CN111747961B - Compound containing multiple heterocycles and application - Google Patents

Compound containing multiple heterocycles and application Download PDF

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CN111747961B
CN111747961B CN202010662481.8A CN202010662481A CN111747961B CN 111747961 B CN111747961 B CN 111747961B CN 202010662481 A CN202010662481 A CN 202010662481A CN 111747961 B CN111747961 B CN 111747961B
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梁现丽
程丹丹
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 the technical field of organic electroluminescent display, and particularly discloses an organic material containing a multi-heterocyclic compound, and also discloses an application of the organic material in an organic electroluminescent device. The compound containing the multi-heterocyclic ring provided by the invention is shown as a general formula (I), can be applied to the field of organic electroluminescence and can be used as an electron transport material. The structural compound provided by the invention is applied to an OLED device, can reduce the driving voltage of the device and improve the luminous efficiency of the device.

Description

Compound containing multiple heterocycles and application
Technical Field
The invention relates to the technical field of organic electroluminescent materials, and particularly discloses a novel compound containing multiple heterocycles, and also discloses application of the 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 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). Compared with liquid crystal display devices, OLEDs do not need backlight sources, have wider viewing angles and low power consumption, and have response speed 1000 times that of the liquid crystal display devices, so the OLEDs have wider application prospects.
Since the first time high efficiency Organic Light Emitting Diodes (OLEDs) were reported, many researchers have been working on improving the performance of OLED devices. Organic charge transport materials are an important material for OLED devices. The organic charge transport material is an organic semiconductor material which can realize the controllable directional ordered movement of carriers under the action of an electric field when the carriers (electrons or holes) are injected, thereby carrying out charge transport. The organic charge transport material mainly transports holes and is called a hole type transport material, and the organic charge transport material mainly transports electrons and is called an electron type transport material or an electron transport material for short. Organic charge transport materials have been developed to date, in which hole transport materials are more diverse and have better performance, and electron transport materials are less diverse and have poorer performance. For example, the currently commonly used electron transport material Alq3 has low electron mobility, which results in higher operating voltage of the device and serious power consumption; part of electron transport materials such as LG201 triplet level is not high, and when a phosphorescent light emitting material is used as a light emitting layer, an exciton blocking layer needs to be added, otherwise the efficiency is reduced; still other materials, such as Bphen, tend to crystallize, resulting in reduced lifetimes. These problems with electron transport materials are bottlenecks that affect the development of organic electroluminescent display devices. Therefore, the development of new electron transport materials with better performance has important practical application value.
Disclosure of Invention
The invention aims to develop an electron transport material of an organic electroluminescent device, which is applied to an OLED device, can reduce driving voltage and improve the luminous efficiency of the device.
Specifically, in a first aspect, the present invention provides a polyheterocycle-containing compound having a structure represented by general formula (i):
Figure BDA0002579125420000021
wherein:
R1～R12optionally selected from H, halogen atom, linear or branched alkyl, cycloalkyl, amino, alkylamino, substituted or unsubstituted aromatic group containing benzene ring and/or aromatic heterocycle, substituted or unsubstituted aromatic group containing hetero atom and having electron withdrawing property, and R1～R12At least one of which is a substituted or unsubstituted heteroatom-containing aromatic group having electron-withdrawing properties, and is linked to the parent nucleus represented by the general formula (I) through a C atom on the substituted or unsubstituted heteroatom-containing aromatic group having electron-withdrawing properties.
As a preferred embodiment of the present invention, in the general formula (I), R1～R12Optionally selected from H, substituted or unsubstituted heteroatom-containing aromatic groups having electron withdrawing properties, and R1～R12Not H at the same time;
the aromatic group is monocyclic aromatic hydrocarbon group or polycyclic aromatic hydrocarbon group, the polycyclic aromatic hydrocarbon group is optionally selected from poly-phenylated aliphatic hydrocarbon group, biphenyl type polycyclic aromatic hydrocarbon group and fused ring aromatic hydrocarbon group, the number of contained heteroatoms is 1-6, and the heteroatoms are optionally selected from N, O, S.
As a preferred embodiment of the present invention, the substituted or unsubstituted heteroatom-containing aromatic group having electron-withdrawing properties is optionally selected from: substituted or unsubstituted benzodiazine group, substituted or unsubstituted oxadiazolyl group, substituted or unsubstituted thiadiazolyl group, substituted or unsubstituted triazolyl group, substituted or unsubstituted benzoxazolyl or naphthoxazolyl group, substituted or unsubstituted benzothiazolyl or naphthothiazolyl group, substituted or unsubstituted benzimidazolyl or naphthoimidazolyl group, aromatic group containing at least one benzene ring substituted by one or more pyridyl groups, substituted or unsubstituted pyridyl group, substituted or unsubstituted bipyridyl group, substituted or unsubstituted phenanthroline group, substituted or unsubstituted benzophenanthroline group, substituted or unsubstituted pyridophenanthroline group, substituted or unsubstituted pyrrolophenanthroline group, substituted or unsubstituted imidazophenanthroline group, substituted or unsubstituted pyrazoloanthroline group, substituted or unsubstituted diazinoanthroline group, One or more triazinyl-substituted aromatic group containing at least one benzene ring, substituted or unsubstituted pyridazinyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted pyrazinyl group, substituted or unsubstituted triazinyl group, substituted or unsubstituted quinolyl group, substituted or unsubstituted isoquinolyl group; the diazine may be a pyridazine, pyrimidine or pyrazine;
the substituted substituents may be 1 to 5, said substituents being optionally selected from: alkyl, phenyl, alkylphenyl, naphthyl, biphenyl, benzo, naphtho, pyridyl, pyrrolyl, imidazolyl, pyrazolyl, diazinyl, quinolyl, isoquinolyl, fluorenyl, oxyfluorenyl, dibenzothiophenyl, carbazolyl; the substitution position of the substituent may be on a carbon atom or on a hetero atom.
As a preferred embodiment of the present invention, the substituted or unsubstituted heteroatom-containing aromatic group having electron-withdrawing properties is optionally selected from: a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted benzoxazolyl group, a substituted or unsubstituted benzothiazolyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted 1, 10-phenanthrolinyl group, a substituted or unsubstituted pyridazinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted benzopyrazinyl group, a substituted or unsubstituted s-triazinyl group, a substituted or unsubstituted quinolyl group, a substituted or unsubstituted isoquinolyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group;
the substituted substituents may be 1 to 5, said substituents being optionally selected from: alkyl, phenyl, biphenyl, quinazolinyl, benzopyrazinyl, triazolyl, oxadiazolyl, benzo, naphtho, benzimidazolyl, naphthyl, pyridyl, pyrido, pyrrolyl, pyrrolo, imidazolyl, imidazo, pyrazolyl, pyrazolo, diazinyl, diazino, 1, 10-phenanthroline, s-triazinyl, fluorenyl, oxyfluorenyl, thiofluorenyl, quinolyl, isoquinolyl, carbazolyl;
the hydrogen on the substituent can be further substituted by any of the following groups of 1-3: alkyl, phenyl, benzo, naphthyl, naphtho, pyridyl, biphenyl, quinazolinyl, benzopyrazinyl, triazolyl, oxadiazolyl, benzimidazolyl, fluorenyl, oxyfluorenyl, and dibenzothiophenyl.
As a further preferred embodiment of the present invention, the substituted or unsubstituted heteroatom-containing aromatic group having electron-withdrawing properties is optionally selected from: a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted benzopyrazinyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted benzothiazolyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted benzoxazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted 1, 10-phenanthrolinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted s-triazinyl group, a substituted or unsubstituted quinolyl group, a substituted or unsubstituted isoquinolyl group, a substituted or unsubstituted pyrimidyl group;
the substituted substituents may be 1 to 3, said substituents being optionally selected from: c1～C5Alkyl, phenyl, biphenyl, quinazolinyl, benzopyrazinyl, triazolyl, oxadiazolyl, benzo, naphtho, benzimidazolyl, naphthyl, pyridyl, 1, 10-phenanthrolino, pyrazino, and the like,S-triazinyl, fluorenyl, oxyfluorenyl, thiofluorenyl, quinolinyl;
the hydrogen on the substituent can be further substituted by any of the following groups of 1-2: c1～C5Alkyl, phenyl, benzo, naphthyl, naphtho, pyridyl, biphenyl, fluorenyl, oxyfluorenyl, or thiofluorenyl.
As a preferred embodiment of the present invention, in the general formula (I), R1～R12Each independently selected from H or the following groups:
Figure BDA0002579125420000041
Figure BDA0002579125420000051
Figure BDA0002579125420000061
and R is1～R12Not H at the same time.
Further preferably, in the general formula (I), R is1～R12Each independently selected from H or the following groups:
Figure BDA0002579125420000062
Figure BDA0002579125420000071
and R is1～R12Not H at the same time.
More preferably, said R1～R12Each independently selected from H or the following groups:
Figure BDA0002579125420000072
Figure BDA0002579125420000081
and R is1～R12Not H at the same time.
In each of the above-mentioned substituent groups, "- - -" represents a substitution position.
As a preferred embodiment of the present invention, in the general formula (I), R is as defined above1～R12At least one is selected from the group consisting of radicals other than H, preferably the R1～R12Wherein 1 to 5 groups are selected from groups other than H, and more preferably R1～R121 to 3 groups selected from the group other than H; when said R is1～R12When two or more groups other than H are selected, the groups other than H may be the same or different.
As a preferred embodiment of the present invention, in the general formula (I), R is as defined above1～R12One of them is selected from groups other than H, and the others are all H; preferably R1、R2、R3、R6、R7、R10Or R11Is a group other than H, more preferably R2、R7Or R10Is a group other than H. For example, R1～R12In R2Is a group other than H, and the others are all H; or R1～R12In R7Is a group other than H, and the others are all H; or R1～R12In R10The radicals other than H are all H.
As a preferred embodiment of the present invention, in the general formula (I), R is as defined above1～R12Two of them are selected from groups other than H, and the others are both H. Preferably R1And R3、R2And R7、R7And R10、R2And R10The radicals other than H are all H. For example, R1～R12In R1And R3Is a group other than H, the others are all H, and R1And R3The groups other than H may be the same or different; or R1～R12In R2And R7Is a group other than H, the others are all H, and R2And R7The groups other than H may be the same or different; or R1～R12In R7And R10Is a group other than H, the others are all H, and R7And R10The groups other than H may be the same or different; or R1～R12In R2And R10Is a group other than H, the others are all H, and R2And R10The groups other than H may be the same or different.
As a preferred embodiment of the present invention, in the general formula (I), R is as defined above1～R12Three of (1) are selected from groups other than H, and the others are all H; preferably R1～R4Wherein one is selected from the group consisting of radicals other than H, R5～R8Wherein one is selected from the group consisting of radicals other than H, R9～R12One of them is selected from the group other than H, and the others are all H; more preferably, R2、R7、R10Is selected from groups other than H, and all others are H.
As a preferred embodiment of the present invention, the compound represented by the general formula (I) is preferably selected from compounds represented by the following structural formulae:
Figure BDA0002579125420000091
Figure BDA0002579125420000101
Figure BDA0002579125420000111
in a second aspect, the invention provides the use of said polyheterocycle containing compound in the preparation of an organic electroluminescent device.
Preferably, the polyheterocycle-containing compound is used as an electron transport material in an organic electroluminescent device.
In a third aspect, the invention provides an organic electroluminescent device comprising an electron transport layer, wherein the electron transport layer comprises a material containing the polyheterocycle-containing compound.
Specifically, the invention provides an organic electroluminescent device, which sequentially comprises a transparent substrate, an anode layer, a hole injection layer, a hole transport layer, an electroluminescent layer, an electron transport layer, an electron injection layer and a cathode layer from bottom to top, wherein an electron transport material of the electron transport layer comprises the compound shown in the general formula (I), namely the compound containing multiple heterocyclic rings.
In a preferred embodiment, the thickness of the electron transport layer may be 10 to 50nm, preferably 20 to 40 nm.
In a fourth aspect, the present invention provides a display device comprising the organic electroluminescent device.
In a fifth aspect, the present invention provides a lighting apparatus comprising the organic electroluminescent device.
The invention provides the compound containing the multi-heterocyclic ring with the structure shown as the general formula (I), wherein R1～R12Optionally selected from H, halogen atom, linear or branched alkyl, cycloalkyl, amino, alkylamino, substituted or unsubstituted aromatic group containing benzene ring and/or aromatic heterocycle, substituted or unsubstituted aromatic group containing hetero atom and having electron withdrawing property, and R1～R12At least one of which is a substituted or unsubstituted heteroatom-containing aromatic group having electron-withdrawing properties, and is linked to the parent nucleus represented by the general formula (I) through a C atom on the substituted or unsubstituted heteroatom-containing aromatic group having electron-withdrawing properties.
Specifically, the substituted or unsubstituted aromatic group containing a heteroatom optionally selected from the group consisting of an N atom, an S atom and an O atom and having an electron-withdrawing property contains at least one heteroatom. The substituted or unsubstituted aromatic group containing heteroatoms and having electron withdrawing property can be monocyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon; the polycyclic aromatic hydrocarbon can be poly-benzene aliphatic hydrocarbon, biphenyl polycyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon. The substituted or unsubstituted aromatic group containing a heteroatom and having an electron-withdrawing property may contain no five-membered ring or at least one five-membered ring.
In a preferred embodiment of the present invention, the substituted or unsubstituted heteroatom-containing aromatic group having an electron-withdrawing property contains a benzene ring and a five-membered ring, and contains one heteroatom, specifically, a N atom, an S atom or an O atom, and the heteroatom may be on the five-membered ring or on the benzene ring.
When the substituted or unsubstituted heteroatom-containing aromatic group having an electron-withdrawing property contains two heteroatoms, the two heteroatoms may be the same or different. Specifically, the two heteroatoms are both N atoms, or both S atoms, or both O atoms, or both N atoms and S atoms, or both N atoms and O atoms, or both S atoms and O atoms. The two heteroatoms may be on the same five-membered ring, may be on two different five-membered rings, may be on the same benzene ring, may be on two different benzene rings, or may be one on the five-membered ring and the other on the benzene ring.
When the substituted or unsubstituted heteroatom-containing aromatic group having an electron-withdrawing property contains three heteroatoms, the three heteroatoms may be the same, any two of the heteroatoms may be the same, or may be different from each other. Specifically, the three heteroatoms are all N atoms, or all S atoms, or all O atoms, or two N atoms and the other S atom, or two N atoms and the other O atom, or two S atoms and the other N atom, or two S atoms and the other O atom, or two O atoms and the other N atom, or two O atoms and the other S atom, or N atom, S atom and O atom, respectively. The three heteroatoms may all be on the same five-membered ring, may all be on the same benzene ring, may be any two of the other on the same five-membered ring on another five-membered ring, may be any two of the other on the same five-membered ring on a benzene ring, may be any two of the other on the same benzene ring on a five-membered ring, may be any two of the other on the same benzene ring on another benzene ring, may be any two of the other on different five-membered rings on a benzene ring, may be any two of the other on different benzene rings on five-membered rings, may be on three different five-membered rings, or may be on three different benzene rings, respectively.
The invention provides a novel compound containing polyheterocycles, which is specifically shown as a general formula (I), wherein a structure containing polyheterocycles is taken as a parent nucleus, and the parent nucleus structure has stronger electron-withdrawing capability and good thermal stability; the compounds of this structure have suitable HOMO and LUMO energy levels and Eg; further by introducing an electron-withdrawing group R into the parent ring structure1～R12The electron injection capability can be effectively enhanced, and the electron transmission performance is improved.
The novel OLED material provided by the invention takes a compound containing a multi-heterocyclic ring structure as a parent nucleus, the parent nucleus structure has strong electron withdrawing capability, and an electron withdrawing group is introduced into the parent nucleus structure to obtain the novel OLED material. The material has high electron transport performance, high film stability and proper molecular energy level, and can be applied to the field of organic electroluminescence and used as an electron transport material of an OLED device. The novel OLED material provided by the invention is a stable and efficient electronic transmission material, can effectively reduce the driving voltage of a device, improves the luminous efficiency of the device and improves the photoelectric property of the device. The novel OLED material containing the compound with the multi-heterocyclic structure can be well applied to OLED devices, and the devices have the characteristics of low driving voltage and high luminous efficiency, and have very important practical application value. The device can be applied in the fields of display and illumination.
Detailed Description
The technical solution of the present invention will be described in detail by specific examples. 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.
Synthesizing intermediate M1-M10
Synthesis of intermediate M1
Figure BDA0002579125420000131
The synthetic route is as follows:
Figure BDA0002579125420000132
the specific operation steps are as follows:
(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, wherein the color of the reaction solution gradually becomes red in the reaction process, and finally gradually becomes deep red. 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), and water (100mL) were added, and the mixture was heated to reflux under nitrogen protection, and the reaction was terminated after refluxing for 3 hours. 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) and 200mL of glycol ether into a 1L three-necked flask, gradually heating to reflux under the protection of nitrogen, 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) Adding M-04(53.0g, 0.1mol) and THF 800mL into a 2L three-necked flask under the protection of nitrogen, cooling to-78 deg.C, slowly adding n-butyllithium (100mL, 0.25mol) dropwise under stirring for about 30mins, flushing a dropping funnel with 50mL of THF after dropping, keeping the temperature at-78 deg.C for 1.5 hours, and adding 20g of freshly sublimed anhydrous AlCl3The mixture is kept at low temperature for 20 minutes, anhydrous acetone (30mL, 0.4mol) is slowly dropped, then a small amount of THF is used for washing a dropping funnel, the temperature is kept for 1 hour after the addition, then the temperature is slowly raised to room temperature, the mixture is stirred at room temperature for reaction for 4 hours, and the reaction is finished. Adjusting to neutrality, separating the organic phase, extracting, drying, performing column chromatography, and spin-drying the solvent to obtain 25g of white solid, namely intermediate M1, with the yield of 61%.
Product MS (m/e): 412.03, respectively; elemental analysis (C)22H15Cl3N2): theoretical value C: 63.87%, H: 3.65%, N: 6.77 percent; found value C: 63.61%, H: 3.42%, N: 6.50 percent.
Synthesis of intermediate M2
Figure BDA0002579125420000141
By using
Figure BDA0002579125420000142
Respectively replace
Figure BDA0002579125420000143
And selecting a proper material ratio, and synthesizing other raw materials and steps which are the same as the intermediate M1 to obtain the intermediate M2.
Product MS (m/e): 378.07, respectively; elemental analysis (C)22H16Cl2N2): theoretical value C: 69.67%, H: 4.25%, N: 7.39 percent; found value C: 69.42%, H: 4.01%, N: 7.12 percent.
Synthesis of intermediate M3
Figure BDA0002579125420000144
By using
Figure BDA0002579125420000145
Instead of the former
Figure BDA0002579125420000146
And selecting a proper material ratio, and synthesizing other raw materials and steps which are the same as the intermediate M1 to obtain the intermediate M3.
Product MS (m/e): 378.07, respectively; elemental analysis (C)22H16Cl2N2): theoretical value C: 69.67%, H: 4.25%, N: 7.39 percent; found value C: 69.41%, H: 4.00%, N: 7.10 percent.
Synthesis of intermediate M4
Figure BDA0002579125420000151
By using
Figure BDA0002579125420000152
Respectively replace
Figure BDA0002579125420000153
Selection boxAccording to a proper material ratio, other raw materials and steps are the same as those of the intermediate M1, and the intermediate M4 is obtained.
Product MS (m/e): 344.11, respectively; elemental analysis (C)22H17ClN2): theoretical value C: 76.63%, H: 4.97%, N: 8.12 percent; found value C: 76.39%, H: 4.72%, N: 7.93 percent.
Synthesis of intermediate M5
Figure BDA0002579125420000154
By using
Figure BDA0002579125420000155
Instead of the former
Figure BDA0002579125420000156
And selecting a proper material ratio, and synthesizing other raw materials and steps which are the same as the intermediate M1 to obtain the intermediate M5.
Product MS (m/e): 378.07, respectively; elemental analysis (C)22H16Cl2N2): theoretical value C: 69.67%, H: 4.25%, N: 7.39 percent; found value C: 69.43%, H: 4.00%, N: 7.11 percent.
Synthesis of intermediate M6
Figure BDA0002579125420000157
By using
Figure BDA0002579125420000161
Instead of the former
Figure BDA0002579125420000162
And selecting a proper material ratio, and synthesizing other raw materials and steps which are the same as the intermediate M1 to obtain the intermediate M6.
Product MS (m/e): 378.07, respectively; elemental analysis (C)22H16Cl2N2): theoretical value C: 69.67%, H: 4.25%, N: 7.39 percent(ii) a Found value C: 69.41%, H: 4.00%, N: 7.08 percent.
Synthesis of intermediate M7
Figure BDA0002579125420000163
By using
Figure BDA0002579125420000164
Respectively replace
Figure BDA0002579125420000165
And selecting a proper material ratio, and synthesizing other raw materials and steps which are the same as the intermediate M1 to obtain the intermediate M7.
Product MS (m/e): 344.11, respectively; elemental analysis (C)22H17ClN2): theoretical value C: 76.63%, H: 4.97%, N: 8.12 percent; found value C: 76.39%, H: 4.72%, N: 7.93 percent.
Synthesis of intermediate M8
Figure BDA0002579125420000166
By using
Figure BDA0002579125420000167
Respectively replace
Figure BDA0002579125420000168
And selecting a proper material ratio, and obtaining the intermediate M8 by the same synthesis of other raw materials and steps as the intermediate M1.
Product MS (m/e): 344.11, respectively; elemental analysis (C)22H17ClN2): theoretical value C: 76.63%, H: 4.97%, N: 8.12 percent; found value C: 76.36%, H: 4.73%, N: 7.90 percent.
Synthesis of intermediate M9
Figure BDA0002579125420000171
The synthetic route is as follows:
Figure BDA0002579125420000172
(1) synthesis of intermediate M9-04:
by using
Figure BDA0002579125420000173
Respectively replace
Figure BDA0002579125420000174
Figure BDA0002579125420000175
Selecting a proper material ratio, and synthesizing other raw materials and steps which are the same as the intermediate M1 to obtain the intermediate M9-04.
(2) Synthesis of intermediate M9:
under the protection of nitrogen, M9-04(51.0g, 0.1mol) and THF 800mL are added into a 2L three-necked bottle, the mixture is cooled to-78 ℃, n-butyllithium (44mL, 0.11mol) is slowly dropped under stirring for about 30mins, the dropping funnel is flushed with 50mL of THF after dropping, the temperature is kept at-78 ℃ for 1.5 hours after dropping, then anhydrous acetone (30mL, 0.4mol) is slowly dropped, then a small amount of THF is used for flushing the dropping funnel, the temperature is kept for 1 hour after adding, then the temperature is slowly raised to room temperature, the reaction is stirred at room temperature for 4 hours, and the reaction is finished. Adjusting to neutrality, separating organic phase, extracting, drying with anhydrous molecular sieve, and pumping off solvent to obtain yellow solid. This solid was dissolved in 300ml of dry CH2Cl2Cooling to 0 deg.C in ice water bath, slowly adding methanesulfonic acid (19.2g, 0.2mol), stirring at 0 deg.C for 2 hr, heating to room temperature, stirring for 1 hr, detecting by TLC, adding saturated NaHCO3The reaction was quenched and adjusted to neutral, washed twice with dichloromethane, combined with organic solvents, dried over anhydrous magnesium sulfate, column chromatographed, solvent dried to give 30.8g of a white solid, intermediate M9, 73% yield.
Product MS (m/e): 422.02, respectively; elemental analysis (C)22H16BrClN2): theoretical value C: 62.36%, H: 3.81%, N: 6.61 percent; found value C: 62.11%, H: 3.54%, N: 6.36 percent.
Synthesis of intermediate M10
Figure BDA0002579125420000181
By using
Figure BDA0002579125420000182
Respectively replace
Figure BDA0002579125420000183
And selecting a proper material ratio, and obtaining an intermediate M10 by the same synthesis method of the intermediate M9 and other raw materials and steps.
Product MS (m/e): 422.02, respectively; elemental analysis (C)22H16BrClN2): theoretical value C: 62.36%, H: 3.81%, N: 6.61 percent; found value C: 62.10%, H: 3.55%, N: 6.38 percent.
Example 1
Figure BDA0002579125420000184
The synthetic route is as follows:
Figure BDA0002579125420000185
the synthesis of the compound I-6 comprises the following specific steps:
A2L three-necked flask was taken, stirred with magnetic force, and after nitrogen substitution, M1(41.2g, 0.1mol), (4-phenylquinazolin-2-yl) boronic acid (75.0g, 0.3mol), cesium carbonate (117g, 0.36mol) and dioxane 800ml were added in this order, followed by stirring. After nitrogen replacement again, (2.2g, 11mmol) tri-tert-butylphosphine and (4.1g, 4.5mmol) tris (dibenzylideneacetone) dipalladium were added. After the addition, heating and raising the temperature, controlling the temperature to be 80-90 ℃ for reaction for 4 hours, and cooling after the reaction is finished. Adjusting to neutrality, separating an organic phase, extracting, drying, performing column chromatography, and spin-drying the solvent to obtain 70.1g of pale yellow solid with the yield of about 76%.
Product MS (m/e): 922.35, respectively; elemental analysis (C)64H42N8): theoretical value C: 83.27%, H: 4.59%, N: 12.14 percent; found value C: 83.03%, H: 4.36%, N: 11.86 percent.
Example 2
Figure BDA0002579125420000191
The synthetic route is as follows:
Figure BDA0002579125420000192
synthesis of Compound I-16: m2 was used instead of M1 and benzo [ d ] thiazol-2-yl boronic acid was used instead of (4-phenylquinazolin-2-yl) boronic acid, the other raw materials and procedures were the same as in example 1, selecting appropriate material ratios, to give 49.5g of a pale yellow solid with a yield of about 86%.
Product MS (m/e): 576.14, respectively; elemental analysis (C)36H24N4S2): theoretical value C: 74.97%, H: 4.19%, N: 9.71 percent; found value C: 74.71%, H: 3.96%, N: 9.48 percent.
Example 3
Figure BDA0002579125420000193
The synthetic route is as follows:
Figure BDA0002579125420000194
synthesis of Compound I-18: m3 was used instead of M1 and naphtho [2,3-d ] oxazol-2-ylboronic acid was used instead of (4-phenylquinazolin-2-yl) boronic acid, the appropriate material ratios were chosen and the other raw materials and procedures were the same as in example 1 to give 50.9g of a pale yellow solid with a yield of about 79%.
Product MS (m/e): 644.22, respectively; elemental analysis (C)44H28N4O2): theoretical value C: 81.97%, H: 4.38%, N: 8.69 percent; found value C: 81.73%, H: 4.12%, N: 8.48 percent.
Example 4
Figure BDA0002579125420000201
The synthetic route is as follows:
Figure BDA0002579125420000202
synthesis of Compound I-23: the appropriate material ratios were chosen using M4 instead of M1, (4, 6-bis ([ [1,1' -biphenyl ] -4-yl) -1,3, 5-triazin-2-yl) boronic acid instead of (4-phenylquinazolin-2-yl) boronic acid, and the other materials and procedures were the same as in example 1 to give 49.9g of a pale yellow solid in about 72% yield.
Product MS (m/e): 693.29, respectively; elemental analysis (C)49H35N5): theoretical value C: 84.83%, H: 5.08%, N: 10.09%; found value C: 84.56%, H: 4.83%, N: 9.79 percent.
Example 5
Figure BDA0002579125420000203
The synthetic route is as follows:
Figure BDA0002579125420000204
synthesis of Compound I-45: using M5 instead of M1 and (4- (pyridin-4-yl) phenyl) boronic acid instead of (4-phenylquinazolin-2-yl) boronic acid, the other raw materials and procedures were the same as in example 1, selecting appropriate material ratios, 47.4g of a pale yellow solid was obtained with a yield of about 77%.
Product MS (m/e): 616.26, respectively; elemental analysis (C)44H32N4): theoretical value C: 85.69%, H: 5.23%, N: 9.08 percent; found value C: 85.44%, H: 5.20%, N: 8.83 percent.
Example 6
Figure BDA0002579125420000211
The synthetic route is as follows:
Figure BDA0002579125420000212
synthesis of Compounds I-48: using M6 instead of M1 and (3, 5-bis (pyridin-4-yl) phenyl) boronic acid instead of (4-phenylquinazolin-2-yl) boronic acid, the appropriate material ratios were chosen and the other starting materials and procedures were the same as in example 1 to give 56.2g of a pale yellow solid with a yield of about 73%.
Product MS (m/e): 770.32, respectively; elemental analysis (C)54H38N6): theoretical value C: 84.13%, H: 4.97%, N: 10.90 percent; found value C: 83.89%, H: 4.71%, N: 10.65 percent.
Example 7
Figure BDA0002579125420000213
The synthetic route is as follows:
Figure BDA0002579125420000214
synthesis of Compound I-52: m7 was used in place of M1, and (1, 10-phenanthrolin-5-yl) boronic acid was used in place of (4-phenylquinazolin-2-yl) boronic acid, and the other raw materials and procedures were the same as in example 1, except that the appropriate material ratio was selected, whereby 42.0g of a pale yellow solid was obtained with a yield of about 86%.
Product MS (m/e): 488.20, respectively; elemental analysis (C)34H24N4): theoretical value C: 83.58%, H: 4.95%, N: 11.47 percent; found value C: 83.33%, H: 4.72%, N: 11.25 percent.
Example 8
Figure BDA0002579125420000221
The synthetic route is as follows:
Figure BDA0002579125420000222
synthesis of Compound I-54: m8 is used for replacing M1, benzo [ f ] [1,10] phenanthroline-6-yl boric acid is used for replacing (4-phenylquinazolin-2-yl) boric acid, a proper material ratio is selected, other raw materials and steps are the same as those in example 11, 43.0g of light yellow solid is obtained, and the yield is about 80%.
Product MS (m/e): 538.22, respectively; elemental analysis (C)38H26N4): theoretical value C: 84.73%, H: 4.87%, N: 10.40 percent; found value C: 84.49%, H: 4.66%, N: 10.13 percent.
Example 9
Figure BDA0002579125420000223
The synthetic route is as follows:
Figure BDA0002579125420000224
the synthesis of the compound I-36 comprises the following specific steps:
into a 1L three-necked flask, M9(42.2g, 0.1mol), (4, 6-bis (quinolin-3-yl) -1,3, 5-triazin-2-yl) boronic acid (37.9g, 0.1mol), sodium carbonate (21.2g,0.2mol), toluene 150mL, ethanol 150mL, and water 150mL were charged, and after the reaction system was purged with nitrogen, Pd (PPh) was added3)4(11.5g, 10 mmol). The reaction was heated under reflux (temperature in the system: about 78 ℃ C.) for 3 hours to stop the reaction. ReducingThe solvent was distilled off, dichloromethane extraction was carried out, anhydrous magnesium sulfate was dried, filtration was carried out, petroleum ether/ethyl acetate (2:1) column chromatography was carried out, the solvent was dried by spinning, ethyl acetate was beaten, and filtration was carried out to obtain 56.9g of pale yellow solid I-36-1 with a yield of about 84%.
A1L three-necked flask was taken, and magnetic stirring was carried out, nitrogen gas was substituted, and then I-36-1(67.7g, 0.1mol), (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) boronic acid (35.3g, 0.1mol), cesium carbonate (39g, 0.12mol) and dioxane (400 ml) were added in this order, and stirring was started. After nitrogen replacement again, (0.8g, 4mmol) tri-tert-butylphosphine and (1.4g, 1.5mmol) tris (dibenzylideneacetone) dipalladium were added. After the addition, heating and raising the temperature, controlling the temperature to be 80-90 ℃ for reaction for 4 hours, and cooling after the reaction is finished. Adjusting to neutrality, separating organic phase, extracting, drying, column chromatography, spin-drying solvent, and filtering to obtain 72.2g pale yellow solid I-36 with yield of about 76%.
Product MS (m/e): 950.36, respectively; elemental analysis (C)64H42N10): theoretical value C: 80.82%, H: 4.45%, N: 14.73%; found value C: 80.59%, H: 4.21%, N: 14.48 percent.
Example 10
Figure BDA0002579125420000231
The synthetic route is as follows:
Figure BDA0002579125420000232
synthesis of Compound I-58: m9 was replaced with M10, and (4- (pyridin-4-yl) phenyl) boronic acid was respectively replaced with (4- (pyridin-4-yl) phenyl) boronic acid instead of (4, 6-bis (quinolin-3-yl) -1,3, 5-triazin-2-yl) boronic acid, (benzo [ f ] [1,10] phenanthroline-6-yl) boronic acid instead of (4- (4, 6-diphenyl-1, 3, 5-triazin-2-yl) phenyl) boronic acid, the appropriate material ratios were selected, and the other materials and procedures were the same as in example 9, to give 49.8g of a pale yellow solid, i.e., I-58, in about 72% yield.
Product MS (m/e): 691.27, respectively; elemental analysis (C)49H33N5): theoretical value C: 85.07%, H: 4.81%, N: 10.12 percent; found value C: 84.86%, H: 4.58%, N: 9.93 percent.
According to the synthesis schemes of the above examples 1 to 10, other compounds in I-1 to I-60 can be synthesized by simply replacing the corresponding raw materials without changing any substantial operation.
Example 11
The embodiment provides a group of OLED blue light fluorescent devices, and the device structure is as follows: ITO/HATCN (1nm)/HT01(40nm)/NPB (30nm)/EML (30 nm)/any of the compounds (30nm)/LiF (1nm)/Al provided in examples 1 to 10, the preparation process comprising:
(1) carrying out ultrasonic treatment on a glass substrate coated with an ITO transparent conductive thin film layer in a commercial cleaning agent, carrying out ultrasonic washing treatment in deionized water, carrying out ultrasonic oil removal in an acetone-ethanol mixed solvent (volume ratio is 1: 1), baking in a clean environment until water is completely removed, cleaning 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 and plating a layer of NPB (N-propyl bromide) on the hole injection layer film to form a hole transport layer, wherein the evaporation rate is 0.1nm/s, and the evaporation film thickness is 30 nm; wherein the structural formulas of HATCN, HT01 and NPB are as follows:
Figure BDA0002579125420000241
(3) EML is evaporated on the hole transport layer in vacuum and used as a light emitting layer of the device, the EML comprises a main material and a dye material, the evaporation rate of the main material ADN is adjusted to be 0.1nm/s, the concentration of the dye material BD01 is adjusted to be 5%, and the total thickness of the evaporation film is 30nm by using a multi-source co-evaporation method; the structural formulas of ADN and BD01 are as follows:
Figure BDA0002579125420000242
(4) taking any one of the compounds provided in the embodiments 1 to 10 as an electron transport material of an electron transport layer of a device for evaporation, wherein the evaporation rate is 0.1nm/s, and the total thickness of the evaporation film is 30 nm;
(5) sequentially vacuum evaporating LiF with the thickness of 1nm on the electron transport layer to serve as an electron injection layer of the device, continuously evaporating a layer of Al on the electron injection layer to serve as a cathode of the device, and evaporating the film with the thickness of 150 nm; obtaining a series of OLED-1-OLED-10 devices provided by the invention.
According to the same procedure as above, only the electron transport material in the step (4) was replaced with the following comparative compound, the structural formula of which is shown below, to obtain a comparative device OLED-11.
Figure BDA0002579125420000251
Comparative compounds.
The performance of the obtained devices OLED-1 to OLED-11 is detected, and the detection results are shown in Table 1.
TABLE 1
Figure BDA0002579125420000252
As can be seen from the results in the table above, the blue fluorescent devices OLED-1 to OLED-10 prepared by using the compound provided by the invention have higher current efficiency, and the working voltage is obviously lower than that of the device OLED-11 using the comparative compound Bphen as an electron transport material under the condition of the same brightness. As described above, the organic material represented by the general formula (I) provided by the invention is a novel electron transport material with good 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. A polyheterocycle containing compound having a structure represented by general formula (i):
Figure FDA0003185106400000011
wherein:
R1～R12optionally selected from H, substituted or unsubstituted heteroatom-containing aromatic groups having electron withdrawing properties, and R1～R12At least one of which is a substituted or unsubstituted heteroatom-containing aromatic group having electron-withdrawing properties and is linked to the parent nucleus represented by the general formula (I) through the C atom on the substituted or unsubstituted heteroatom-containing aromatic group having electron-withdrawing properties;
the substituted or unsubstituted heteroatom-containing aromatic group having electron-withdrawing properties is optionally selected from: a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted benzopyrazinyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted benzothiazolyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted benzoxazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted 1, 10-phenanthrolinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted s-triazinyl group, a substituted or unsubstituted quinolyl group, a substituted or unsubstituted isoquinolyl group, a substituted or unsubstituted pyrimidyl group;
the substituted substituents may be 1 to 3, said substituents being optionally selected from: c1～C5Alkyl, phenyl, biphenyl, quinazolinyl, benzopyrazinyl, triazolyl, oxadiazolyl, benzo, naphtho, benzimidazolyl, naphthyl, pyridyl, 1, 10-phenanthrolino, pyrazino, s-triazinyl, fluorenyl, oxyfluorenyl, thiofluorenyl, quinolyl;
said substitutionThe hydrogen on the group can be further substituted by any of the following groups of 1-2: c1～C5Alkyl, phenyl, benzo, naphthyl, naphtho, pyridyl, biphenyl, fluorenyl, oxyfluorenyl, or thiofluorenyl.
2. A compound of claim 1, wherein R is1～R12Each independently selected from H or the following groups:
Figure FDA0003185106400000012
Figure FDA0003185106400000021
Figure FDA0003185106400000031
Figure FDA0003185106400000041
and R is1～R12Not H at the same time.
3. A compound according to claim 1 or 2, wherein R is1～R121 to 3 groups selected from the group other than H; when said R is1～R12When two or more groups other than H are selected, the groups other than H may be the same or different.
4. A compound of claim 3, wherein R is1～R12One of them is selected from groups other than H, and the others are all H; wherein R is1、R2、R3、R6、R7、R10Or R11Is a group other than H;
or, said R1～R12Two of them are selected from groups other than H, and the others are both H; wherein R is1And R3、R2And R7、R7And R10、R2And R10Is a group other than H, and the others are all H;
or, said R1～R12Three of (1) are selected from groups other than H, and the others are all H; r1～R4Wherein one is selected from the group consisting of radicals other than H, R5～R8Wherein one is selected from the group consisting of radicals other than H, R9～R12One of them is selected from the group consisting of radicals other than H, and the others are all H.
5. The compound of claim 1, wherein the compound is selected from the group consisting of compounds represented by the following structural formulae:
Figure FDA0003185106400000042
Figure FDA0003185106400000051
Figure FDA0003185106400000061
6. use of a polyheterocycle containing compound of any one of claims 1 to 5 in the preparation of an organic electroluminescent device.
7. The use according to claim 6, wherein the polyheterocycle containing compound is used as an electron transport material in an organic electroluminescent device.
8. An organic electroluminescent device comprising an electron transport layer, wherein the electron transport layer comprises a polyheterocycle-containing compound according to any one of claims 1 to 5.
9. A display device comprising the organic electroluminescent element according to claim 8.
10. A lighting device comprising the organic electroluminescent element according to claim 8.
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