 ℃ C.) to react for 4 hours, and the reaction was ended. The mixture was neutralized, the organic phase was separated, extracted, dried, column chromatographed and the solvent was dried by spin-drying to give 47.6g of pale yellow solid I-1, yield 76.3%.
Product MS (m/e): 624.3; elemental analysis (C) 46 H 28 D 8 N 2 ): theoretical value C:88.42%, H:7.10%, N:4.48%; measured value C:88.39%, H:7.14%, N:4.52%.
EXAMPLE 2 Synthesis of Compound I-3
The synthetic route is as follows:
n- (4-isopropyl-cyclohexyl) aniline was used instead of diphenylamine, and other raw materials and steps were the same as in example 1 except for selecting a proper material ratio to obtain 51.2g of a pale yellow solid I-3 in 71.1% yield.
Product MS (m/e): 720.5; elemental analysis (C) 52 H 52 D 8 N 2 ): theoretical value C:86.61%, H:9.50%, N:3.88%; measured value C:86.64%, H:9.58%, N:3.89%.
EXAMPLE 3 Synthesis of Compound I-12
The synthetic route is as follows:
n- (4-isopropyl-cyclohexyl) benzene-d 5-amine was used instead of diphenylamine, and the other raw materials and steps were the same as in example 1 except for selecting an appropriate material ratio, to obtain 50.3g of compound I-12 as pale yellow solid, with a yield of 68.9%.
Product MS (m/e): 730.6; elemental analysis (C) 52 H 42 D 18 N 2 ): theoretical value C:85.42%, H:10.75%, N:3.83%; measured value C:85.47%, H:10.85%, N:3.86%.
EXAMPLE 4 Synthesis of Compound I-15
The synthetic route is as follows:
N-Phenanthrophenanthrene-9-amine is used for replacing diphenylamine, a proper material ratio is selected, other raw materials and steps are the same as those of the example 1, and 54.2g of pale yellow solid I-15 is obtained, and the yield is 65.8%.
Product MS (m/e): 824.4; elemental analysis (C) 62 H 36 D 8 N 2 ): theoretical value C:90.25%, H:6.35%, N:3.40%; measured value C:90.33%, H:6.37%, N:3.41%.
EXAMPLE 5 Synthesis of Compound I-29
The synthetic route is as follows:
A2L three-necked flask was stirred magnetically, and after nitrogen substitution, sodium tert-butoxide (28.8 g,0.3 mol), 4-cyclopentyl-N-phenylaniline (47.4 g,0.2 mol) and 400ml of toluene were added in this order. After nitrogen substitution again, (0.4 g,2 mmol) tri-tert-butylphosphine and (0.92 g,1 mmol) dibenzyl acetone dipalladium were added sequentially. After the addition, the temperature was raised to 85 ℃. A solution of (48.0 g,0.1 mol) M2 and 100ml toluene was started to be added dropwise, and the mixture was heated to reflux (110-120 ℃ C.) to react for 4 hours, and the reaction was ended. The mixture was neutralized, the organic phase was separated, extracted, dried, column chromatographed and the solvent was dried by spin-drying to give 61.5g of pale yellow solid I-29 in 77.4% yield.
Product MS (m/e): 794.5; elemental analysis (C) 58 H 42 D 14 N 2 ): theoretical value C:87.61%, H:8.87%, N:3.52%; measured value C:87.62%, H:8.89%, N:3.48%.
EXAMPLE 6 Synthesis of Compound I-32
The synthetic route is as follows:
4- (cyclopropyl-2, 3-d 4) -N- (4-isopropylphenyl) aniline was used instead of 4-cyclopentyl-N-phenylaniline, and the other raw materials and the procedure were the same as in example 5 except for selecting the appropriate ratio to obtain 59.0g of Compound I-32 as a pale yellow solid, yield 71.0%.
Product MS (m/e): 830.6; elemental analysis (C) 60 H 38 D 22 N 2 ): theoretical value C:86.69%, H:9.94%, N:3.37%; measured value C:86.67%, H:10.02%, N:3.41%.
EXAMPLE 7 Synthesis of Compound I-38
The synthetic route is as follows:
7H-benzofuran [2,3-b ] carbazole is used for replacing 4-cyclopentyl-N-phenylaniline, appropriate material ratios are selected, other raw materials and steps are the same as in example 5, and 54.7g of a pale yellow solid I-38 is obtained, and the yield is 65.6%.
Product MS (m/e): 834.4; elemental analysis (C) 60 H 26 D 14 N 2 O 2 ): theoretical value C:86.30%, H:6.52%, N:3.35%; measured value C:86.35%, H:6.61%, N:3.39%.
EXAMPLE 8 Synthesis of Compound I-51
The synthetic route is as follows:
A2L three-necked flask was stirred magnetically, and after nitrogen substitution, sodium tert-butoxide (28.8 g,0.3 mol), N- (p-tolyl) naphthalen-2-amine (46.6 g,0.2 mol) and 400ml of toluene were sequentially added. After nitrogen substitution again, (0.4 g,2 mmol) tri-tert-butylphosphine and (0.92 g,1 mmol) dibenzyl acetone dipalladium were added sequentially. After the addition, the temperature was raised to 85 ℃. A solution of (51.2 g,0.1 mol) M3 and 100ml toluene was started to be added dropwise, and the mixture was heated to reflux (110-120 ℃ C.) to react for 4 hours, and the reaction was ended. The mixture was neutralized, the organic phase was separated, extracted, dried, column chromatographed, and the solvent was dried by spin-drying to give 51.1g of pale yellow solid I-51, yield 62.4%.
Product MS (m/e): 818.5; elemental analysis (C) 60 H 34 D 18 N 2 ): theoretical value C:87.97%, H:8.61%, N:3.42%; measured value C:87.95%, H:8.63%, N:3.44%.
EXAMPLE 9 Synthesis of Compound I-54
The synthetic route is as follows:
the procedure of example 8 was followed except for using 7, 7-dimethyl-5, 7-indano [2,1-b ] carbazole instead of N- (p-tolyl) naphthalen-2-amine to give 61.9g of Compound I-54 as a pale yellow solid in 67.4% yield.
Product MS (m/e): 918.6; elemental analysis (C) 68 H 38 D 18 N 2 ): theoretical value C:88.84%, H:8.11%, N:3.05%; measured value C:88.86%, H:8.14%, N:3.02%.
EXAMPLE 10 Synthesis of Compound I-57
The synthetic route is as follows:
A2L three-necked flask was stirred magnetically, and after nitrogen substitution, sodium tert-butoxide (28.8 g,0.3 mol), bis (4- (methyl-d 3) phenyl) amine (40.6 g,0.2 mol) and toluene (400 ml) were added in this order. After nitrogen substitution again, (0.4 g,2 mmol) tri-tert-butylphosphine and (0.92 g,1 mmol) dibenzyl acetone dipalladium were added sequentially. After the addition, the temperature was raised to 85 ℃. A solution of (54.4 g,0.1 mol) M4 and 100ml toluene was started to be added dropwise, and the mixture was heated to reflux (110-120 ℃ C.) to react for 4 hours, and the reaction was ended. The mixture was neutralized, the organic phase was separated, extracted, dried, column chromatographed and the solvent was dried by spin-drying to give 62.4g of pale yellow solid I-57 in 78.9% yield.
Product MS (m/e): 790.7; elemental analysis (C) 56 H 22 D 34 N 2 ): theoretical value C:85.00%, H:11.46%, N:3.54%; measured value C:84.98%, H:11.51%, N:3.57%.
EXAMPLE 11 Synthesis of Compound I-67
The synthetic route is as follows:
n- ([ 1,1' -biphenyl ] -3-yl) naphthalene-1-amine was used instead of bis (4- (methyl-d 3) phenyl) amine, and the other raw materials and steps were the same as in example 10, except that the appropriate material ratio was selected, to give 64.3g of a pale yellow solid I-67 as a compound, and the yield was 66.0%.
Product MS (m/e): 974.6; elemental analysis (C) 72 H 38 D 22 N 2 ): theoretical value C:88.66%, H:8.47%, N:2.87%; measured value C:88.63%, H:8.52%, N:2.89%.
EXAMPLE 12 Synthesis of Compound I-74
The synthetic route is as follows:
n- (phenyl-d 5) dibenzo [ b, d ] thiophen-2-amine was used instead of bis (4- (methyl-d 3) phenyl) amine, and a suitable material ratio was selected, and the other materials and the procedure were the same as in example 10, to obtain 60.1g of Compound I-74 as a pale yellow solid, yield 63.6%.
Product MS (m/e): 944.6; elemental analysis (C) 64 H 20 D 32 N 2 S 2 ): theoretical value C:81.31%, H:8.95%, N:2.96%; measured value C:81.34%, H:8.97%, N:2.93%.
EXAMPLE 13 Synthesis of Compound I-77
Using M5 instead of M4, the other materials and steps were the same as in example 10, except that the appropriate material ratio was selected, to give 53.4g of Compound I-77 as a pale yellow solid, with a yield of 64.9%.
Product MS (m/e): 822.7; elemental analysis (C) 58 H 22 D 38 N 2 ): theoretical value C:84.61%, H:11.99%, N:3.40%; measured value C:84.65%, H:12.07%, N:3.32%.
EXAMPLE 14 Synthesis of Compound I-84
The procedure of example 10 was repeated except for using 4- (tert-butyl) -N-cyclohexylaniline instead of bis (4- (methyl-d 3) phenyl) amine and M6 instead of M4 to give 55.9g of a pale yellow solid I-84 as a yield of 61.4%.
Product MS (m/e): 910.9; elemental analysis (C) 64 H 54 D 30 N 2 ): theoretical value C:84.33%, H:12.60%, N:3.07%; measured value C:84.29%, H:12.64%, N:3.05%.
EXAMPLE 15 Synthesis of Compound I-85
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Bis (4- (prop-2-yl-2-d) phenyl) amine was used instead of bis (4- (methyl-d 3) phenyl) amine and M7 was used instead of M4, and the appropriate material ratio was selected, and other raw materials and steps were the same as in example 10, to obtain 55.8g of a pale yellow solid I-85, yield 65.9%.
Product MS (m/e): 846.5; elemental analysis (C) 60 H 46 D 10 N 2 O 2 ): theoretical value C:85.07%, H:7.85%, N:3.31%; measured value C:85.11%, H:7.88%, N: 3.43%.
EXAMPLE 16 Synthesis of Compound I-90
N- ([ 1,1 '-biphenyl ] -4-yl-2', 3',4',5',6' -d 5) naphthalene-1-amine was used instead of bis (4- (methyl-d 3) phenyl) amine, M8 was used instead of M4, and a suitable material ratio was selected, and other raw materials and steps were the same as in example 10, to give 58.8g of compound as pale yellow solid I-90, yield 60.7%.
Product MS (m/e): 968.4; elemental analysis (C) 68 H 28 D 16 N 2 S 2 ): theoretical value C:84.26%, H:6.24%, N:2.89%; measured value C:84.31%, H:6.25%, N:2.84%.
EXAMPLE 17 Synthesis of Compound I-94
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The procedure of example 10 was followed except for using 7, 7-dimethyl-5, 7-indano [2,1-b ] carbazole instead of bis (4- (methyl-d 3) phenyl) amine and M9 instead of M4 to give 65.4g of Compound I-94 as a pale yellow solid in 58.9% yield.
Product MS (m/e): 1110.5; elemental analysis (C) 82 H 38 D 14 N 2 O 2 ): theoretical value C:88.62%, H:5.98%, N:2.52%; measured value C:88.64%, H:5.93%, N:2.57%.
EXAMPLE 18 Synthesis of Compound I-100
N- (phenyl-d 5) dibenzo [ b, d ] thiophen-2-amine was used instead of bis (4- (methyl-d 3) phenyl) amine, M10 was used instead of M4, and a suitable material ratio was selected, and the other materials and steps were the same as in example 10, to obtain 68.0g of a pale yellow solid I-100, yield 59.8%.
Product MS (m/e): 1136.4; elemental analysis (C) 76 H 20 D 24 N 2 S 4 ): theoretical value C:80.24%, H:6.02%, N:2.46%; measured value C:80.16%, H:6.06%, N:2.51%.
According to the technical schemes of examples 1 to 18, other compounds in I-1 to I-100 were synthesized by simply replacing the corresponding raw materials without changing any substantial operation.
Example 19: stability verification experiment
Using compound BD, compound D-1, compound D-2 and compound D-3 in the prior art as control compounds, taking 5g of each of compound BD, compound D-1, compound D-2, compound D-3 and the compound I-1 prepared by the invention, respectively, placing the obtained mixture in a high vacuum sublimation instrument at a temperature of 6.0 x 10 -4 Sublimation was performed at 300℃under vacuum of Pascal for 20 hours, and the sublimation results are shown in Table 1.
The structural formula of the compound in the prior art selected by the invention is shown as follows:
table 1:
as can be seen from the data in Table 1, the purity of the compound I-1 provided by the invention after sublimation is relatively improved to a larger extent than that of the compound BD, the compound D-1, the compound D-2 and the compound D-3 in the prior art after sublimation. Therefore, the cyclization strategy adopted by the invention can effectively improve the thermal stability of the prepared fluorescent material.
Specific examples of organic electroluminescent devices prepared using representative compounds of the present invention are described below.
The application examples of the OLED device of the compound of the invention are as follows, and the embodiment provides a group of OLED blue light devices, the structure of the devices is as follows: ITO/HATCN (1 nm)/HT 01 (60 nm)/TAPC (40 nm)/BH 5% fluorescent phosphor compound of the invention (40 nm)/TPBI (5 nm) ET01: liQ (1:1) (30 nm)/LiF (1 nm)/Al.
The molecular structure of each functional layer material is as follows:
device example 1: preparation of OLED-1 devices
The compound I-1 prepared by the method is selected as a fluorescent luminescent material, the doping concentration is 5%, and the OLED device is prepared by the specific preparation method as follows:
(1) Ultrasonic treating the glass plate coated with the ITO transparent conductive layer in a commercial cleaning agent, flushing in deionized water, ultrasonic degreasing in a mixed solvent of acetone and ethanol (volume ratio is 1:1), baking in a clean environment until the moisture is completely removed, cleaning with ultraviolet light and ozone, and bombarding the surface with a low-energy cation beam;
(2) Placing the above glass substrate with anode in vacuum chamber, and vacuumizing to 1×10 -5 ～9×10 -3 Pa, vacuum evaporating HATCN as a hole injection layer on the anode layer film, wherein the evaporation rate is 0.1nm/s, and the total film thickness of evaporation is 1nm; evaporating the first cavity layer HT01 at the evaporation rate of 0.1nm/s and thickness of 60nm; evaporating a second hole transport layer TAPC, wherein the evaporation rate is 0.1nm/s, and the thickness of the evaporation film is 40nm;
(3) Vacuum evaporating EML on the hole transmission layer as a light-emitting layer of the device, wherein the EML comprises a main material BH and the dye material I-1, the doping mass percentage concentration is 5%, an organic light-emitting layer of the device is formed, the evaporation rate is 0.2nm/s, and the total evaporation film thickness is 40nm; evaporating TPBI of 5nm to form a hole blocking layer, wherein the evaporation rate is 0.1nm/s;
(4) Evaporating ET01: QLi with the mass ratio of 1:1 on the hole blocking layer as an electron transport material of the electron transport layer of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness of the evaporation is 30nm;
(5) LiF with the thickness of 1nm is sequentially and vacuum-evaporated on the electron transport layer to serve as an electron injection layer, and an Al layer with the thickness of 150nm serves as a cathode of the device. And packaging to obtain the OLED-1 device.
Device examples 2 to 3: preparation of OLED-2 to OLED-3 devices
According to the preparation method of the OLED-1 device, the doping concentration of the dye material I-1 in the main material BH in the step (3) is changed from 5% to 8% and 10% respectively, so that the OLED-2 and OLED-3 devices are prepared.
The performance of the devices OLED-1 to OLED-3 was tested, and the specific performance test results are shown in Table 2.
Table 2:
from the results of comparing the above three light emitting devices in table 2, it can be seen that the light emitting device OLED-2 has the best performance, that is, the highest luminance and the highest efficiency when the doping concentration is about 8%.
Device examples 4 to 14: preparation of OLED-4 to OLED-20
According to the preparation method of the OLED-1 device, the dye material I-1 in the step (3) is replaced by the compounds I-3, I-12, I-15, I-29, I-32, I-38, I-51, I-54, I-57, I-67, I-74, I-77, I-84, I-85, I-90, I-94 and I-100 respectively, and the doping concentration in the main material BH is 8%, so that the OLED-4-OLED-20 device is prepared.
The contrast device 1 was prepared by using the compound BD of a structure known in the prior art as a dye material instead of the dye material I-1 in the OLED-1 device, and the doping concentration in the host material BH was 8%.
The contrast device 2 was prepared by using the compound D-1 of a structure known in the prior art as a dye material to replace the dye material I-1 in the OLED-1 device, and the doping concentration in the host material BH was 8%.
The contrast device 3 was prepared by using the compound D-2 of a structure known in the prior art as a dye material instead of the dye material I-1 in the OLED-1 device, and the doping concentration in the host material BH was 8%.
The contrast device 4 was prepared by using the compound D-3 of a structure known in the prior art as a dye material to replace the dye material I-1 in the OLED-1 device, and the doping concentration in the host material BH was 8%.
The performance of the devices OLED-2, OLED-4 to OLED-20 and comparative device 1 to comparative device 4 prepared above were tested, and the results of the performance tests of the devices are shown in Table 3.
Table 3:
as can be seen from the results in Table 3 above, the device performance of the compounds employing the deuterated group-containing structures of the present invention was better than the device performance of the comparative compounds of the prior art, namely BD, D-1, D-2, and D-3. Because the stability of the compound is improved, the luminous efficiency of the corresponding device is improved, and the service life is obviously prolonged. The organic compound has different molecular structures, has different photoelectric properties and service lives, and can be used for connecting different substituents to a mother nucleus, so that on one hand, the luminous color can be regulated, the photoelectric properties and service lives of the corresponding devices can be obviously influenced, the wide adjustability of the luminous properties and the device data of the compound can be shown, and a solution can be provided for different customer demands. Therefore, the fluorescent luminescent material provided by the invention can effectively solve the problems of the conventional fluorescent material in terms of color purity, luminous efficiency, service life and the like, and the organic electroluminescent device prepared by using the fluorescent luminescent material provided by the invention has the advantages of high purity, high brightness and high efficiency.
The present invention is illustrated by the above examples, but is not limited to the above detailed methods, and under the guidance of the inventive concept, those skilled in the art may make various modifications and improvements, and the equivalent substitution of each raw material of the product of the present invention, the addition of auxiliary components, the selection of specific modes, etc. fall within the scope of protection and disclosure of the present invention.

Claims (9)

1. The organic electroluminescent device comprises a substrate, and an anode layer, a plurality of light-emitting unit layers and a cathode layer which are sequentially formed on the substrate, and is characterized in that the light-emitting unit layers comprise a light-emitting layer and one or more of a hole injection layer, a hole transport layer, an electron blocking layer and the like, and luminescent dye in the light-emitting layer is an organic compound with a structure shown as a formula (II):
in formula (II):
R 2 and R is 6 Each independently selected from one of the following groups, wherein the dotted line represents the site of attachment to the parent nucleus:
A 1 and A 2 Each independently selected from one of the following groups, wherein the dotted line represents the site of attachment to the parent nucleus:
the doping concentration of the organic compound with the structure shown in the formula (II) in the main material of the luminescent layer is 3-12%, and the doping concentration is the mass percentage concentration.
2. The organic electroluminescent device according to claim 1, wherein the organic compound of the structure represented by formula (ii) has a doping concentration of 5% to 10% in the host material of the light-emitting layer.
3. The organic electroluminescent device according to claim 1, wherein the organic compound of the structure represented by formula (ii) has a doping concentration of 7% to 9% in the host material of the light-emitting layer.
4. The organic electroluminescent device according to claim 1, wherein the organic compound of the structure represented by formula (ii) has a doping concentration of 8% in the host material of the light-emitting layer.
5. An organic compound having a structure represented by the general formula (ii):
in formula (II):
R 2 and R is 6 Each independently selected from one of the following groups, wherein the dotted line represents the site of attachment to the parent nucleus:
A 1 and A 2 Each independently selected from one of the following groups, wherein the dotted line represents the site of attachment to the parent nucleus:
6. an organic compound having a structure represented by the general formula (ii):
in formula (II):
R 2 and R is 6 Each independently selected from one of the following groups, wherein the dotted line represents the site of attachment to the parent nucleus:
A 1 and A 2 Is of the structure shown in formula (1), A 1 And A 2 Identical to or different from each other:
ar described in formula (1) 1 、Ar 2 Each independently selected from the following groups: phenyl, biphenyl, indenyl, naphthyl, acenaphthylenyl, fluorenyl, spirobifluorenyl, phenanthryl, anthracenyl, fluoranthracenyl, pyrenyl, triphenylenyl, xanthenyl, acridinyl, carbazolyl, dibenzofuranyl or dibenzothiophenyl.
7. The organic compound according to claim 5, wherein a is 1 And A 2 Each independently selected from one of the following groups, wherein the dotted line represents the site of attachment to the parent nucleus:
/>
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8. the organic compound according to claim 5, wherein the compound is selected from the group consisting of the specific structural compounds shown below:
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9. use of the organic electroluminescent device as claimed in claim 1 in a display device or in a lighting device.
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