CN111635421A - Organic material with multi-heterocyclic structure and application thereof - Google Patents

Organic material with multi-heterocyclic structure and application thereof Download PDF

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CN111635421A
CN111635421A CN202010662497.9A CN202010662497A CN111635421A CN 111635421 A CN111635421 A CN 111635421A CN 202010662497 A CN202010662497 A CN 202010662497A CN 111635421 A CN111635421 A CN 111635421A
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organic material
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CN111635421B (en
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梁现丽
李仲庆
范洪涛
段陆萌
杭德余
曹占广
班全志
陈婷
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Beijing Yanhua Jilian Optoelectronic Technology Co ltd
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Abstract

The invention relates to an organic material with a multi-heterocyclic structure. The organic compound takes a multi-heterocyclic structure as a matrix, has good thermal stability, and obtains a novel organic material which has higher triplet state energy level, better carrier mobility, can be matched with adjacent energy levels, and has higher thermal stability and film forming stability by introducing a group with stronger electron donating capability into a proper position in the matrix structure, namely by introducing an arylamine structure, a carbazole structure or a benzo-heterocyclic structure with stronger electron donating capability into the structure. The organic light emitting diode is applied to an OLED device and used as a main material, and the photoelectric property of the device can be effectively improved. The device can be applied to the field of display or illumination.

Description

Organic material with multi-heterocyclic structure and application thereof
Technical Field
The invention relates to the technical field of organic electroluminescent display, in particular to an organic material with a multi-heterocyclic structure and application thereof.
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 for the performance of flat panel display devices are higher and higher. The main display technologies at present are plasma display devices, field emission display devices, and organic electroluminescent display devices (OLEDs). The OLED has a series of advantages of self luminescence, low-voltage direct current driving, full curing, wide viewing angle, rich colors and the like, and compared with a liquid crystal display device, the OLED does not need a backlight source, has a wider viewing angle and low power consumption, has the response speed 1000 times that of the liquid crystal display device, and has a wider application prospect.
Since OLEDs were first reported, many scholars have been working on how to improve device efficiency and stability. Forrest and Thompson research groups find that the transition metal complex can be applied to Ph OLEDs (phosphorescent OLEDs), the phosphorescent material has strong spin-orbit coupling effect, and singlet excitons and triplet excitons can be simultaneously utilized, so that the quantum efficiency in the phosphorescent electroluminescent device theoretically reaches 100%. However, phosphorescent materials have a longer excited state lifetime, and are prone to form triplet-triplet quenching and triplet-polaron- quenching when the triplet exciton concentration is higher. Phosphorescent materials are often incorporated as guest into host materials to reduce self-concentration quenching processes. Therefore, it is also an important matter to select a suitable host material in Phosphorescent organic electroluminescent devices (Ph OLEDs). Essential characteristics of the host material: (1) the high triplet state energy level is possessed; (2) the carrier mobility is better and can be matched with the energy level of the adjacent layer; (3) has high thermal stability and film forming stability.
At present, OLED display and illumination are widely commercialized and applied, the requirements of a client terminal on the photoelectricity and service life of an OLED screen body are continuously improved, in order to meet the requirements, in addition to the refinement and refinement on the OLED panel manufacturing process, the development of OLED materials capable of meeting higher device indexes is very important. Therefore, a stable and efficient main body material is developed, so that the driving voltage is reduced, the luminous efficiency of the device is improved, the service life of the device is prolonged, and the method has important practical application value.
Disclosure of Invention
The invention aims to provide a stable and efficient novel organic material which can be used for red and green phosphorescent organic electroluminescent devices, has higher triplet state energy level, better carrier mobility, higher thermal stability and higher film forming stability, and can be matched with adjacent energy levels. The material is applied to corresponding red and green phosphorescent OLED devices, can reduce driving voltage and improve the luminous efficiency of the devices.
Specifically, the organic material provided by the invention has a structure shown as a general formula (I):
Figure BDA0002579131850000021
in the general formula (I), R1～R12In which at least one group is
Figure BDA0002579131850000022
The remaining groups each independently represent a hydrogen atom, a halogen, a linear or branched alkyl group, a cycloalkyl group, an amino group, an alkylamino group, a substituted or unsubstituted aromatic group containing a benzene ring and/or an aromatic heterocyclic ring.
Ar is1、Ar2Each independently represents a substituted or unsubstituted aromatic group containing a benzene ring and/or an aromatic heterocyclic ring, and Ar1、Ar2May be the same or different; ar is1、Ar2May be independently present, may be fused with an adjacent benzene ring or heterocyclic ring, or two adjacent in position may be linked to form a ring, or form a ring through other atoms (NR, CR 'R', O, S, etc.). The R, R 'and R' are independently selected from one of hydrogen, alkyl of C1-C8, cycloalkyl of C5-C10, aryl of substituted or unsubstituted C6-C30, and heterocyclic aryl of substituted or unsubstituted C3-C30, or their combination.
As a preferable mode of the present invention, Ar is1、Ar2Each independently represents a substituted or unsubstituted benzene ring, a substituted or unsubstituted heteroaromatic ring, a substituted or unsubstituted polyphenylalkyl hydrocarbon, a substituted or unsubstituted fused-ring aromatic hydrocarbon, a substituted or unsubstituted biaromatic hydrocarbon, or a substituted or unsubstituted spirobifluorene group. When the above groups are substituted, the substituents are preferably: halogen, straight-chain or branched alkyl (preferably C1-5 straight-chain or branched alkyl), naphthenic base, aryl, amino, alkylamino, arylamine, heteroaryl, monocyclic aryl, benzo, pyrido, phenanthro, naphtho, indo (such as N-benzene indo), benzothiophene and benzofurano, wherein the number of the substituent groups is an integer of 1-7.
As a preferable mode of the present invention, Ar is1、Ar2Each independently represents a substituted or unsubstituted benzene ring, heteroaromatic ring, biphenyl, indene, naphthalene, acenaphthylene, fluorene, spirobifluorene, phenanthrene, anthracene, fluoranthene, pyrene, triphenylene, benzo (a) anthracene, benzo (b) fluoranthene, benzo (k) fluoranthene, benzo (a) pyrene, xanthene, acridine, carbazole, dibenzofuran or dibenzothiophene. When the above groups are substituted, the substituents are preferably: halogen, C1-5 linear or branched alkyl, C3-6 cycloalkyl, phenyl, diphenylamino, benzo, pyrido, phenanthro, naphtho, indo (e.g., N-benzindolyl), benzothieno, and the like,Benzofuro group, the number of the substituent groups is an integer of 1-3.
As a preferable mode of the present invention, the above-mentioned
Figure BDA0002579131850000023
In particular selected from the following groups:
Figure BDA0002579131850000024
Figure BDA0002579131850000031
Figure BDA0002579131850000041
Figure BDA0002579131850000051
more preferably, the
Figure BDA0002579131850000052
In particular selected from the following groups:
Figure BDA0002579131850000053
Figure BDA0002579131850000061
further preferably, the
Figure BDA0002579131850000062
In particular selected from the following groups:
Figure BDA0002579131850000063
Figure BDA0002579131850000071
in each of the above-mentioned substituent groups, "- - -" represents a substitution position.
As a preferable embodiment of the present invention, in the general formula (I), R1～R12Any one of the groups is
Figure BDA0002579131850000072
Further preferred is R1、R2、R3、R4、R6、R7、R10Or R11Is composed of
Figure BDA0002579131850000073
Except for representing
Figure BDA0002579131850000074
In addition to the groups (a), the remaining groups each independently represent a hydrogen atom, a halogen, a linear or branched alkyl group, a cycloalkyl group, an amino group, an alkylamino group, a substituted or unsubstituted aromatic group containing a benzene ring and/or an aromatic heterocyclic ring; as a specific embodiment, the remaining groups are all hydrogen atoms.
As a preferable embodiment of the present invention, in the general formula (I), R1～R12Any two radicals in are
Figure BDA0002579131850000075
The two groups may be located on different benzene rings, or may be located on the same benzene ring. When located on different phenyl rings, R is further preferred in the present invention1And R6、R1And R7、R1And R8、R2And R7、R2And R10、R3And R10、R3And R11、R6And R10、R6And R11、R7And R10Or R7And R11Is composed of
Figure BDA0002579131850000076
The present invention is further advantageous when located on the same benzene ringR is selected1And R3、R6And R8Or R9And R11Represents
Figure BDA0002579131850000077
Both of the above representatives
Figure BDA0002579131850000078
The groups (A) may be the same as or different from each other. Except for representing
Figure BDA0002579131850000079
In addition to the groups (a), the remaining groups each independently represent a hydrogen atom, a halogen, a linear or branched alkyl group, a cycloalkyl group, an amino group, an alkylamino group, a substituted or unsubstituted aromatic group containing a benzene ring and/or an aromatic heterocyclic ring; as a specific embodiment, the remaining groups are all hydrogen atoms.
As a preferable embodiment of the present invention, in the general formula (I), R1～R12Any three radicals in are
Figure BDA0002579131850000081
Preferably, the three groups are each located on a different phenyl ring. Further preferred according to the invention is R2、R7And R10Is composed of
Figure BDA0002579131850000082
The three above representatives
Figure BDA0002579131850000083
The groups (A) may be the same as each other, may be any two of the same but different from each other, or may be different from each other. Except for representing
Figure BDA0002579131850000084
In addition to the groups (a), the remaining groups each independently represent a hydrogen atom, a halogen, a linear or branched alkyl group, a cycloalkyl group, an amino group, an alkylamino group, a substituted or unsubstituted aromatic group containing a benzene ring and/or an aromatic heterocyclic ring; as a specific embodiment, the remaining groups are all hydrogen atoms.
Further preferred in the present invention is that the organic material is selected from the group consisting of compounds represented by the following general formulae I-1 to I-112:
Figure BDA0002579131850000085
Figure BDA0002579131850000091
Figure BDA0002579131850000101
Figure BDA0002579131850000111
Figure BDA0002579131850000121
the organic compound takes a multi-heterocyclic ring structure as a matrix, the matrix structure has good thermal stability and also has proper HOMO and LUMO energy levels and Eg, and a group with strong electron donating capability is introduced into a proper position in the matrix structure, namely, an arylamine structure, a carbazole structure or a benzo-heterocyclic ring structure with strong electron donating capability is introduced into the structure, so that a novel OLED material which has high triplet state energy level, good carrier mobility, high thermal stability and high film forming stability and can be matched with adjacent energy levels is obtained. The organic light emitting diode is applied to an OLED device and used as a main material, and the photoelectric property of the device can be effectively improved. The device can be applied to the field of display or illumination. Because the parent nucleus of the series of compounds has electron withdrawing effect, when the parent nucleus is connected with the strong electron donating arylamine group, the series of compounds can be used as a red light main body material; when the organic electroluminescent material is connected with a carbazole group and other groups, the organic electroluminescent material can be used as a green light main body material, is applied to an OLED device, can reduce the driving voltage, and improves the luminous efficiency of the device.
A second object of the present invention is to provide use of the organic material in an organic electroluminescent device, a display device, or a lighting device.
It is a third object of the present invention to provide an organic electroluminescent device. The organic material provided by the invention is used as a main body material of an EML (electron emission luminescence) layer in an organic electroluminescent device. The thickness of the EML layer can be 10-50 nm, and preferably 20-40 nm.
As a preferable embodiment of the present invention, the organic electroluminescent device comprises, in order from bottom to top, a transparent substrate, an anode layer, a hole transport layer, an electroluminescent layer comprising the host material of the present invention, an electron transport layer, an electron injection layer, and a cathode layer.
It is a fourth object of the present invention to provide a display device containing the organic material or the organic electroluminescent device according to the present invention.
It is a fifth object of the present invention to provide a lighting device, which contains the organic material or the organic electroluminescent device of the present invention.
Detailed Description
The following examples are intended to illustrate the present invention, but are not intended to limit the scope of the present invention, and other equivalent changes or modifications made without departing from the spirit of the present invention are intended to be included within the scope of the appended claims.
According to the preparation method provided by the present invention, a person skilled in the art can use known common means to implement, such as further selecting a suitable catalyst and a suitable solvent, and determining a suitable reaction temperature, a suitable reaction time, a suitable material ratio, and the like, which are not particularly limited in the present invention. If not specifically stated, the starting materials for the preparation of solvents, catalysts, bases, etc. may be obtained by published commercial routes or by methods known in the art.
Example 1: synthesis of intermediate M1
Figure BDA0002579131850000131
The synthetic route is as follows:
Figure BDA0002579131850000132
the method comprises the following specific steps:
(1) adding 4-chloro-1-fluoro-2-nitrobenzene (17.5g, 0.1mol) and 2-bromo-4-chloroaniline (30.8g, 0.15mol) into a 2L three-necked bottle with mechanical stirring, protecting with argon, heating to 180 ℃, keeping the temperature for reaction for more than 30 hours, and gradually changing the color into red and finally into deep red in the reaction process. After the reaction is finished, an organic phase is separated, extracted, dried, subjected to column chromatography, and subjected to spin-drying to obtain 30g of orange-red solid M-01 with the yield of 83%.
(2) In a 1L three-necked flask equipped with a mechanical stirrer, M-01(36.0g, 0.1mol), sodium sulfide nonahydrate (96g, 0.4mol), ethanol (200mL), water (100mL) and nitrogen were added, and the mixture was heated to reflux and refluxed for 3 hours to complete the reaction. Separating organic phase, extracting, drying, column chromatography and spin-drying solvent to obtain 26.5g white solid M-02 with yield of 80%.
(3) In a 1L three-necked flask with mechanical stirring, adding M-02(33.0g, 0.1mol) and 300mL of acetone for complete dissolution, adding a solution of KOH (11.2g,0.2mol) dissolved in water (50mL), slowly dropwise adding 2-bromo-4-chlorobenzoyl chloride (25.2g, 0.1mol) into the reaction flask, gradually precipitating solids in the reaction flask, reacting at normal temperature for 2 hours after the dropwise adding is finished, and finishing the reaction. Adjusting to neutrality, separating an organic phase, extracting, drying, performing column chromatography, and spin-drying the solvent to obtain 43.8g of white solid M-03 with the yield of 79%.
(4) Adding M-03(54.8g, 0.1mol) into a 1L three-necked bottle, adding 200mL of glycol ether under the protection of nitrogen, gradually heating to reflux, gradually dissolving the solid, magnetically stirring, keeping the temperature and reacting for 3 hours, and finishing the reaction. The organic phase was separated, extracted, dried, column chromatographed, and the solvent was spin-dried to give 40g of M-04 as a pale red solid in 76% yield.
(5) Under the protection of nitrogen, adding M-04(53.0g, 0.1mol) and THF 800mL into a 2L three-necked flask, cooling to-78 ℃, slowly dropwise adding n-butyllithium (100mL, 0.25mol) under stirring for about 30mins, flushing a dropping funnel with 50mL of THF after dropwise addition, and preserving heat for 1.5 hours after dropwise addition to obtain a reaction solution of M-05. Slowly dropwise adding sulfur dichloride (16mL, 0.25mol) into a low-temperature system at-78 ℃, then flushing a dropping funnel with a small amount of THF, preserving the temperature for 1 hour after the addition is finished, slowly heating to room temperature, stirring at room temperature for reacting for 4 hours, and finishing the reaction. Adjusting to neutrality, separating an organic phase, extracting, drying, performing column chromatography, and spin-drying the solvent to obtain 26.6g of intermediate M1 as a white solid with the yield of 66%.
Product MS (m/e): 401.96, respectively; elemental analysis (C)19H9Cl3N2S): theoretical value C: 56.53%, H: 2.25%, N: 6.94 percent; found value C: 56.32%, H: 2.11%, N: 6.82 percent.
Example 2: synthesis of intermediate M2
Figure BDA0002579131850000141
By using
Figure BDA0002579131850000142
Respectively replace
Figure BDA0002579131850000143
The intermediate M2 was obtained by selecting the appropriate material ratio and the other raw materials and procedures were the same as in example 1.
Product MS (m/e): 367.99, respectively; elemental analysis (C)19H10Cl2N2S): theoretical value C: 61.80%, H: 2.73%, N: 7.59 percent; found value C: 61.55%, H: 2.61%, N: 7.48 percent.
Example 3: synthesis of intermediate M3
Figure BDA0002579131850000151
By using
Figure BDA0002579131850000152
Respectively replace
Figure BDA0002579131850000153
Selecting proper material ratio, other raw materials and steps are all the same as the examples1 to give intermediate M3.
Product MS (m/e): 367.99, respectively; elemental analysis (C)19H10Cl2N2S): theoretical value C: 61.80%, H: 2.73%, N: 7.59 percent; found value C: 61.56%, H: 2.60%, N: 7.44 percent.
Example 4: synthesis of intermediate M4
Figure BDA0002579131850000154
By using
Figure BDA0002579131850000155
Respectively replace
Figure BDA0002579131850000156
The intermediate M4 was obtained by selecting the appropriate material ratio and the other raw materials and procedures were the same as in example 1.
Product MS (m/e): 367.99, respectively; elemental analysis (C)19H10Cl2N2S): theoretical value C: 61.80%, H: 2.73%, N: 7.59 percent; found value C: 61.55%, H: 2.61%, N: 7.45 percent.
Example 5: synthesis of intermediate M5
Figure BDA0002579131850000157
By using
Figure BDA0002579131850000158
Respectively replace
Figure BDA0002579131850000159
The intermediate M5 was obtained by selecting the appropriate material ratio and the other raw materials and procedures were the same as in example 1.
Product MS (m/e): 334.03, respectively; elemental analysis (C)19H11ClN2S): theoretical value C: 68.16%, H: 3.31%, N: 8.37 percent; found value C: 68.01%, H: 3.16%, N: 8.25 percent.
Example 6: synthesis of intermediate M6
Figure BDA0002579131850000161
By using
Figure BDA0002579131850000162
Respectively replace
Figure BDA0002579131850000163
The intermediate M6 was obtained by selecting the appropriate material ratio and the other raw materials and procedures were the same as in example 1.
Product MS (m/e): 334.03, respectively; elemental analysis (C)19H11ClN2S): theoretical value C: 68.16%, H: 3.31%, N: 8.37 percent; found value C: 68.02%, H: 3.11%, N: 8.26 percent.
Example 7: synthesis of intermediate M7
Figure BDA0002579131850000164
By using
Figure BDA0002579131850000165
Respectively replace
Figure BDA0002579131850000166
The intermediate M7 was obtained by selecting the appropriate material ratio and the other raw materials and procedures were the same as in example 1.
Product MS (m/e): 334.03, respectively; elemental analysis (C)19H11ClN2S): theoretical value C: 68.16%, H: 3.31%, N: 8.37 percent; found value C: 68.02%, H: 3.11%, N: 8.26 percent.
Example 8: synthesis of intermediate M8
Figure BDA0002579131850000167
By using
Figure BDA0002579131850000168
Instead of the former
Figure BDA0002579131850000169
The intermediate M8 was obtained by selecting the appropriate material ratio and the other raw materials and procedures were the same as in example 1.
Product MS (m/e): 367.99, respectively; elemental analysis (C)19H10Cl2N2S): theoretical value C: 61.80%, H: 2.73%, N: 7.59 percent; found value C: 61.55%, H: 2.61%, N: 7.45 percent.
Example 9: synthesis of intermediate M9
Figure BDA0002579131850000171
By using
Figure BDA0002579131850000172
Instead of the former
Figure BDA0002579131850000173
The intermediate M9 was obtained by selecting the appropriate material ratio and the other raw materials and procedures were the same as in example 1.
Product MS (m/e): 367.99, respectively; elemental analysis (C)19H10Cl2N2S): theoretical value C: 61.80%, H: 2.73%, N: 7.59 percent; found value C: 61.55%, H: 2.61%, N: 7.45 percent.
Example 10: synthesis of intermediate M10
Figure BDA0002579131850000174
Figure BDA0002579131850000175
(1) Synthesis of intermediate M10-04:
by using
Figure BDA0002579131850000176
Respectively replace
Figure BDA0002579131850000177
The material ratio is selected to be proper, other raw materials and steps are the same as those of the example 1, and M10-04 is obtained firstly.
(2) Synthesis of intermediate M10: in N2Under protection, M10-04(58.8g,0.1mol) and 500ml of anhydrous THF were added into a 2L three-necked flask, the reaction system was cooled to-78 ℃ with stirring by a liquid nitrogen ethanol bath, 70ml of a 1.6M hexane solution of n-butyllithium (0.11mol) was slowly added at this temperature, after completion of the dropwise addition, the temperature was maintained at this temperature for 15 minutes, sublimed sulfur powder (3.2g,0.1mol) was then added, after completion of the addition, the reaction system was stirred at-78 ℃ for 1 hour, and then the reaction system was slowly heated to-20 ℃ and kept at this temperature for 30 minutes. The reaction was then cooled further to-78 ℃ and CuCl (10g, 0.1mol) was added, the temperature was held at this temperature for 30 minutes, then the cold bath was removed, the reaction was allowed to warm to room temperature naturally, stirred for 2h, then the reaction was heated to reflux and reacted for 2 h. Cooling to room temperature, slowly adding saturated ammonium chloride solution, adding ethyl acetate 250ml, separating organic phase, extracting aqueous phase with ethyl acetate for 3 times, combining organic phases, drying anhydrous magnesium chloride, spin-drying solvent, and separating by column chromatography to obtain intermediate M10 total 18.6g, white solid with yield about 45%.
Product MS (m/e): 411.94, respectively; elemental analysis (C)19H10BrClN2S): theoretical value C: 55.16%, H: 2.44%, N: 6.77 percent; found value C: 55.02%, H: 2.21%, N: 6.59 percent.
Example 11: synthesis of intermediate M11
Figure BDA0002579131850000181
By using
Figure BDA0002579131850000182
Respectively replace
Figure BDA0002579131850000183
Selecting proper material ratio and other raw materialsThe procedure was the same as in example 10 to give intermediate M11.
Product MS (m/e): 411.94, respectively; elemental analysis (C)19H10BrClN2S): theoretical value C: 55.16%, H: 2.44%, N: 6.77 percent; found value C: 55.02%, H: 2.21%, N: 6.59 percent.
Example 12: synthesis of Compound I-12
Figure BDA0002579131850000184
The synthetic route is as follows:
Figure BDA0002579131850000185
A1L three-necked flask was stirred with magnetic stirring, and potassium tert-butoxide (33.6g, 0.3mol), diphenylamine (50.7g, 0.3mol) and toluene (400 ml) were added in this order after nitrogen substitution. After nitrogen replacement again, (1.2g, 6mmol) of tri-tert-butylphosphine and (0.7g, 3mmol) of palladium acetate were added in this order. After the addition, the temperature was raised to 85 ℃. A solution of (40.2g, 0.1mol) M1 and 100ml toluene was added dropwise, and the reaction was terminated by controlling the temperature at 80-120 ℃ for 4 hours. Adjusting to neutrality, separating organic phase, extracting, drying, column chromatography, and spin-drying solvent to obtain 60.1g pale yellow solid with yield of about 75%.
Product MS (m/e): 801.29, respectively; elemental analysis (C)55H39N5S): theoretical value C: 82.37%, H: 4.90%, N: 8.73 percent; found value C: 82.17%, H: 4.72%, N: 9.11 percent.
EXAMPLE 13 Synthesis of Compound I-15
Figure BDA0002579131850000191
The synthetic route is as follows:
Figure BDA0002579131850000192
using M2 instead of M1 and bis (4-isopropylphenyl) amine instead of diphenylamine, the appropriate material ratios were chosen and the other starting materials and procedures were the same as in example 12 to give 65.8g of a pale yellow solid with a yield of about 82%.
Product MS (m/e): 802.41, respectively; elemental analysis (C)55H54N4S): theoretical value C: 82.25%, H: 6.78%, N: 6.98 percent; found value C: 82.05%, H: 6.67%, N: 7.29 percent.
EXAMPLE 14 Synthesis of Compound I-20
Figure BDA0002579131850000193
The synthetic route is as follows:
Figure BDA0002579131850000194
using M3 instead of M1 and dinaphthylamine instead of diphenylamine, the appropriate material ratios were chosen and the other raw materials and procedures were the same as in example 12 to give 66.7g of a pale yellow solid with a yield of about 80%.
Product MS (m/e): 834.28, respectively; elemental analysis (C)59H38N4S): theoretical value C: 84.86%, H: 4.59%, N: 6.71 percent; found value C: 84.56%, H: 4.76%, N: 6.75 percent.
EXAMPLE 15 Synthesis of Compound I-26
Figure BDA0002579131850000201
The synthetic route is as follows:
Figure BDA0002579131850000202
using M4 instead of M1 and bis ([1,1' -biphenyl ] -4-yl) amine instead of diphenylamine, the other raw materials and procedures were the same as in example 12 except for selecting an appropriate material ratio, 61.0g of a pale yellow solid was obtained in a yield of about 71%.
Product MS (m/e): 938.34, respectively; elemental analysis (C)67H46N4S): theory of the inventionThe value C: 85.68%, H: 4.94%, N: 5.97 percent; found value C: 85.54%, H: 4.95%, N: 5.96 percent.
EXAMPLE 16 Synthesis of Compound I-29
Figure BDA0002579131850000203
The synthetic route is as follows:
Figure BDA0002579131850000204
m5 was used instead of M1 and N- (naphthalen-2-yl) phenanthreneanthracene-9-amine was used instead of diphenylamine, and the other raw materials and procedures were the same as in example 12, selecting an appropriate material ratio, to give 50.0g of a pale yellow solid with a yield of about 81%.
Product MS (m/e): 617.19, respectively; elemental analysis (C)43H27N3S): theoretical value C: 83.60%, H: 4.41%, N: 6.80 percent; found value C: 83.41%, H: 4.45%, N: 6.88 percent.
EXAMPLE 17 Synthesis of Compound I-33
Figure BDA0002579131850000211
The synthetic route is as follows:
Figure BDA0002579131850000212
m6 was used in place of M1 and N- (9, 9-dimethyl-9H-fluoren-2-yl) triphenyl-2-amine was used in place of diphenylamine, and the other raw materials and procedures were the same as in example 12, except that the appropriate material ratio was selected, whereby 55.9g of a pale yellow solid was obtained in a yield of about 76%.
Product MS (m/e): 733.26, respectively; elemental analysis (C)52H35N3S): theoretical value C: 85.10%, H: 4.80%, N: 5.73 percent; found value C: 84.90%, H: 4.78%, N: 5.62 percent.
EXAMPLE 18 Synthesis of Compound I-35
Figure BDA0002579131850000213
The synthetic route is as follows:
Figure BDA0002579131850000214
m7 was used instead of M1 and N- ([ [1,1 '-biphenyl ] -4-yl) -9,9' -spirobis [ fluorene ] -2-amine was used instead of diphenylamine, and the other raw materials and procedures were the same as in example 12, except that the appropriate material ratio was selected, to obtain 65g of a pale yellow solid with a yield of about 84%.
Product MS (m/e): 781.26, respectively; elemental analysis (C)56H35N3S): theoretical value C: 86.01%, H: 4.51%, N: 6.37 percent; found value C: 85.96%, H: 4.43%, N: 6.25 percent.
EXAMPLE 19 Synthesis of Compound I-37
Figure BDA0002579131850000221
The synthetic route is as follows:
Figure BDA0002579131850000222
m8 was used in place of M1 and N- ([ [1,1' -biphenyl ] -4-yl ] dibenzo [ b, d ] furan-3-amine was used in place of diphenylamine, and the other raw materials and procedures were the same as in example 12 except for selecting an appropriate material ratio, whereby 77.3g of a pale yellow solid was obtained in a yield of about 76%.
Product MS (m/e): 966.30, respectively; elemental analysis (C)67H42N4O2S): theoretical value C: 83.21%, H: 4.38%, N: 5.79 percent; found value C: 83.02%, H: 4.26%, N: 5.71 percent.
EXAMPLE 20 Synthesis of Compound I-45
Figure BDA0002579131850000223
The synthetic route is as follows:
Figure BDA0002579131850000224
the method comprises the following specific steps:
under the protection of nitrogen, a 2L three-necked flask is stirred by magnetic force, M10(41.2g, 0.1mol), N- (naphthalene-2-yl) -9-phenyl-9H-carbazole-3-amine (38.4g, 0.1mol), copper powder (6.3g, 0.1mol), 18-crown-6 (26.4g, 0.1mol), potassium carbonate (20.7g, 0.15mol) and 800ml of o-dichlorobenzene are added in sequence after nitrogen replacement. And heating and refluxing for reaction for 20 hours under the protection of nitrogen, and finishing the reaction. Cooling, adding water, and distilling off o-dichlorobenzene. The solid product is washed by water, filtered and dried, and is separated by column chromatography and dried to obtain 30.8g of light yellow solid I-45-1 with the yield of about 43 percent.
A1 liter three-necked flask was stirred with magnetic stirring and then purged with nitrogen, followed by sequentially adding potassium tert-butoxide (11.2g, 0.1mol), bis ([1,1' -biphenyl ] -4-yl) amine (32.1g, 0.1mol) and toluene (400 ml). After nitrogen replacement again, (0.4g, 2mmol) of tri-tert-butylphosphine and (0.2g, 1mmol) of palladium acetate were added in this order. After the addition, the temperature was raised to 85 ℃. A solution of (71.6g, 0.1mol) I-45-1 and 100ml toluene was initially added dropwise, the temperature being controlled at 80-120 ℃. Cooling to 50 deg.C, adding 100ml deionized water for hydrolysis, stirring for 10 min, filtering, boiling the filter cake with DMF for several times, and filtering to obtain 75.1g light yellow solid with yield of about 75%.
Product MS (m/e): 1001.36, respectively; elemental analysis (C)71H47N5S): theoretical value C: 85.09%, H: 4.72%, N: 6.99 percent; found value C: 84.95%, H: 4.79%, N: 6.88 percent.
EXAMPLE 21 Synthesis of Compound I-102
Figure BDA0002579131850000231
The synthetic route is as follows:
Figure BDA0002579131850000232
using M8 instead of M1, 3, 7-diisopropyl-10H-phenothiazine instead of diphenylamine, the appropriate material ratios were chosen and the other starting materials and procedures were the same as in example 12 to give 66.4g of a pale yellow solid with a yield of about 77%.
Product MS (m/e): 862.32, respectively; elemental analysis (C)55H50N4S3): theoretical value C: 76.53%, H: 5.84%, N: 6.49 percent; found value C: 76.21%, H: 5.75%, N: 6.42 percent.
EXAMPLE 22 Synthesis of Compound I-58
Figure BDA0002579131850000233
The synthetic route is as follows:
Figure BDA0002579131850000234
m2 was used instead of M1, 3, 6-diphenyl-9H-carbazole instead of diphenylamine, and the other raw materials and procedures were the same as in example 12, except that the appropriate material ratio was selected, whereby 76.6g of a pale yellow solid was obtained in a yield of about 82%.
Product MS (m/e): 934.31, respectively; elemental analysis (C)67H42N4S): theoretical value C: 86.05%, H: 4.53%, N: 5.99 percent; found value C: 85.88%, H: 4.44%, N: 5.78 percent.
EXAMPLE 23 Synthesis of Compound I-62
Figure BDA0002579131850000241
The synthetic route is as follows:
Figure BDA0002579131850000242
m3 was used instead of M1, 7H-benzo [ c ] carbazole instead of diphenylamine, and the other raw materials and procedures were the same as in example 12, except that the appropriate material ratio was selected, to obtain 61.3g of a pale yellow solid with a yield of about 84%.
Product MS (m/e): 730.22, respectively; elemental analysis (C)51H30N4S): theoretical value C: 83.81%, H: 4.14%, N: 7.67 percent; found value C: 83.62%, H: 4.11%, N: 7.56 percent.
EXAMPLE 24 Synthesis of Compound I-65
Figure BDA0002579131850000243
The synthetic route is as follows:
Figure BDA0002579131850000244
using M4 instead of M1 and bis ([1,1' -biphenyl ] -4-yl) amine instead of diphenylamine, the other starting materials and procedures were the same as in example 12, except that the appropriate material ratios were selected, 53g of a pale yellow solid was obtained with a yield of about 62%.
Product MS (m/e): 830.25, respectively; elemental analysis (C)59H34N4S): theoretical value C: 85.28%, H: 4.12%, N: 6.74 percent; found value C: 85.13%, H: 4.03%, N: 6.45 percent.
EXAMPLE 25 Synthesis of Compound I-71
Figure BDA0002579131850000251
The synthetic route is as follows:
Figure BDA0002579131850000252
the method comprises the following specific steps:
m5 was used instead of M1, 7H-triphenylo [ a, c, g ] carbazole instead of diphenylamine, and the other raw materials and procedures were the same as in example 12, except that the appropriate material ratio was selected, 49.8g of pale yellow solid was obtained with a yield of about 81%.
Product MS (m/e): 615.18, respectively; elemental analysis (C)43H25N3S): theoretical value C: 83.88%, H: 4.09%, N: 6.82 percent; found value C: 83.64%, H: 4.01%, N: 6.63 percent.
EXAMPLE 26 Synthesis of Compound I-76
Figure BDA0002579131850000253
The synthetic route is as follows:
Figure BDA0002579131850000254
m6 was used in place of M1 and N- (9, 9-dimethyl-9H-fluoren-2-yl) triphenyl-2-amine was used in place of diphenylamine, and the other raw materials and procedures were the same as in example 12 except that the appropriate material ratio was selected to obtain 51.0g of a pale yellow solid with a yield of about 83%.
Product MS (m/e): 615.18, respectively; elemental analysis (C)43H25N3S): theoretical value C: 83.88%, H: 4.09%, N: 6.82 percent; found value C: 83.62%, H: 4.01%, N: 6.63 percent.
EXAMPLE 27 Synthesis of Compound I-81
Figure BDA0002579131850000261
The synthetic route is as follows:
Figure BDA0002579131850000262
m7 was used in place of M1, 12-phenyl-9H-dibenzo [ a, c ] carbazole in place of diphenylamine, and the other raw materials and procedures were the same as in example 12 except for selecting an appropriate material ratio, whereby 56.3g of a pale yellow solid was obtained in a yield of about 85%.
Product MS (m/e): 641.19, respectively; elemental analysis (C)45H27N3S): theoretical value C: 84.22%, H: 4.24%, N: 6.55 percent; found value C: 84.02%, H: 4.14%, N: 6.45 percent.
EXAMPLE 28 Synthesis of Compound I-86
Figure BDA0002579131850000263
The synthetic route is as follows:
Figure BDA0002579131850000264
the diphenylamine was replaced by M1, 5-phenyl-5, 10-indolino [3,2-b ] indole using M9 in the appropriate ratio and the other starting materials and procedures were the same as in example 12 to give 62g of a pale yellow solid in about 73% yield.
Product MS (m/e): 860.27, respectively; elemental analysis (C)59H36N6S): theoretical value C: 82.30%, H: 4.21%, N: 9.76 percent; found value C: 82.13%, H: 4.12%, N: 9.55 percent.
EXAMPLE 29 Synthesis of Compound I-100
Figure BDA0002579131850000265
The synthetic route is as follows:
Figure BDA0002579131850000271
substituting M11 for M10, 12H-benzo [4,5] thieno [3,2-a ] carbazole for N- (naphthalen-2-yl) -9-phenyl-9H-carbazol-3-amine, and 10-phenyl-5, 10-dihydroindeno [1,2-b ] indole for bis ([1,1' -biphenyl ] -4-yl) amine, the appropriate material ratios were chosen and the other raw materials and procedures were the same as in example 20 to give 63.8g of I-100 as a pale yellow solid in about 75% yield.
Product MS (m/e): 850.22, respectively; elemental analysis (C)58H34N4S2): theoretical value C: 81.86%, H: 4.03%, N: 6.58 percent; found value C: 81.65%, H: 3.96%, N: 6.37 percent.
According to the technical schemes of the embodiment 1 to the embodiment 29, other compounds I-1 to I-112 can be synthesized only by simply replacing corresponding raw materials and not changing any substantial operation.
Device example 1 Using the Compound of the present invention as a Red host Material
The embodiment provides a group of OLED red light devices OLED-1, and the structures of the devices are as follows:
ITO/HATCN (1nm)/HT01(40nm)/NPB (30nm)/EML (30nm) (containing I-12)/Bphen (30nm)/LiF (1 nm)/Al.
The molecular structure of each functional layer material is as follows:
Figure BDA0002579131850000272
the preparation method comprises the following steps:
(1) carrying out ultrasonic treatment on the glass plate coated with the ITO transparent conductive layer in a commercial cleaning agent, washing the glass plate in deionized water, ultrasonically removing oil in an acetone-ethanol mixed solvent (the volume ratio is 1: 1), baking the glass plate in a clean environment until the water is completely removed, cleaning the glass plate by using ultraviolet light and ozone, and bombarding the surface by using low-energy cationic beams;
(2) placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3Pa, performing vacuum evaporation on the anode layer film to form HATCN as a first hole injection layer, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 1 nm; then evaporating a second hole injection layer HT01 at the evaporation rate of 0.1nm/s and the thickness of 40 nm; then evaporating a hole transport layer at the evaporation rate of 0.1nm/s and the thickness of the evaporated film of 30 nm;
(3) EML is evaporated on the hole transport layer in vacuum and used as a light emitting layer of the device, the EML comprises the red main body material I-12 and the dye material, the evaporation rate of the main body material is adjusted to be 0.1nm/s by utilizing a multi-source co-evaporation method, and the dye material Ir (piq)2The acac concentration is 5%, and the total film thickness of evaporation plating is 30 nm; PRH01 was used as a contrast material for the host material;
(4) taking Bphen as an electron transport layer material of the device, wherein the evaporation rate is 0.1nm/s, and the total film thickness of evaporation is 30 nm;
(5) LiF with the thickness of 1nm is sequentially subjected to vacuum evaporation 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.
According to the same steps as the above, only replacing I-12 in the step (3) with I-15, I-20, I-26, I-29, I-33, I-35, I-37, I-45 and I-102 respectively, and using the materials as red light host materials to obtain the OLED-2-OLED-10 respectively provided by the invention.
Following the same procedure as above, only I-12 in step (3) was replaced with PRH01 (comparative compound), giving comparative example OLED-11 provided by the present invention. The PRH01 has the following structure:
Figure BDA0002579131850000281
the performance of the obtained devices OLED-1 to OLED-11 is detected, and the detection results are shown in Table 1.
Table 1: performance test result of OLED device
Figure BDA0002579131850000282
Device example 2 Using the Compound of the present invention as a Green host Material
The embodiment provides a group of OLED green light devices OLED-12, the structure of the device is as follows:
ITO/HATCN (1nm)/HT01(40nm)/NPB (20nm)/EML (30nm) (containing I-58)/Bphen (40nm)/LiF (1 nm)/Al.
The molecular structure of each functional layer material is as follows:
Figure BDA0002579131850000291
(1) ultrasonically cleaning a glass substrate coated with an ITO transparent conductive film in cleaning solution, ultrasonically treating the glass substrate in deionized water, ultrasonically removing oil in a mixed solution of acetone and ethanol (the volume ratio is 1: 1), baking the glass substrate in a clean environment until the water is completely removed, carrying out etching and ozone treatment by using an ultraviolet lamp, and bombarding the surface by using low-energy cation beams;
(2) placing the glass substrate with the anode in a vacuum chamber, and vacuumizing to 1 × 10-5～9×10-3Pa, performing vacuum evaporation on the anode layer film to form HATCN as a first hole injection layer, wherein the evaporation rate is 0.1nm/s, and the total evaporation film thickness is 1 nm; followed by evaporation of a second hole injection layer HT01,the evaporation rate is 0.1nm/s, and the thickness is 40 nm; then evaporating a hole transport layer NPB with the evaporation rate of 0.1nm/s and the evaporation film thickness of 20 nm;
(3) vacuum evaporating EML (Electron cyclotron resonance) on the hole transport layer to serve as a light emitting layer of the device, wherein the EML comprises the green light host material (I-58) and the dye material, placing the host material serving as the light emitting layer in a chamber of vacuum vapor deposition equipment by using a multi-source co-evaporation method, and adding Ir (ppy) serving as a dopant3Placing in another chamber of vacuum vapor deposition equipment, and adjusting evaporation rate of main material to 0.1nm/s, Ir (ppy)3The concentration of (2) is 10%, and the total film thickness of evaporation plating is 30 nm;
(4) evaporating Bphen on the luminescent layer in vacuum to form an electron transport layer with the thickness of 40nm, wherein the evaporation rate is 0.1 nm/s;
(5) LiF with the thickness of 1nm is sequentially subjected to vacuum evaporation 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.
According to the same steps as the above, only replacing I-58 in the step (3) with I-62, I-65, I-71, I-76, I-81, I-86 and I-100 respectively, and using the materials as green host materials, the OLED-13 to OLED-19 provided by the invention are obtained respectively.
Following the same procedure as above, only replacing I-58 in step (3) with CBP (comparative compound), comparative example OLED-20 provided by the present invention was obtained. The structure of the CBP is specifically as follows:
Figure BDA0002579131850000292
the performance of the obtained devices OLED-12 to OLED-20 is detected, and the detection results are shown in Table 2.
Table 2: performance test result of OLED device
Figure BDA0002579131850000293
Figure BDA0002579131850000301
From the above, the organic material shown in formula I containing the arylamine structure provided by the invention is used as the red light main body material, the current efficiency of the prepared device is higher, and under the condition of the same brightness, the working voltage is obviously lower than that of a comparison device, so that the red light main body material is good in performance. The organic material containing the carbazole structure and shown in the formula I is used as a green light main body material, the current efficiency of the prepared device is higher, the working voltage is obviously lower than that of a comparison device under the condition of the same brightness, and the green light main body material is good in performance.
Although the invention has been described in detail hereinabove by way of general description, specific embodiments and experiments, it will be apparent to those skilled in the art that many modifications and improvements can be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.

Claims (10)

1. An organic material with a multi-heterocyclic structure, which is characterized by having a structure shown as a general formula (I):
Figure FDA0002579131840000011
in the general formula (I), R1～R12In which at least one group is
Figure FDA0002579131840000012
The remaining groups each independently represent a hydrogen atom, a halogen, a linear or branched alkyl group, a cycloalkyl group, an amino group, an alkylamino group, a substituted or unsubstituted aromatic group containing a benzene ring and/or an aromatic heterocyclic ring.
2. The organic material of claim 1, wherein Ar is Ar1、Ar2Each independently represents a substituted or unsubstituted aromatic group containing a benzene ring and/or an aromatic heterocyclic ring, and Ar1、Ar2May be the same or different; ar is1、Ar2Can be independently existed, can be condensed with adjacent benzene ring or heterocyclic ring, or two adjacent positions can be connected to form a ring, or form a ring through NR, CR 'R', O or S; r, R 'and R' are respectively and independently selected from one of hydrogen, alkyl of C1-C8, cycloalkyl of C5-C10, substituted or unsubstituted aryl of C6-C30, substituted or unsubstituted heterocyclic aryl of C3-C30, or the combination of the hydrogen, the alkyl of C1-C8 and the substituted or unsubstituted heterocyclic aryl;
preferably, Ar is1、Ar2Each independently represents a substituted or unsubstituted benzene ring, a substituted or unsubstituted heteroaromatic ring, a substituted or unsubstituted polyphenylalkyl hydrocarbon, a substituted or unsubstituted fused-ring aromatic hydrocarbon, a substituted or unsubstituted biaromatic hydrocarbon, or a substituted or unsubstituted spirobifluorene; when the above groups are substituted, the substituents are selected from: halogen, linear or branched alkyl, cycloalkyl, aryl, amino, alkylamino, arylamino, heteroaryl, monocyclic aryl, benzo, pyrido, phenanthro, naphtho, indolo, benzothieno, benzofuro; the number of the substituent groups is an integer from 1 to 7;
more preferably, Ar is1、Ar2Each independently represents a substituted or unsubstituted benzene ring, heteroaromatic ring, biphenyl, indene, naphthalene, acenaphthylene, fluorene, spirobifluorene, phenanthrene, anthracene, fluoranthene, pyrene, triphenylene, benzo (a) anthracene, benzo (b) fluoranthene, benzo (k) fluoranthene, benzo (a) pyrene, xanthene, acridine, carbazole, dibenzofuran or dibenzothiophene; when the above groups are substituted, the substituents are selected from: halogen, C1-5 straight-chain or branched-chain alkyl, C3-6 cycloalkyl, phenyl, diphenylamino, benzo, pyrido, phenanthro, naphtho, indo, benzothieno, benzofuro; the number of the substituent groups is an integer of 1 to 3.
3. The organic material of claim 1, wherein the organic material is selected from the group consisting of
Figure FDA0002579131840000013
Selected from the group consisting of:
Figure FDA0002579131840000014
Figure FDA0002579131840000021
Figure FDA0002579131840000031
Figure FDA0002579131840000041
4. the organic material of claim 1, wherein R is1～R12Any one of the groups is
Figure FDA0002579131840000042
Or, R1～R12Any two radicals in are
Figure FDA0002579131840000043
The two groups are located on different benzene rings, or on the same benzene ring; the two groups are the same or different from each other;
or, R1～R12Any three radicals in are
Figure FDA0002579131840000044
Preferably, the three groups are located on different benzene rings; the three groups are the same as each other, or any two are the same and different from one another, or are different from one another.
5. The organic material of claim 1, wherein R is1～R12In addition to represent
Figure FDA0002579131840000045
In addition to the groups (a), the remaining groups all represent a hydrogen atom.
6. The organic material according to claim 1, characterized in that it is selected from the following compounds:
Figure FDA0002579131840000046
Figure FDA0002579131840000051
Figure FDA0002579131840000061
Figure FDA0002579131840000071
Figure FDA0002579131840000081
Figure FDA0002579131840000091
7. use of the organic material according to any one of claims 1 to 6 in an organic electroluminescent device, a display device or a lighting device.
8. An organic electroluminescent device comprising the organic material according to any one of claims 1 to 6;
preferably, the organic material is used as a host material of a light emitting layer in the organic electroluminescent device.
9. A display device comprising the organic material according to any one of claims 1 to 6 or the organic electroluminescent element according to claim 8.
10. A lighting device comprising the organic material according to any one of claims 1 to 6 or the organic electroluminescent element according to claim 8.
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CN112175016A (en) * 2020-11-05 2021-01-05 北京燕化集联光电技术有限公司 Organic electrophosphorescent luminescent material and application thereof
CN113173935A (en) * 2021-04-13 2021-07-27 武汉市晟承宇科技有限公司 Compound and application thereof

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