WO2020133833A1 - 一种二苯并杂环化合物及其制备方法和应用 - Google Patents

一种二苯并杂环化合物及其制备方法和应用 Download PDF

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WO2020133833A1
WO2020133833A1 PCT/CN2019/083653 CN2019083653W WO2020133833A1 WO 2020133833 A1 WO2020133833 A1 WO 2020133833A1 CN 2019083653 W CN2019083653 W CN 2019083653W WO 2020133833 A1 WO2020133833 A1 WO 2020133833A1
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ring
unsubstituted
substituted
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dibenzoheterocyclic
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魏定纬
谢坤山
陈志宽
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宁波卢米蓝新材料有限公司
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Definitions

  • the invention relates to the field of organic electroluminescent materials, in particular to a dibenzoheterocyclic compound and its preparation method and application.
  • Organic light-emitting devices have advantages in low driving voltage, high luminous efficiency, high contrast, high color saturation, low energy consumption, active light emission, wide viewing angle, fast response, etc.
  • the lighting field has great application prospects, and it has been paid more and more attention.
  • the OLED device uses conductive indium tin oxide (ITO) as the cathode, and the aromatic amine derivative and tris(8-hydroxyquinoline) aluminum are sequentially deposited on it.
  • the anode material uses magnesium-silver alloy to obtain high brightness ( 1000cd/m 2 ) green light emitting device.
  • a hole transport layer formed of an aromatic amine derivative is added, realizing higher luminous brightness and luminous efficiency, and lowering the driving voltage below 10V. Since then, the study of organic electroluminescent materials has attracted the attention of scientists from various countries, and has become a research hotspot in academia and industry.
  • Fluorescent materials are the earliest first-generation OLED materials, but the devices composed of these materials have low efficiency, and can only use 25% of the singlet excitons to emit light, and 75% of the triplet state electrical excitons due to spin The resistance returns to the ground state in the form of non-radiative inactivation, which greatly limits the efficiency of the device.
  • Baldo et al. reported for the first time that by introducing iridium (III), platinum (II) and osmium (II) and other metals into small organic molecules to form complexes, the triplet excitons of the material can be radiated through spin coupling The transition emits phosphorescence and obtains a theoretical internal quantum efficiency of 100%.
  • Blue light emitting materials are mainly planar aromatic ring molecules with simple conjugated fragments, which have low thermal stability and are easily decomposed by heat during film formation and use, which affects the efficiency and life of the device.
  • planar aromatic ring molecules are stacked on each other, which is easy to form exciton diplexes. The increased energy of excitons produces annihilation, which reduces the luminous efficiency of the device, shortens the service life, and changes the luminescent color and causes color shift.
  • the technical problem to be solved by the present invention is to overcome the defects in the prior art that the blue light emitting material has low thermal stability, exciton is prone to annihilation, and the luminous efficiency of the device is reduced, and the service life is shortened.
  • the present invention provides a dibenzoheterocyclic compound having the structure shown in formula (I):
  • R 1 and R 2 are independently selected from hydrogen, substituted or unsubstituted C 1 -C 60 alkyl groups, substituted or unsubstituted C 1 -C 60 alkenyl groups, substituted or unsubstituted C 1- C 60 alkynyl, substituted or unsubstituted C 3 -C 60 cycloalkyl, substituted or unsubstituted C 3 -C 60 cycloalkenyl, substituted or unsubstituted C 3 -C 60 cycloalkynyl , Substituted or unsubstituted C 1 -C 60 alkoxy, substituted or unsubstituted C 1 -C 60 alkenyloxy, substituted or unsubstituted C 1 -C 60 alkynyloxy, substituted or unsubstituted C 1 -C 60 alkylthio, substituted or unsubstituted C 1 -C 60 alkenylthio, substituted or unsub
  • Y 1 -Y 10 are independently selected from hydrogen, halogen, cyano, substituted or unsubstituted C 1 -C 60 alkyl, substituted or unsubstituted C 1 -C 60 alkenyl, substituted or unsubstituted C 1 -C 60 alkynyl, substituted or unsubstituted C 1 -C 60 alkylamino, substituted or unsubstituted C 1 -C 60 enamine, substituted or unsubstituted C 1 -C 60 Alkynylamino, substituted or unsubstituted C 1 -C 60 alkoxy, substituted or unsubstituted C 1 -C 60 alkenyloxy, substituted or unsubstituted C 1 -C 60 alkynyloxy, substituted Or unsubstituted C 1 -C 60 thioalkoxy, substituted or unsubstituted C 1 -C 60 thioalkenyloxy, substituted
  • the above dibenzoheterocyclic compound Preferably, the above dibenzoheterocyclic compound,
  • the R 1 and R 2 are independently selected from a substituted or unsubstituted C 1 -C 10 alkyl group, a substituted or unsubstituted C 1 -C 10 alkenyl group, a substituted or unsubstituted C 1 -C 10 Alkynyl, substituted or unsubstituted C 1 -C 10 alkoxy, substituted or unsubstituted C 1 -C 10 alkylthio;
  • the Y 1 -Y 10 are independently selected from hydrogen, substituted or unsubstituted C 4 -C 30 monocyclic aryl, substituted or unsubstituted C 3 -C 30 fused ring aryl, substituted or unsubstituted C 3 -C 30 monocyclic heteroaryl groups, substituted or unsubstituted C 3 -C 30 fused ring heteroaryl groups, substituted or unsubstituted C 4 -C 30 aromatic amine groups.
  • the Y 1 -Y 10 are independently selected from hydrogen, substituted or unsubstituted the following groups:
  • Ar 1 -Ar 5 are independently selected from hydrogen, C 1 -C 6 alkoxy, C 1 -C 6 alkylthio , Phenyl, biphenyl, terphenyl, pentenyl, indenyl, naphthyl, azulenyl, heptenyl, adamantyl, pentenyl, triphenylene, indole, acenaphthyl , Fluorenyl, spiro-difluorenyl, benzofluorenyl, dibenzofluorenyl, phenenyl, phenanthrenyl, anthracenyl, fluoranthenyl, benzophenanthrenyl, pyrenyl, quinyl, naphthacene Group, perylene group, perylene group, amyl group, pentacene group, rutile group,
  • the ring A is selected from the ring A 1 formed by Y 9 and Y 10 , the ring A 2 formed by Y 10 and Y 1 , and the ring A 3 formed by Y 2 and Y 1 , ring a 4, Y 4 a 5 are the Y formed of 3 Y 2 and Y 3 is formed, Y. 8 ring a forms with Y 7 6, Y 6 is formed with Y 7 ring a 7, Y 6 and Y 5 At least one of ring A 8 formed, and ring A 9 formed by Y 9 and Y 5 ;
  • the ring A 1 -ring A 9 are independently selected from a 3- to 7-membered saturated or partially unsaturated carbocyclic ring, a 3- to 7-membered saturated or partially unsaturated heterocyclic ring, a biphenyl ring, a terphenyl Rings, pendene rings, indene rings, naphthalene rings, azulene rings, heptadiene rings, adamantane rings, bowlene rings, triphenylene rings, indole provincial rings, acenaphthene rings, fluorene rings, spiro-bifluorene rings, Benzofluorene ring, dibenzofluorene ring, phenalene ring, phenanthrene ring, anthracene ring, fluoranthene ring, benzophenanthrene ring, pyrene ring, quinone ring, naphthacene ring, perylene ring, pery
  • the above dibenzoheterocyclic compound has the following structure:
  • the present invention provides a method for preparing the above dibenzoheterocyclic compound.
  • the synthesis steps of the dibenzoheterocyclic compound represented by formula (I) are as follows:
  • intermediate 1 is reacted with triphenylphosphine to form intermediate 2;
  • intermediate 2 is represented by formula (B) It shows that the compound undergoes Wittig reaction to obtain intermediate 3; intermediate 3 undergoes a condensation reaction with the compound represented by formula (C) to obtain intermediate 4; intermediate 4 and at least one compound of Y 1 -Y 8 , Y 1 -Y 8 of at least one borate, or a cyclic compound that forms any adjacent group in Y 1 -Y 8 reacts to produce an intermediate represented by formula (I');
  • the intermediate represented by formula (I′) is the dibenzoheterocyclic compound represented by the formula (I); when at least one of Y 9 and Y 10 is not hydrogen , The intermediate represented by the formula (I′) undergoes halogenation reaction to obtain the intermediate represented by the formula (I′′), and the intermediate represented by the formula (I′′) undergoes halogenation reaction with at least one of Y 9 -Y 10 Species or a cyclic compound that forms Y 9 and Y 10 to obtain a dibenzoheterocyclic compound represented by formula (I);
  • X 1 -X 4 are independently selected from halogen, and R 3 -R 10 are independently selected from halogen or hydrogen;
  • the synthetic route of the dibenzoheterocyclic compound represented by the formula (I) is as follows:
  • the present invention provides an application of the aforementioned dibenzoheterocyclic compound as an organic electroluminescent material.
  • the present invention provides an application of the above dibenzoheterocyclic compound in a blue light-emitting device.
  • the present invention provides an organic electroluminescence device. At least one functional layer of the organic electroluminescence device contains the above-mentioned dibenzoheterocyclic compound.
  • the functional layer is a light-emitting layer.
  • the light-emitting layer material includes a host material and a guest luminescent dye, and the guest luminescent material is the dibenzoheterocyclic compound.
  • the present invention provides a display device including the above-mentioned organic electroluminescent device.
  • Alkyl refers to: a fully saturated linear or branched hydrocarbon group.
  • alkyl includes but is not limited to methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, neopentyl, N-hexyl, 3-methylhexyl, 2,2-dimethylpentyl, 2,3-dimethylpentyl, n-heptyl, n-octyl, n-nonyl, n-decyl, etc.
  • Alkenyl refers to a linear or branched hydrocarbon group containing at least one olefinic bond.
  • alkenyl includes but is not limited to vinyl, allyl, etc.
  • Alkynyl refers to a straight-chain or branched hydrocarbon group containing at least one alkyne bond. For example: ethynyl, propynyl, etc.
  • Alkoxy refers to a group formed by connecting an alkyl group with an oxygen atom.
  • alkoxy includes but is not limited to methoxy (-OCH 3 ), ethoxy (-OCH 2 CH 3 ), etc.
  • Alkenyloxy refers to a group formed by connecting an alkenyl group with an oxygen atom.
  • Alkynyloxy refers to a group formed by connecting an alkynyl group with an oxygen atom.
  • alkynyloxy includes but is not limited to ethynyloxy (-OC ⁇ CH), propynyloxy (-OCH 2 C ⁇ CH), etc.
  • the aryloxy group refers to a group formed by connecting an aromatic hydrocarbon group and an oxygen atom.
  • aryloxy includes but is not limited to Wait.
  • alkylthio group refers to a group formed by connecting an alkyl group with a sulfur atom.
  • alkylthio groups include but are not limited to methylthio (-SCH 3 ), ethylthio (-SCH 2 CH 3 ), etc.
  • Alkenylthio refers to a group formed by connecting an alkenyl group with a sulfur atom.
  • Alkynylthio refers to a group formed by connecting an alkynyl group with a sulfur atom.
  • alkynylthio includes but is not limited to ethynylthio (-SC ⁇ CH), propynylthio (-SCH 2 C ⁇ CH), etc.
  • the alkylamine group refers to a group formed by connecting an alkyl group and an amine group (-NH 2 ).
  • alkylamino groups include but are not limited to methylamino (-NHCH 3 ), ethylamino (-NHCH 2 CH 3 ), etc.
  • the enamine group refers to a group formed by connecting an alkenyl group and an amine group.
  • the alkynylamino group refers to a group formed by connecting an alkynyl group and an amine group.
  • alkynylamino includes but is not limited to ethynylamino (-NHC ⁇ CH), propynylamino (-NHCH 2 C ⁇ CH), etc.
  • the aromatic amine group refers to a group formed by connecting an aromatic hydrocarbon group and an amine group (-NH 2 ).
  • aromatic amine groups include but are not limited to aniline, diphenylamine, etc.
  • the dibenzoheterocyclic compound provided by the present invention has a structure represented by formula (I).
  • the above compounds have a dibenzo seven-membered heterocyclic ring as the core structure.
  • the stilbene structure reduces the LUMO energy level of the dibenzo heterocyclic compound.
  • the dibenzo heterocyclic compound is used as a light emitting material, the light emitting layer
  • the LUMO energy level of the material molecule is more closely matched with the adjacent electron transport layer, which is conducive to the injection of electrons into the light-emitting layer, to balance the ratio of electrons and holes, improve the probability of carrier recombination, and improve the luminous efficiency of the device.
  • the dibenzoheterocyclic compound with the structure shown in formula (I) has a HOMO energy level matching the hole transport layer, and the dibenzoheterocyclic compound has good hole transport performance, which is conducive to hole injection and Transport, to further balance the injection and transport of carriers, to avoid the recombination of holes and electrons in the area near the electrode, resulting in the annihilation of excitons. Since the HOMO and LUMO energy levels of the dibenzoheterocyclic compound are matched with the hole transport layer and the electron transport layer, the barriers to be overcome for the injection of holes and electrons into the light emitting layer are reduced, and the operating voltage of the device is reduced.
  • the dibenzoheterocyclic compound exhibits a "butterfly configuration" in space structure, and its three-dimensional configuration results in no molecular stacking of material molecules, which can avoid energy transfer due to molecular stacking and avoid high-energy excitons. Production, effectively reduce the annihilation due to the presence of high-energy excitons.
  • the dibenzoheterocyclic compound can obtain more stable excitons after recombination of electrons and holes, which is helpful to reduce the roll-off of device efficiency due to the annihilation of excitons.
  • Dibenzoheterocyclic compounds have excellent film-forming properties and can form uniform amorphous films without pinholes; dibenzoheterocyclic compounds have high thermal decomposition temperature (T d ) and high thermal stability, which can avoid The material is decomposed by heat during film formation or use, to avoid loss of function of the material layer, and to improve the luminous efficiency and luminous performance of the device.
  • T d thermal decomposition temperature
  • the dibenzoheterocyclic compound of the structure represented by formula (I) emits light in the blue region, because its low LUMO energy level matches well with the LUMO energy level and the HOMO energy level of the electron transport layer and the hole transport layer, and the thermal decomposition temperature is high , High thermal stability, the spatial structure of the material molecule allows it to form stable excitons. Therefore, the dibenzoheterocyclic compound can now emit light in the blue region with high efficiency, and has a high luminescence stability, which can effectively reduce the color shift.
  • the dibenzoheterocyclic compound provided by the present invention can further introduce an electron-withdrawing group (pyridine, pyrimidine, triazine, pyrazine) into the dibenzoheterocyclic compound by selecting a substituent group of Y 1 -Y 8 , Oxadiazole, thiadiazole, quinazoline, imidazole, quinoxaline, quinoline, etc.), or electron-donating groups (diphenylamine, triphenylamine, fluorene, etc.), making the material molecule's HOMO energy level Increased, the LUMO energy level is reduced, and further matches the hole transport layer and the electron transport layer on both sides, which is beneficial to further improve the injection and transport of electrons and holes, and improve the recombination probability of electrons and holes.
  • an electron-withdrawing group pyridine, pyrimidine, triazine, pyrazine
  • the HOMO energy level is distributed in the electron-donating group, the LOMO level electron-withdrawing group, the HOMO energy level and the LOMO energy level are relatively separated, and a small single-triplet energy level difference ( ⁇ E ST ), triplet excitons can be obtained (T 1) by crossing between a reverse (RISC) is converted to singlet excitons (S 1), by a singlet exciton emission, theoretically achieve an internal quantum efficiency of 100%.
  • RISC reverse
  • S 1 singlet excitons
  • the starting materials are easy to obtain, the reaction conditions are mild, and the operation steps are simple, which provides a simple and easy to implement for the large-scale production of the above dibenzoheterocyclic compounds ⁇ Preparation method.
  • At least one functional layer of the organic electroluminescence device contains the above-mentioned dibenzoheterocyclic compound.
  • the functional layer is a light-emitting layer.
  • the dibenzoheterocyclic compound As a material for the light-emitting layer, the dibenzoheterocyclic compound has a low LUMO energy level and is well matched with the energy level of the electron transport layer, which is conducive to electron injection and transport; the dibenzoheterocyclic compound has good
  • the hole-transporting performance of the IC is matched with the energy level of the hole-transporting layer, which is beneficial to balance the injection and transport of electrons and holes, improve the carrier recombination probability, and can obtain blue OLED devices with high luminous efficiency.
  • the spatial configuration of the dibenzoheterocyclic compound makes the exciton in the light-emitting layer highly stable, and the efficiency roll-off of the OLED device due to the annihilation of the exciton; the HOMO and LUMO energy levels of the dibenzoheterocyclic compound and the hole transport layer and The matching of the electron transport layer reduces the potential barrier to be overcome when holes and electrons are injected into the light-emitting layer, so that the working voltage of the device is reduced.
  • the dibenzoheterocyclic compound has high thermal stability and stable film-forming performance, and can obtain a blue OLED device with high luminous efficiency, long service life, and high color stability.
  • a dibenzoheterocyclic compound with thermally activated delayed fluorescence properties is obtained, which converts triplet excitons into singlet excitons, and utilizes singlet excitons to emit light to further increase the height of the blue device.
  • the efficient solution of blue light emission solves the problem of low luminous efficiency of the blue OLED device due to the high blue light energy.
  • the dibenzoheterocyclic compound when it has both an electron-withdrawing group and an electron-donating group, it can also be used as the host material of the light-emitting layer, so that the host material has a bipolar and narrow energy gap, which is conducive to electrons and space.
  • the holes are recombined on the host material, which increases the recombination area, reduces the concentration of excitons, effectively reduces the quenching of excitons, and solves the problems of low efficiency and short life due to exciton quenching.
  • the high anti-intersystem crossing (RISC) rate of dibenzoheterocyclic compounds as host materials T 1 to S 1 can inhibit the Dexter energy transfer from host materials to guest luminescent dyes (DET), promote Energy transfer improves the ratio of singlet excitons and suppresses triplet excitons, thereby greatly reducing the exciton loss of Dexter energy transfer (DET), effectively reducing the efficiency roll-off of OLED devices, and improving the external quantum efficiency of the device .
  • RISC intersystem crossing
  • Example 1 is a schematic structural view of an organic electroluminescent device in Example 11 to Example 19 and Comparative Example 1 of the present invention
  • This embodiment provides a dibenzoheterocyclic compound having a structure represented by the following formula SP-01:
  • the preparation method of the dibenzoheterocyclic compound represented by formula SP-01 includes the following steps:
  • This embodiment provides a dibenzoheterocyclic compound having a structure represented by the following formula SP-02:
  • the synthetic route of the dibenzoheterocyclic compound represented by formula SP-02 is as follows:
  • the preparation method of the dibenzoheterocyclic compound represented by formula SP-02 includes the following steps:
  • This embodiment provides a dibenzoheterocyclic compound having a structure represented by the following formula SP-03:
  • the preparation method of the dibenzoheterocyclic compound represented by formula SP-03 includes the following steps:
  • This embodiment provides a dibenzo heterocyclic compound having a structure represented by the following formula SP-04:
  • the preparation method of the dibenzoheterocyclic compound represented by formula SP-04 includes the following steps:
  • This embodiment provides a dibenzoheterocyclic compound having a structure represented by the following formula SP-32:
  • the preparation method of the dibenzoheterocyclic compound represented by formula SP-32 includes the following steps:
  • This embodiment provides a dibenzoheterocyclic compound having a structure represented by the following formula SP-34:
  • the preparation method of the dibenzoheterocyclic compound represented by formula SP-34 includes the following steps:
  • This embodiment provides a dibenzoheterocyclic compound having a structure represented by the following formula SP-36:
  • the synthetic route of the dibenzoheterocyclic compound represented by formula SP-36 is as follows:
  • the preparation method of the dibenzoheterocyclic compound represented by formula SP-36 includes the following steps:
  • This embodiment provides a dibenzoheterocyclic compound having a structure represented by the following formula SP-38:
  • the preparation method of the dibenzoheterocyclic compound represented by formula SP-38 includes the following steps:
  • This embodiment provides a dibenzoheterocyclic compound having a structure represented by the following formula SP-55:
  • the preparation method of the dibenzoheterocyclic compound represented by formula SP-55 includes the following steps:
  • This embodiment provides a dibenzoheterocyclic compound having a structure represented by the following formula SP-56:
  • the synthetic route of the dibenzoheterocyclic compound represented by formula SP-56 is as follows:
  • the preparation method of the dibenzoheterocyclic compound represented by formula SP-56 includes the following steps:
  • This embodiment provides a dibenzoheterocyclic compound having a structure represented by the following formula SP-42:
  • the synthetic route of the dibenzoheterocyclic compound represented by formula SP-42 is as follows:
  • the preparation method of the dibenzoheterocyclic compound represented by formula SP-56 includes the following steps:
  • This embodiment provides an organic electroluminescent device. As shown in FIG. 1, it includes an anode 1, a hole injection layer 2, a hole transport layer 3, a light emitting layer 4, and an electron transport layer 5, which are sequentially stacked on a substrate. Electron injection layer 6 and cathode 7.
  • the anode is made of ITO material; the cathode 7 is made of metal Al;
  • the material of hole injection layer 2 is PEDOT:PSS, which has the following chemical structure:
  • the material of the hole transport layer 3 is NPB, which has the chemical structure shown below:
  • TPBI The material of electron transport layer 5 is TPBI.
  • TPBI has the following chemical structure:
  • the material of electron injection layer 6 is doped with TPBI and electron injection material LiF;
  • the light-emitting material of the light-emitting layer 32 in the organic electroluminescent device is a dibenzo heterocyclic compound represented by formula SP-01:
  • the organic electroluminescent device forms the following specific structure: ITO (anode)/PEDOT: PSS (hole injection layer, 30nm)/NPB (hole transport layer, 40nm)/SP-01 (blue light emitting layer, 40nm)/TPBI ( Electron injection layer, 35 nm)/TPBI: LiF (electron transport layer, 40 nm) aluminum (cathode, 5 nm/150 nm).
  • the material of the light-emitting layer is a dibenzoheterocyclic compound SP-01, and its light-emitting color coordinate is located in the blue light-emitting region, and a blue light-emitting device can be obtained. Due to the presence of stilbene groups in the core structure, compound SP-01 has a low LUMO energy level (-1.35eV), which is beneficial to match the energy level of the electron transport layer and promote the injection and transport of electrons.
  • the dibenzoheterocyclic compound SP-01 is connected with an electron-donating substituent
  • the material molecule has good hole transport performance, and its HOMO energy level is suitable for matching the adjacent hole transport layer, which is beneficial to balance the electrons and holes in the light-emitting layer, improve the probability of electron and hole recombination, and make the OLED device
  • the blue light emitting efficiency has been improved.
  • the spatial configuration of the dibenzoheterocyclic compound SP-01 is a butterfly configuration, which avoids the generation of high-energy excitons caused by the stacking of material molecules, effectively reduces the annihilation of excitons in the light-emitting layer, and avoids the roll-off of the efficiency of blue devices.
  • the blue color coordinate drift is prevented, and a blue light device with high luminous stability is obtained.
  • the suitable HOMO energy level and LUMO energy level of the dibenzoheterocyclic compound SP-01 are beneficial to reduce the barriers to be overcome when electrons and holes are transported to the light-emitting layer, and the working voltage of the device is reduced.
  • the dibenzoheterocyclic compound shown in SP-01 has high thermal decomposition temperature, high thermal stability and morphological stability, and excellent film-forming properties. As a light-emitting layer material, it is not easy to decompose and crystallize, which further enhances OLED devices Performance and luminous efficiency.
  • the guest light-emitting material of the light-emitting layer may also be any dibenzoheterocyclic compound represented by formula (SP-02) to formula (SP-65).
  • the guest light-emitting material of the light-emitting layer may also be any other dibenzoheterocyclic compound having the chemical structure represented by the general formula (I).
  • This embodiment provides an organic electroluminescent device, which differs from the organic electroluminescent device provided in embodiment 12 only in that the light-emitting layer material uses a dibenzoheterocyclic compound of the following structure:
  • This embodiment provides an organic electroluminescent device, which differs from the organic electroluminescent device provided in embodiment 12 only in that the light-emitting layer material uses a dibenzoheterocyclic compound of the following structure:
  • This embodiment provides an organic electroluminescent device, which differs from the organic electroluminescent device provided in embodiment 12 only in that the light-emitting layer material uses a dibenzoheterocyclic compound of the following structure:
  • This embodiment provides an organic electroluminescent device, which differs from the organic electroluminescent device provided in embodiment 12 only in that the light-emitting layer material uses a dibenzoheterocyclic compound having the following structure:
  • This embodiment provides an organic electroluminescent device, which differs from the organic electroluminescent device provided in embodiment 12 only in that the light-emitting layer material uses a dibenzoheterocyclic compound of the following structure:
  • This embodiment provides an organic electroluminescent device, which differs from the organic electroluminescent device provided in embodiment 12 only in that the light-emitting layer material uses a dibenzoheterocyclic compound of the following structure:
  • This embodiment provides an organic electroluminescent device, which differs from the organic electroluminescent device provided in embodiment 12 only in that the light-emitting layer material uses a dibenzoheterocyclic compound of the following structure:
  • This comparative example provides an organic electroluminescent device, which differs from the organic electroluminescent device provided in Example 12 only in that: the light-emitting layer material uses a compound of the following structure:
  • T d thermal decomposition temperature
  • the thermal decomposition temperature test of the patented material was carried out using a thermogravimetric analyzer (TGA).
  • TGA thermogravimetric analyzer
  • the electrochemical workstation was used to test the HOMO and LUMO energy levels of the patented material using cyclic voltammetry (CV), with platinum wire (Pt) as the counter electrode and silver/silver chloride (Ag/AgCl) as the reference electrode.
  • CV cyclic voltammetry
  • Pt platinum wire
  • Ag/AgCl silver/silver chloride
  • test in a dichloromethane electrolyte containing 0.1M tetrabutylammonium hexafluorophosphate at a scan rate of 100 mV/s perform potential calibration with ferrocene, set the potential of ferrocene in vacuum
  • the absolute HOMO energy level in the state is -4.8eV:
  • the dibenzoheterocyclic compound provided by the present invention has a high thermal decomposition temperature and high thermal stability after film formation, and the material molecules are not easy to decompose with the heat generated during the use of the device Or crystallization, can keep the function of the light-emitting layer stable, avoid device collapse, and extend the service life of the device.
  • dibenzoheterocyclic compounds have a low LUMO energy level (-1.30 to -1.57eV), which is conducive to the injection and transport of electrons to the light-emitting layer and improves the proportion of electrons, because the hole transport performance of semiconductor materials is generally higher than that of electrons. Transmission performance, dibenzoheterocyclic compounds are conducive to balancing electrons and holes, so that the luminous efficiency of the device is improved.
  • the dibenzoheterocyclic compound provided by the present invention is used as a light-emitting layer material, which is beneficial to reduce the operating voltage of the device, improve the luminous efficiency of the device, and obtain a blue light-emitting device with high efficiency and stable performance.

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Abstract

本发明公开了一种二苯并杂环化合物，具有式(I)所示结构。二苯并杂环化合物的LUMO能级低，能够与电子传输材料良好匹配，有利于电子的注入与传输。二苯并杂环化合物具有良好的空穴传输性能，作为发光层材料能够平衡发光层中电子和空穴的比例，提高复合几率，使器件发光效率提升。二苯并杂环化合物的空间构型能够避免材料分子堆叠，进而避免分子间能量传递导致高能激子产生，减轻激子湮灭，抑制效率滚降。同时，二苯并杂环化合物具有良好的热稳定性，能够实现高效稳定的蓝光发光。本发明还公开了一种有机电致发光器件，至少有一个功能层中含有上述的二苯并杂环化合物，能够得到具有高蓝光发光效率和低工作电压的蓝光器件。

Description

一种二苯并杂环化合物及其制备方法和应用
交叉引用
本申请要求在2018年12月29日提交中国专利局、申请号为201811643571.1、发明名称为“一种二苯并杂环化合物及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及有机电致发光材料领域，具体涉及一种二苯并杂环化合物及其制备方法和应用。
背景技术
有机电致发光器件(organic light-emitting diodes，OLED)由于有驱动电压低、发光效率高、对比度高、色饱和度高、能耗低、主动发光、视角宽、响应快等优点，在显示和照明领域有极大的应用前景，越来越受到人们的重视。
1987年，美国Kodak公司的Tang等利用真空沉积镀膜的方法制备出多层结构的OLED器件。OLED器件以导电的氧化铟锡(ITO)作为阴极，并在上面依序蒸镀芳香胺衍生物与三(8-羟基喹啉)铝，阳极材料则使用镁银合金，得到了具有高亮度(1000cd/m 2)的绿光发光器件。同时，由于对器件结构进行优化，增加了以芳香胺衍生物形成的空穴传输层，实现了较高的发光亮度和发光效率，并使驱动电压降低到10V以下。此后，有机电致发光材料的研究引起了各国科学家的关注，成为了学术界和产业界的研究热点。
荧光材料是最早应用的第一代OLED材料，但是此类材料所组成的器件效率低，仅仅能利用材料25％的单线态激子发光，75％的三线态态电致激子由于自旋禁阻作用以非辐射失活的形式回到基态，很大程度上限制了器件的效率。直到1998年，Baldo等首次报道通过在有机小分子中引入铱(III)、铂(II)以及锇(II)等金属形成配合物，可以通过自旋耦合作用使得材料的三线态激子能够辐射跃迁发出磷光，获得了理论上100％的内量子效率。2012年日本九州大学Chihaya Adachi教授发现了具有小的单线态-三线态能级差(ΔE ST)的TADF材料，TADF材料的三线态激子可以通过反系间窜越(RISC)转变成单线态激子发光，充分利用了之前无法利用的75％的三线态激子，器件的内量子效率可以达到100％。
目前，磷光材料和TADF材料的开发使得红色、绿色的发光材料已经能够满足有机电致发光器件的发光性能要求。然而，蓝光发光材料由于吸收光谱的波长较短、LUMO与HOMO间的带隙宽，使的蓝光发光材料的辐射发光需要获得更多能量，限制了蓝光器件的发光效率。蓝光发光材料主要是共轭片段简单的平面芳香环分子，热稳定性低，在成膜和使用过程中容易因热量而发生分解，影响器件的效率和寿命。同时，平面型的芳香环分子发生相互堆叠，容易形成激基双体，激子的能量增高产生湮灭，使器件的发光效率降低，使用寿命缩短，发光颜色也会发生改变、产生色偏。
发明内容
因此，本发明要解决的技术问题在于克服现有技术中的蓝光发光材料热稳定性低、激子易发生湮灭，使器件的发光效率降低、使用寿命缩短的缺陷。
为此，本发明提供如下技术方案：
第一方面，本发明提供了一种二苯并杂环化合物，具有如式(I)所示的结构：
Figure PCTCN2019083653-appb-000001
其中，R 1、R 2彼此独立地选自氢、取代或未取代的C 1-C 60的烷基、取代或未取代的C 1-C 60的烯基、取代或未取代的C 1-C 60的炔基、取代或未取代的C 3-C 60的环烷基、取代或未取代的C 3-C 60的环烯基、取代或未取代的C 3-C 60的环炔基、取代或未取代的C 1-C 60的烷氧基、取代或未取代的C 1-C 60的烯氧基、取代或未取代的C 1-C 60的炔氧基、取代或未取代的C 1-C 60的烷基硫基、取代或未取代的C 1-C 60的烯基硫基、取代或未取代的C 1-C 60的炔基硫基、取代或未取代的C 1-C 60的酯基，或者取代或未取代的C 1-C 60的酰胺基；
Y 1-Y 10彼此独立地选自氢、卤素、氰基、取代或未取代的C 1-C 60的烷基、取代或未取代的C 1-C 60的烯基、取代或未取代的C 1-C 60的炔基、取代或未取代的C 1-C 60的烷胺基、取代或未取代的C 1-C 60的烯胺基、取代或未取代的C 1-C 60的炔胺基、取代或未取代的C 1-C 60的烷氧基、取代或未取代的C 1-C 60的烯氧基、取代或未取代的C 1-C 60的炔氧基、取代或未取代的C 1-C 60的硫代烷氧基、取代或未取代的C 1-C 60的硫代烯氧基、取代或未取代的C 1-C 60的硫代炔氧基、取代或未取代的C 1-C 60的烷硼基、取代或未取代的C 1-C 60的烯硼基、取代或 未取代的C 1-C 60的炔硼基、取代或未取代的C 1-C 60的酯基、取代或未取代的C 1-C 60的酰胺基、取代或未取代的C 4-C 60的芳基、取代或未取代的C 3-C 60的杂芳基、取代或未取代的C 4-C 60的芳氧基、取代或未取代的C 4-C 60的芳香胺基、取代或未取代的C 4-C 60的硫代芳氧基、取代或未取代的C 4-C 60的芳硼基；或者Y 1-Y 10中任意相邻的两个基团结合形成环A，所述环A选自3元到7元的饱和或部分不饱和的碳环、3元到7元的饱和或部分不饱和的杂环、C 4-C 60的稠环芳基或C 3-C 30的稠环杂芳基。
优选地，上述的二苯并杂环化合物，
所述R 1、R 2彼此独立地选自取代或未取代的C 1-C 10的烷基、取代或未取代的C 1-C 10的烯基、取代或未取代的C 1-C 10的炔基、取代或未取代的C 1-C 10的烷氧基、取代或未取代的C 1-C 10的烷基硫基；
所述Y 1-Y 10彼此独立地选自氢、取代或未取代的C 4-C 30的单环芳基、取代或未取代的C 3-C 30的稠环芳基、取代或未取代的C 3-C 30的单环杂芳基、取代或未取代的C 3-C 30的稠环杂芳基、取代或未取代的C 4-C 30的芳香胺基。
优选地，上述的二苯并杂环化合物，所述Y 1-Y 10彼此独立地选自氢、取代或未取代的下述基团：
苯基、联苯基、三联苯基、戊搭烯基、茚基、萘基、薁基、庚搭烯基、金刚烷基、碗烯基、三亚苯基、引达省基、苊基、芴基、螺-二芴基、苯并芴基、二苯并芴基、非那烯基、菲基、蒽基、荧蒽基、苯并菲基、芘基、屈基、并四苯基、苉基、苝基、戊芬基、并五苯基、玉红省基、蔻基、卵苯基、吡啶基、吡嗪基、嘧啶基、哒嗪基、三嗪基、噻吩基、呋喃基、喹啉基、咔唑基、吡喃基、噻喃基、酞嗪基、吩嗪基、吡咯基、吡唑基、咪唑基、噁唑基、噻唑基、吲哚基、吲哚并咔唑基、菲啶基、吖啶基、呸啶基、蝶啶基、喹唑啉基、喹喔啉基、噌啉基、菲咯琳基、咔啉基、苯并呋喃基、苯并噻吩基、二苯并呋喃基、二苯并噻吩基、苯并萘并呋喃基、二萘并呋喃基、苯并咔唑基、二苯并咔唑基、二苯并噻咯基、苯并萘并噻咯基、二萘并噻咯基、苯并咪唑基、咪唑并吡啶基、
Figure PCTCN2019083653-appb-000002
或者由上述基团形成的稠环基、螺环基或连环基；
其中，p为1-5的整数，q为1-5的整数，Ar 1-Ar 5彼此独立的选自氢、C 1-C 6的烷氧基、C 1-C 6的烷基硫基、苯基、联苯基、三联苯基、戊搭烯基、茚基、萘基、薁基、庚搭烯基、金刚烷基、碗烯基、三亚苯基、引达省基、苊基、芴基、螺-二芴基、苯并芴基、二苯并芴基、非那烯基、菲基、蒽基、荧蒽基、苯并菲基、芘基、屈基、并四苯基、苉基、苝基、戊芬基、并五苯基、玉红省基、蔻基、卵苯基、吡啶基、吡嗪基、嘧啶基、哒嗪基、三嗪基、噻吩基、呋喃基、喹啉基、咔唑基、吡喃基、噻喃基、酞嗪基、吩嗪基、吡咯基、吡唑基、咪唑基、噁唑基、噻唑基、吲哚基、吲哚并咔唑基、菲啶基、吖啶基、呸啶基、蝶啶基、喹唑啉基、喹喔啉基、噌啉基、菲咯琳基、咔啉基、苯并呋喃基、苯并噻吩基、二苯并呋喃基、二苯并噻吩基、苯并萘并呋喃基、二萘并呋喃基、苯并咔唑基、二苯并咔唑基、二苯并噻咯基、苯并萘并噻咯基、二萘并噻咯基、苯并咪唑基、咪唑并吡啶基，或者由上述基团形成的稠环基、螺环基或连环基。
优选地，上述的二苯并杂环化合物，所述环A选自Y 9与Y 10形成的环A 1、Y 10与Y 1形成的环A 2、Y 2与Y 1形成的环A 3、Y 2与Y 3形成的环A 4、Y 4与Y 3形成的环A 5、Y 8与Y 7形成的环A 6、Y 6与Y 7形成的环A 7、Y 6与Y 5形成的环A 8，和Y 9与Y 5形成的环A 9中的至少一种；
所述环A 1-环A 9彼此独立地选自3元到7元的饱和或部分不饱和的碳环、3元到7元的饱和或部分不饱和的杂环、联苯环、三联苯环、戊搭烯环、茚环、萘环、薁环、庚搭烯环、金刚烷环、碗烯环、三亚苯环、引达省环、苊环、芴环、螺-二芴环、苯并芴环、二苯并芴环、非那烯环、菲环、蒽环、荧蒽环、苯并菲环、芘环、屈环、并四苯环、苉环、苝环、戊芬环、并五苯环、玉红省环、蔻环、卵苯环、吡啶环、吡嗪环、嘧啶环、哒嗪环、三嗪环、噻吩环、呋喃环、喹啉环、咔唑环、吡喃环、噻喃环、酞嗪环、吩嗪环、吡咯环、吡唑环、咪唑环、噁唑环、噻唑环、吲哚环、吲哚并咔唑环、菲啶环、吖啶环、呸啶环、蝶啶环、喹唑啉环、喹喔啉环、噌啉环、菲咯琳环、咔啉环、苯并呋喃环、苯并噻吩环、二苯并呋喃环、二苯并噻吩环、苯并萘并呋喃环、二萘并呋喃环、苯并咔唑环、二苯并咔唑环、二苯并噻咯环、苯并萘并噻咯环、二萘并噻咯环、苯并咪唑环、咪唑并吡啶环，或者由上述基团形成的稠环、螺环或连环。
优选地，上述的二苯并杂环化合物，具有如下所示结构：
Figure PCTCN2019083653-appb-000003
Figure PCTCN2019083653-appb-000004
Figure PCTCN2019083653-appb-000005
Figure PCTCN2019083653-appb-000006
Figure PCTCN2019083653-appb-000007
Figure PCTCN2019083653-appb-000008
第二方面，本发明提供了一种上述的二苯并杂环化合物的制备方法，所述式(I)所示二苯并杂环化合物的合成步骤如下所示：
以式(A)所示的化合物为起始原料，在催化剂作用下经卤化反应，得到中间体1，中间体1与三苯磷反应，生成中间体2；中间体2与式(B)所示化合物发生维悌希反应，得到中间体3；中间体3与式(C)所示化合物发生缩合反应，得到中间体4；中间体4与Y 1-Y 8中至少一种的化合物、Y 1-Y 8的至少一种的硼酸化物，或形成Y 1-Y 8中任意相邻基团的环状化合物反应，生成式(I’)所示的中间体；
Y 9、Y 10分别为氢时，式(I’)所示的中间体即为所述式(I)所示二苯并杂环化合物；Y 9、Y 10中的至少一个不为氢时，式(I’)所示的中间体发生卤化反应，得到式(I”)所示的中间体，式(I”)所示的中间体发生卤化反应，与Y 9-Y 10中至少一种的化合物或形成Y 9、Y 10的环状化合物反应，得到式(I)所示二苯并杂环化合物；
其中，X 1-X 4彼此独立地选自卤素，R 3-R 10彼此独立地选自卤素或氢；
所述式(I)所示二苯并杂环化合物的合成路线如下所示：
Figure PCTCN2019083653-appb-000009
Figure PCTCN2019083653-appb-000010
第三方面，本发明提供了一种上述的二苯并杂环化合物作为有机电致发光材料的应用。
第四方面，本发明提供了一种上述的二苯并杂环化合物在蓝光发光器件中的应用。
第五方面，本发明提供了一种有机电致发光器件，所述有机电致发光器件的至少有一个功能层中含有上述的二苯并杂环化合物。
优选地，上述的有机电致发光器件，所述功能层为发光层。
进一步优选的，上述的有机电致发光器件，所述发光层材料包括主体材料和客体发光染料，所述客体发光材料为所述二苯并杂环化合物。
第六方面，本发明提供了一种显示装置，包括上述的有机电致发光器件。
除非有另外说明，本发明的权利要求书和说明书的术语具有下述含义：
烷基是指：完全饱和的直链的或支链的烃基。例如：烷基包括但不限于甲基、乙基、正丙基、异丙基、正丁基、仲丁基、异丁基、叔丁基、正戊基、异戊基、新戊基、正己基、3-甲基己基、2,2-二甲基戊基、2,3-二甲基戊基、正庚基、正辛基、正壬基、正癸基等。烯基是指：含有至少一个烯键的直链的或支链的烃基。例如：烯基包括但不限于乙烯基、烯丙基等。炔基是指：含有至少一个炔键的直链的或支链的烃基。例如：乙炔基、丙炔基等。
烷氧基是指：烷基与氧原子连结后的生成基团。例如：烷氧基包括但不限于甲氧基(-OCH 3)、乙氧基(-OCH 2CH 3)等。烯氧基是指：烯基与氧原子连结后的生成基团。例如：烯氧基包括但不限于乙烯氧基(-OCH＝CH 2)、丙烯氧基(-OCH 2CHCH 2)等。炔氧基是指：炔基与氧原子连结后的生成基团。例如：炔氧基包括但不限于乙炔氧基(-OC≡CH)、丙炔氧基(-OCH 2C≡CH)等。芳氧基是指：芳烃基与氧原子连结后的生成基团。例如：芳氧基包括但不限于
Figure PCTCN2019083653-appb-000011
等。
烷基硫基是指：烷基与硫原子连结后的生成基团。例如：烷基硫基包括但不限于甲基硫基(-SCH 3)、乙基硫基(-SCH 2CH 3)等。烯基硫基是指：烯基与硫原子连结后的生成基团。例如：烯基硫基包括但不限于乙烯基硫基(-SCH＝CH 2)、丙烯基硫基(-SCH 2CHCH 2)等。炔基硫基是指：炔基与硫原子连结后的生成基团。例如：炔基硫基包括但不限于乙炔基硫基(-SC≡CH)、丙炔基硫基(-SCH 2C≡CH)等。
烷胺基是指：烷基与胺基(-NH 2)连结后的生成基团。例如：烷胺基包括但不限于甲胺基(-NHCH 3)、乙胺基(-NHCH 2CH 3)等。烯胺基是指：烯基与胺基连结后的生成基团。例如：烯胺基包括但不限于乙烯胺基(-NHCH＝CH 2)、丙烯胺基(-NHCH 2CHCH 2)等。炔胺基是指：炔基与胺基连结后的生成基团。例如：炔胺基包括但不限于乙炔胺基(-NHC≡CH)、丙炔胺基(-NHCH 2C≡CH)等。芳香胺基是指：芳烃基与胺基(-NH 2)连结后的生成基团。例如：芳香胺基包括但不限于苯胺、二苯胺等。
本发明技术方案，具有如下优点：
1.本发明提供的二苯并杂环化合物，具有式(I)所示的结构。上述的化合物以二苯并七元杂环为母核结构，其中的二苯乙烯结构使二苯并杂环化合物的LUMO能级降低，二苯并杂环化合物在作为发光材料时，使发光层材料分子的LUMO能级与相邻的电子传输层更加匹配，有利于电子向发光层中的注入，以平衡电子和空穴的比例，提高载流子复合的几率，使器件的发光效率提升。同时，式(I)所示结构的二苯并杂环化合物具有与空穴传输层相匹配的HOMO能级，二苯并杂环化合物具有良好的空穴传输性能，有利于空穴的注入与传输，进一步平衡载流子的注入与传输，避免空穴和电子在靠近电极的区域复合、导致激子湮灭。由于二苯并杂环化合物的HOMO与LUMO能级与空穴传输层和电子传输层相匹配，降低了空穴和电子向发光层注入需要克服的势垒，使器件的工作电压降低。
另一方面，二苯并杂环化合物在空间结构上呈现“蝴蝶构型”，其立体构型的结构导致材料分子不会发生分子堆叠，能够避免由于分子堆叠导致的能量传递，避免高能激子的产生，有效减少由于高能激子存在产生的湮灭。二苯并杂环化合物在电子与空穴复合后能够得到更加稳定的激子，有利于减少由于激子湮灭发生的器件效率滚降。
二苯并杂环化合物的成膜性能优异，能够形成无针孔的均一无定形薄膜；二苯并杂环化合物的热分解温度(T d)高，具有较高的热稳定性，能够避免在成膜或使用过程材料受热分解，避免材料层功能的丧失，提高器件的发光效率和发光性能。
式(I)所示结构的二苯并杂环化合物在蓝光区域发光，由于其LUMO能级低、与电子传输层和空穴传输层的LUMO能级和HOMO能级匹配良好，热分解温度高、热稳定性高，材料分子的空间结构使其能够形成稳定的激子。因此，二苯并杂环化合物能够现在蓝光区域的高效发光，且具有较高的发光稳定性，能够有效减少色偏。
2.本发明提供的二苯并杂环化合物，通过选择Y 1-Y 8的取代基团，能够在二苯并杂环化合物中进一步引入吸电子基团(吡啶，嘧啶，三嗪，吡嗪，恶二唑，噻二唑，喹唑啉，咪唑，喹喔啉，喹啉等等)，或者是给电子基团(二苯胺，三苯胺，芴等等)，使材料分子的HOMO能级提高，LUMO能级降低，进一步与两侧的空穴传输层和电子传输层相匹配，有利于进一步提高电子与空穴的注入和传输，提高电子和空穴的复合几率。另一方面，HOMO能级分布于给电子集团，LOMO能级吸电子基团，HOMO能级与LOMO能级相对分离，能够获得小的单-三线态能级差(ΔE ST)，三线态激子(T 1)通过反向系间窜越(RISC)转换为单线态激子(S 1)，通过单线态激子发光，达到理论上100％的内量子效率。通过调节取代基团，得到具有热活化延迟荧光性能的二苯并杂环化合物，实现高发光效率和发光稳定性的蓝光发光。
3.本发明提供的二苯并杂环化合物的制备方法，起始原料易于获得，反应条件温和，操作步骤简单，为上述二苯并杂环化合物的大规模生产提供了一种简单、易于实现的制备方法。
4.本发明提供的有机电致发光器件(OLED)，有机电致发光器件的至少有一个功能层中含有上述的二苯并杂环化合物。其中，所述功能层为发光层。
二苯并杂环化合物作为发光层材料，由于二苯并杂环化合物LUMO能级低，与电子传输层的能级匹配良好，有利于电子的注入与传输；二苯并杂环化合物的具有良好的空穴传输性能，与空穴传输层的能级相匹配，有利于平衡电子和空穴的注入与传输，提高载流子复合几率，能够得到具有高发光效率的蓝光OLED器件。二苯并杂环化合物的空间构型使发光层内激子的稳定性高，OLED器件由于激子湮灭发生效率滚降；二苯并杂环化合物的HOMO与LUMO能级与空穴传输层和电子传输层相匹配，降低了空穴和电子向发光层注入需要克服的势垒，使器件的工作电压降低。同时，二苯并杂环化合物的热稳定性高，成膜性能稳定，能够得到发光效率高、使用寿命长、色稳定性高的蓝光OLED器件。
进一步的，通过调节取代基团，得到具有热活化延迟荧光性能的二苯并杂环化合物，使三线态激子上转换为单线态激子，利用单线态激子发光，进一步提高蓝光器件的高效率的蓝光发光解，决了蓝光OLED器件由于蓝光能量高导致的器件发光效率低的问题。
另外，在二苯并杂环化合物兼具吸电子基团和给电子基团时，还能够作为发光层的主体材料，使主体材料具有双极性和较窄的能隙，有利于电子和空穴在主体材料上复合，增大了复合区域，降低激子浓度，有效减少激子淬灭，解决了由于激子淬灭造成的效率低和寿命短的问题。另外，相比传统的主体材料，二苯并杂环化合物作为主体材料T 1向S 1转化的高反系间穿越(RISC)速率可以抑制从主体材料到客体发光染料的德克斯特能量转移(DET)，促进
Figure PCTCN2019083653-appb-000012
能量转移，提高单线态激子比例，同时抑制三线态激子，从而大大减少德克斯特能量转移(DET)的激子损失，有效降低了OLED器件的效率滚降，器件的外量子效率提高。
附图说明
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。
图1是本发明一个实施例11-实施例19和对比例1中的有机电致发光器件的结构示意图；
图2为本申请中实施例5提供的式SP-32所示的化合物的HOMO能级、LUMO能级和△E st的理论计算结果图；
附图标记：
1-阳极，2-空穴注入层，3-空穴传输层，4-发光层，5-电子传输层，6-电子注入层，7-阴极。
具体实施方式
下面将对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。此外，下面所描述的本发明不同实施方式中所涉及的技术特征只要彼此之间未构成冲突就可以相互结合。
在本发明的描述中，需要说明的是，术语“第一”、“第二”、“第三”仅用于描述目的，而不能理解为指示或暗示相对重要性。
本发明可以以许多不同的形式实施，而不应该被理解为限于在此阐述的实施例。相反，提供这些实施例，使得本公开将是彻底和完整的，并且将把本发明的构思充分传达给本领域技术人员，本发明将仅由权利要求来限定。在附图中，为了清晰起见，会夸大层和区域的尺寸和相对尺寸。应当理解的是，当元件例如层被称作“形成在”或“设置在”另一元件“上”时，该元件可以直接设置在所述另一元件上，或者也可以存在中间元件。相反，当元件被称作“直接形成在”或“直接设置在”另一元件上时，不存在中间元件。
实施例1
本实施提供一种二苯并杂环化合物，具有如下式SP-01所示的结构：
Figure PCTCN2019083653-appb-000013
式SP-01所示的二苯并杂环化合物的合成路径如下所示：
Figure PCTCN2019083653-appb-000014
式SP-01所示的二苯并杂环化合物的制备方法包括以下步骤：
1、制备中间体1-1
取500毫升双颈圆底瓶并放入搅拌子与上接回流管，干燥后充入氮气；先分别加入化合物A-1(20.548克，1.0当量)、NBS(N-溴代琥珀酰亚胺，19.578克，1.1当量)、及AIBN(偶氮二异丁腈，0.821克，0.5摩尔百分比)，接着加入四氯化碳(250毫升)并搅拌混合10分钟，最后再加热至回流并反应24小时；待其回温后加入水(200毫升)，接着用乙酸乙酯(3×200毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/10)，得到中间体1-1(21.044克，产率74％)。
2、制备中间体2-1
取500毫升双颈圆底瓶并放入搅拌子与上接回流管，干燥后充入氮气；先分别加入中间体1-1(20.000克， 1.0当量)和三苯磷(19.369克，1.05当量)，接着加入甲苯(250毫升)并搅拌混合10分钟，最后再加热至回流并反应18小时；待其回温后过滤，接着用己烷(3×80毫升)清洗所得到的固体，得到中间体2-1的粗产物(38.231克)。
3、制备中间体3-1
取500毫升双颈圆底瓶并放入搅拌子，干燥后充入氮气；先分别加入中间体2-1(35.000克，1.0当量)和叔丁醇钾(21.553克，3.0当量)，接着加入四氢呋喃(150毫升)并在0℃下搅拌混合10分钟，接着逐滴加入2-溴-6-氯苯甲醛(式B-1所示化合物，14.051克，1.0当量)于四氢呋喃(100毫升)中之溶液，最后在室温反应24小时；待其回温后加入水(50毫升)，接着用乙醚(3×300毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/75)，得到中间体3-1(23.969克，产率92％)。
4、制备中间体4-1
取500毫升双颈圆底瓶并放入搅拌子与上接回流管，干燥后充入氮气；先加入中间体3-1(20.346克，1.0当量)，接着加入无水四氢呋喃(180毫升)并在-78℃下搅拌混合10分钟，接着逐滴加入2.5M丁基锂于己烷中之溶液(43毫升，2.15当量)后反应30分钟，再逐滴加入N,N,N’,N’-四甲基-1,2-乙二胺(17毫升，2.3当量)并反应2小时，最后逐滴加入二甲基二氯硅烷(式C-1所示化合物，6.6毫升，1.1当量)；待其回温后以饱和碳酸氢钠水溶液(50毫升)终止反应，接着用乙酸乙酯(3×150毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/30)，得到中间体4-1(9.616克，产率63％)。
5、制备式SP-01所示的二苯并杂环化合物
取100毫升双颈圆底瓶并内置搅拌子与上接回流管，干燥后充入氮气；先分别加入中间体4-1(3.053克，1.0当量)、N-(1-萘基)-苯胺(4.495克，2.05当量)、Pd 2(dba) 3(0.275克，3摩尔百分比)、及叔丁醇钾(2.018克，2.1当量)，接着加入无水甲苯(40毫升)并搅拌混合10分钟，接着加入叔丁基磷于甲苯中之溶液(0.03M，10毫升)，最后再加热至回流并反应6小时；待其回温后加入水(30毫升)，接着用乙酸乙酯(3×20毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/20)，得到化合物SP-01(6.441克，产率96％)。
元素分析：(C 48H 38N 2Si)理论值：C,85.93；H,5.71；N,4.18；Si,4.19；实测值：C,85.81；H,5.74；N,4.21；Si,4.24；HRMS(ESI)m/z(M+)：理论值：670.9310；实测值：679.9313。
实施例2
本实施提供一种二苯并杂环化合物，具有如下式SP-02所示的结构：
Figure PCTCN2019083653-appb-000015
式SP-02所示的二苯并杂环化合物的合成路径如下所示：
Figure PCTCN2019083653-appb-000016
式SP-02所示的二苯并杂环化合物的制备方法包括以下步骤：
1、制备中间体1-2
取500毫升双颈圆底瓶并放入搅拌子与上接回流管，干燥后充入氮气；先分别加入化合物A-2(20.548克，1.0当量)、NBS(N-溴代琥珀酰亚胺，19.578克，1.1当量)、及AIBN(偶氮二异丁腈，0.821克，0.5摩尔百分比)，接着加入四氯化碳(250毫升)并搅拌混合10分钟，最后再加热至回流并反应24小时；待其回温后加入水(200毫升)，接着用乙酸乙酯(3×200毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/10)，得到中间体1-2(20.191克，产率71％)。
2、制备中间体2-2
取500毫升双颈圆底瓶并放入搅拌子与上接回流管，干燥后充入氮气；先分别加入中间体1-2(20.000克，1.0当量)和三苯磷(19.369克，1.05当量)，接着加入甲苯(250毫升)并搅拌混合10分钟，最后再加热至回流并反应18小时；待其回温后过滤，接着用己烷(3×80毫升)清洗所得到的固体，得到中间体2-2的粗产物(38.466克)。
3、制备中间体3-2
取500毫升双颈圆底瓶并放入搅拌子，干燥后充入氮气；先分别加入中间体2-2(35.000克，1.0当量)和叔丁醇钾(21.553克，3.0当量)，接着加入四氢呋喃(150毫升)并在0℃下搅拌混合10分钟，接着逐滴加入2-溴-5-氯苯甲醛(式B-2所示化合物，14.051克，1.0当量)于四氢呋喃(100毫升)中之溶液，最后在室温反应24小时；待其回温后加入水(50毫升)，接着用乙醚(3×300毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/70)，得到中间体3-2(23.187克，产率89％)。
4、制备中间体4-2
取500毫升双颈圆底瓶并放入搅拌子与上接回流管，干燥后充入氮气；先加入中间体3-2(20.346克，1.0当量)，接着加入无水四氢呋喃(180毫升)并在-78℃下搅拌混合10分钟，接着逐滴加入2.5M丁基锂于己烷中之溶液(43毫升，2.15当量)后反应30分钟，再逐滴加入N,N,N’,N’-四甲基-1,2-乙二胺(17毫升，2.3当量)并反应2小时，最后逐滴加入二甲基二氯硅烷(式C-1所示化合物，6.6毫升，1.1当量)；待其回温后以饱和碳酸氢钠水溶液(50毫升)终止反应，接着用乙酸乙酯(3×150毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/30)，得到中间体4-2(7.784克，产率51％)。
5、制备式SP-02所示的二苯并杂环化合物
取100毫升双颈圆底瓶并内置搅拌子与上接回流管，干燥后充入氮气；先分别加入中间体4-2(3.053克，1.0当量)、N-(1-萘基)-苯胺(4.495克，2.05当量)、Pd 2(dba) 3(0.275克，3摩尔百分比)、及叔丁醇钾(2.018克，2.1当量)，接着加入无水甲苯(40毫升)并搅拌混合10分钟，接着加入叔丁基磷于甲苯中之溶液(0.03M，10毫升)，最后再加热至回流并反应6小时；待其回温后加入水(30毫升)，接着用乙酸乙酯(3×20毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/20)，得到化合物SP-02(5.166克，产率77％)。
元素分析：(C 48H 38N 2Si)理论值：C,85.93；H,5.71；N,4.18；Si,4.19；实测值：C,85.91；H,5.72；N,4.16；Si,4.21；HRMS(ESI)m/z(M +)：理论值：670.9310；实测值：679.9311。
实施例3
本实施提供一种二苯并杂环化合物，具有如下式SP-03所示的结构：
Figure PCTCN2019083653-appb-000017
式SP-03所示的二苯并杂环化合物的合成路径如下所示：
Figure PCTCN2019083653-appb-000018
式SP-03所示的二苯并杂环化合物的制备方法包括以下步骤：
1、制备中间体1-3
取500毫升双颈圆底瓶并放入搅拌子与上接回流管，干燥后充入氮气；先分别加入化合物A-3(20.548克，1.0当量)、NBS(N-溴代琥珀酰亚胺，19.578克，1.1当量)、及AIBN(偶氮二异丁腈，0.821克，0.5摩尔百分比)，接着加入四氯化碳(250毫升)并搅拌混合10分钟，最后再加热至回流并反应24小时；待其回温后加入水(200毫升)，接着用乙酸乙酯(3×200毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/10)，得到中间体1-3(23.604克，产率83％)。
2、制备中间体2-3
取500毫升双颈圆底瓶并放入搅拌子与上接回流管，干燥后充入氮气；先分别加入中间体1-3(20.000克，1.0当量)和三苯磷(19.369克，1.05当量)，接着加入甲苯(250毫升)并搅拌混合10分钟，最后再加热至回流并反应18小时；待其回温后过滤，接着用己烷(3×80毫升)清洗所得到的固体，得到中间体2-3的粗产物(38.316克)。
3、制备中间体3-3
取500毫升双颈圆底瓶并放入搅拌子，干燥后充入氮气；先分别加入中间体2-3(35.000克，1.0当量)和叔丁醇钾(21.553克，3.0当量)，接着加入四氢呋喃(150毫升)并在0℃下搅拌混合10分钟，接着逐滴加入2-溴-4-氯苯甲醛(式B-3所示化合物，14.051克，1.0当量)于四氢呋喃(100毫升)中之溶液，最后在室温反应24小时；待其回温后加入水(50毫升)，接着用乙醚(3×300毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/80)，得到中间体3-3(24.750克，产率89％)。
4、制备中间体4-3
取500毫升双颈圆底瓶并放入搅拌子与上接回流管，干燥后充入氮气；先加入中间体3-3(20.346克，1.0当量)，接着加入无水四氢呋喃(180毫升)并在-78℃下搅拌混合10分钟，接着逐滴加入2.5M丁基锂于己烷中之溶液(43毫升，2.15当量)后反应30分钟，再逐滴加入N,N,N’,N’-四甲基-1,2-乙二胺(17毫升，2.3当量)并反应2小时，最后逐滴加入二甲基二氯硅烷(式C-1所示化合物，6.6毫升，1.1当量)；待其回温后以饱和碳酸氢钠水溶液(50毫升)终止反应，接着用乙酸乙酯(3×150毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/30)，得到中间体4-3(10.531克，产率69％)。
5、制备式SP-03所示的二苯并杂环化合物
取100毫升双颈圆底瓶并内置搅拌子与上接回流管，干燥后充入氮气；先分别加入中间体4-3(3.053克，1.0当量)、N-(1-萘基)-苯胺(4.495克，2.05当量)、Pd 2(dba) 3(0.275克，3摩尔百分比)、及叔丁醇钾(2.018克，2.1当量)，接着加入无水甲苯(40毫升)并搅拌混合10分钟，接着加入叔丁基磷于甲苯中之溶液(0.03M，10毫升)，最后再加热至回流并反应6小时；待其回温后加入水(30毫升)，接着用乙酸乙酯(3×20毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/25)，得到化合物SP-03(6.441克，产率95％)。
元素分析：(C 48H 38N 2Si)理论值：C,85.93；H,5.71；N,4.18；Si,4.19；实测值：C,85.96；H,5.72； N,4.16；Si,4.16；HRMS(ESI)m/z(M +)：理论值：670.9310；实测值：679.9313。
实施例4
本实施提供一种二苯并杂环化合物，具有如下式SP-04所示的结构：
Figure PCTCN2019083653-appb-000019
式SP-04所示的二苯并杂环化合物的合成路径如下所示：
Figure PCTCN2019083653-appb-000020
式SP-04所示的二苯并杂环化合物的制备方法包括以下步骤：
1、制备中间体1-4
取500毫升双颈圆底瓶并放入搅拌子与上接回流管，干燥后充入氮气；先分别加入化合物A-4(20.548克，1.0当量)、NBS(N-溴代琥珀酰亚胺，19.578克，1.1当量)、及AIBN(偶氮二异丁腈，0.821克，0.5摩尔百分比)，接着加入四氯化碳(250毫升)并搅拌混合10分钟，最后再加热至回流并反应24小时；待其回温后加入水(200毫升)，接着用乙酸乙酯(3×200毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/10)，得到中间体1-4(23.867克，产率65％)。
2、制备中间体2-4
取500毫升双颈圆底瓶并放入搅拌子与上接回流管，干燥后充入氮气；先分别加入中间体1-4(20.000克，1.0当量)和三苯磷(19.369克，1.05当量)，接着加入甲苯(250毫升)并搅拌混合10分钟，最后再加热至回流并反应18小时；待其回温后过滤，接着用己烷(3×80毫升)清洗所得到的固体，得到中间体2-4的粗产物(37.831克)。
3、制备中间体3-4
取500毫升双颈圆底瓶并放入搅拌子，干燥后充入氮气；先分别加入中间体2-4(35.000克，1.0当量)和叔丁醇钾(21.553克，3.0当量)，接着加入四氢呋喃(150毫升)并在0℃下搅拌混合10分钟，接着逐滴加入2-溴-3-氯苯甲醛(式B-4所示化合物，14.051克，1.0当量)于四氢呋喃(100毫升)中之溶液，最后在室温反应24小时；待其回温后加入水(50毫升)，接着用乙醚(3×300毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/75)，得到中间体3-4(22.525克，产率81％)。
4、制备中间体4-4
取500毫升双颈圆底瓶并放入搅拌子与上接回流管，干燥后充入氮气；先加入中间体3-4(20.346克，1.0当量)，接着加入无水四氢呋喃(180毫升)并在-78℃下搅拌混合10分钟，接着逐滴加入2.5M丁基锂 于己烷中之溶液(43毫升，2.15当量)后反应30分钟，再逐滴加入N,N,N’,N’-四甲基-1,2-乙二胺(17毫升，2.3当量)并反应2小时，最后逐滴加入二甲基二氯硅烷(式C-1所示化合物，6.6毫升，1.1当量)；待其回温后以饱和碳酸氢钠水溶液(50毫升)终止反应，接着用乙酸乙酯(3×150毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/30)，得到中间体4-4(7.173克，产率47％)。
5、制备式SP-04所示的二苯并杂环化合物
取100毫升双颈圆底瓶并内置搅拌子与上接回流管，干燥后充入氮气；先分别加入中间体4-4(3.053克，1.0当量)、N-(1-萘基)-苯胺(4.495克，2.05当量)、Pd 2(dba) 3(0.275克，3摩尔百分比)、及叔丁醇钾(2.018克，2.1当量)，接着加入无水甲苯(40毫升)并搅拌混合10分钟，接着加入叔丁基磷于甲苯中之溶液(0.03M，10毫升)，最后再加热至回流并反应6小时；待其回温后加入水(30毫升)，接着用乙酸乙酯(3×20毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/20)，得到化合物SP-04(5.288克，产率78％)。
元素分析：(C 48H 38N 2Si)理论值：C,85.93；H,5.71；N,4.18；Si,4.19；实测值：C,85.89；H,5.75；N,4.21；Si,4.15；HRMS(ESI)m/z(M +)：理论值：670.9310；实测值：679.9308。
实施例5
本实施提供一种二苯并杂环化合物，具有如下式SP-32所示的结构：
Figure PCTCN2019083653-appb-000021
式SP-32所示的二苯并杂环化合物的合成路径如下所示：
Figure PCTCN2019083653-appb-000022
式SP-32所示的二苯并杂环化合物的制备方法包括以下步骤：
1、以实施例3提供的方法，制备得到中间体3-3。
2、制备中间体4-5
取500毫升双颈圆底瓶并放入搅拌子与上接回流管，干燥后充入氮气；先加入中间体3-3(20.346克，1.0当量)，接着加入无水四氢呋喃(180毫升)并在-78℃下搅拌混合10分钟，接着逐滴加入2.5M丁基锂于己烷中之溶液(43毫升，2.15当量)后反应30分钟，再逐滴加入N,N,N’,N’-四甲基-1,2-乙二胺(17毫升，2.3当量)并反应2小时，最后逐滴加入二乙基二氯硅烷(式C-2所示化合物，8.2毫升，1.1当量)；待其回温后以饱和碳酸氢钠水溶液(50毫升)终止反应，接着用乙酸乙酯(3×150毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/30)，得到中间体4-5(10.333克，产率62％)。
3、制备式SP-32所示的二苯并杂环化合物
取100毫升双颈圆底瓶并内置搅拌子与上接回流管，干燥后充入氮气；先分别加入中间体4-5(3.333克，1.0当量)、N-(1-萘基)-苯胺(4.495克，2.05当量)、Pd 2(dba) 3(0.275克，3摩尔百分比)、及叔丁醇钾(2.018 克，2.1当量)，接着加入无水甲苯(40毫升)并搅拌混合10分钟，接着加入叔丁基磷于甲苯中之溶液(0.03M，10毫升)，最后再加热至回流并反应6小时；待其回温后加入水(30毫升)，接着用乙酸乙酯(3×20毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/20)，得到化合物SP-32(6.774克，产率97％)。
元素分析：(C 50H 42N 2Si)理论值：C,85.92；H,6.06；N,4.01；Si,4.02；实测值：C,85.88；H,6.07；N,4.04；Si,4.01；HRMS(ESI)m/z(M +)：理论值：698.3117；实测值：698.3112。
实施例6
本实施提供一种二苯并杂环化合物，具有如下式SP-34所示的结构：
Figure PCTCN2019083653-appb-000023
式SP-34所示的二苯并杂环化合物的合成路径如下所示：
Figure PCTCN2019083653-appb-000024
式SP-34所示的二苯并杂环化合物的制备方法包括以下步骤：
1、以实施例5提供的方法，制备得到中间体4-5。
2、制备式SP-34所示的二苯并杂环化合物
取100毫升双颈圆底瓶并内置搅拌子与上接回流管，干燥后充入氮气；先分别加入中间体4-5(3.333克，1.0当量)、N,N-二-(1,3,5-三甲基)胺(5.194克，2.05当量)、Pd 2(dba) 3(0.275克，3摩尔百分比)、及叔丁醇钾(2.018克，2.1当量)，接着加入无水甲苯(40毫升)并搅拌混合10分钟，接着加入叔丁基磷于甲苯中之溶液(0.03M，10毫升)，最后再加热至回流并反应6小时；待其回温后加入水(30毫升)，接着用乙酸乙酯(3×20毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/20)，得到化合物SP-34(6.828克，产率89％)。
元素分析：(C 54H 62N 2Si)理论值：C,84.54；H,8.15；N,3.65；Si,3.66；实测值：C,84.55；H,8.12；N,3.69；Si,3.64；HRMS(ESI)m/z(M +)：理论值：767.1890；实测值：767.1887。
实施例7
本实施提供一种二苯并杂环化合物，具有如下式SP-36所示的结构：
Figure PCTCN2019083653-appb-000025
式SP-36所示的二苯并杂环化合物的合成路径如下所示：
Figure PCTCN2019083653-appb-000026
式SP-36所示的二苯并杂环化合物的制备方法包括以下步骤：
1、以实施例5提供的方法，制备得到中间体4-5。
2、制备式SP-36所示的二苯并杂环化合物
取100毫升双颈圆底瓶并内置搅拌子与上接回流管，干燥后充入氮气；先分别加入中间体4-5(3.333克，1.0当量)、N,N-二-(4-联苯基)胺(6.589克，2.05当量)、Pd 2(dba) 3(0.275克，3摩尔百分比)、及叔丁醇钾(2.018克，2.1当量)，接着加入无水甲苯(40毫升)并搅拌混合10分钟，接着加入叔丁基磷于甲苯中之溶液(0.03M，10毫升)，最后再加热至回流并反应6小时；待其回温后加入水(30毫升)，接着用乙酸乙酯(3×20毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/20)，得到化合物SP-36(8.491克，产率94％)。
元素分析：(C 66H 54N 2Si)理论值：C,87.76；H,6.03；N,3.10；Si,3.11；实测值：C,87.71；H,6.04；N,3.09；Si,3.16；HRMS(ESI)m/z(M +)：理论值：903.2570；实测值：903.2566。
实施例8
本实施提供一种二苯并杂环化合物，具有如下式SP-38所示的结构：
Figure PCTCN2019083653-appb-000027
式SP-38所示的二苯并杂环化合物的合成路径如下所示：
Figure PCTCN2019083653-appb-000028
式SP-38所示的二苯并杂环化合物的制备方法包括以下步骤：
1、以实施例5提供的方法，制备得到中间体4-5。
2、制备式SP-38所示的二苯并杂环化合物
取100毫升双颈圆底瓶并内置搅拌子与上接回流管，干燥后充入氮气；先分别加入中间体4-5(3.333克，1.0当量)、4-(N,N-二苯胺基)苯硼酸(6.650克，2.3当量)、Pd(PPh 3) 4(0.578克，5摩尔百分比)、及碳酸钠(2.649克，2.5当量)，接着加入无水甲苯(40毫升)和水(4毫升)，并搅拌混合10分钟，最后再加热至回流并反应18小时；待其回温后加入水(30毫升)，接着用乙酸乙酯(3×20毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/20)，得到化合物SP-38(5.858克，产率78％)。
元素分析：(C 54H 46N 2Si)理论值：C,86.36；H,6.17；N,3.73；Si,3.74；实测值：C,86.39；H,6.18；N,3.71；Si,3.72；HRMS(ESI)m/z(M +)：理论值：751.0610；实测值：751.0613。
实施例9
本实施提供一种二苯并杂环化合物，具有如下式SP-55所示的结构：
Figure PCTCN2019083653-appb-000029
式SP-55所示的二苯并杂环化合物的合成路径如下所示：
Figure PCTCN2019083653-appb-000030
式SP-55所示的二苯并杂环化合物的制备方法包括以下步骤：
1、以实施例5提供的方法，制备得到中间体4-5。
2、制备式SP-55所示的二苯并杂环化合物
取100毫升双颈圆底瓶并内置搅拌子与上接回流管，干燥后充入氮气；先分别加入中间体4-5(3.333克，1.0当量)、4-甲氧基苯硼酸(1.520克，1.0当量)、Pd(PPh 3) 4(0.578克，5摩尔百分比)、及碳酸钠(2.649克，2.5当量)，接着加入无水甲苯(40毫升)和水(4毫升)，并搅拌混合10分钟，最后再加热至回流并反应8小时；将反应回温后加入4-氰基苯硼酸(1.616克，1.1当量)并搅拌混合10分钟，再加热至回流并反应12小时；待其回温后加入水(30毫升)，接着用乙酸乙酯(3×20毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/20)，得到化合物SP-55(3.396克，产率72％)。
元素分析：(C 32H 29NOSi)理论值：C,81.49；H,6.20；N,2.97；O,3.39；Si,5.95；m/z:471.2018(100.0％),472.2052(34.6％),473.2086(5.8％),472.2014(5.1％),473.1987(3.3％),473.2048(1.8％),474.2020(1.2％)；HRMS(ESI)m/z(M +)：理论值：471.2018；实测值：471.6750。
实施例10
本实施提供一种二苯并杂环化合物，具有如下式SP-56所示的结构：
Figure PCTCN2019083653-appb-000031
式SP-56所示的二苯并杂环化合物的合成路径如下所示：
Figure PCTCN2019083653-appb-000032
式SP-56所示的二苯并杂环化合物的制备方法包括以下步骤：
1、以实施例5提供的方法，制备得到中间体4-5。
2、制备式SP-56所示的二苯并杂环化合物
取100毫升双颈圆底瓶并内置搅拌子与上接回流管，干燥后充入氮气；先分别加入中间体4-5(3.333克，1.0当量)、4-甲氧基-苯硼酸(3.495克，2.3当量)、Pd(PPh 3) 4(0.578克，5摩尔百分比)、及碳酸钠(2.649克，2.5当量)，接着加入无水甲苯(40毫升)和水(4毫升)，并搅拌混合10分钟，最后再加热至回流并反应18小时；待其回温后加入水(30毫升)，接着用乙酸乙酯(3×20毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/20)，得到化合物SP-56(5.858克，产率86％)。
元素分析：(C 32H 32O 2Si)理论值：C,80.63；H,6.77；O,6.71；Si,5.89；实测值：C,80.60；H,6.72；O,6.75；Si,5.93；HRMS(ESI)m/z(M +)：理论值：476.6910；实测值：476.6907。
实施例11
本实施提供一种二苯并杂环化合物，具有如下式SP-42所示的结构：
Figure PCTCN2019083653-appb-000033
式SP-42所示的二苯并杂环化合物的合成路径如下所示：
Figure PCTCN2019083653-appb-000034
式SP-56所示的二苯并杂环化合物的制备方法包括以下步骤：
1、以实施例3提供的方法，制备得到中间体3-3。
2、制备中间体4-6
取500毫升双颈圆底瓶并放入搅拌子与上接回流管，干燥后充入氮气；先加入中间体3-3(20.346克，1.0当量)，接着加入无水四氢呋喃(180毫升)并在-78℃下搅拌混合10分钟，接着逐滴加入2.5M丁基锂于己烷中之溶液(43毫升，2.15当量)后反应30分钟，再逐滴加入N,N,N’,N’-四甲基-1,2-乙二胺(17毫升，2.3当量)并反应2小时，最后逐滴加入二甲氧基二氯硅烷(8.858克，1.1当量，式C-3所示化合物)；待其回温后以饱和碳酸氢钠水溶液(50毫升)终止反应，接着用乙酸乙酯(3×150毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/25)，得到中间体4-6(8.600克，产率51％)。
3、制备中间体I’
取500毫升双颈圆底瓶并内置搅拌子与上接回流管，干燥后充入氮气；先分别加入中间体4-6(8.432克，1.0当量)、4-(N,N-二苯胺基)苯硼酸(18.238克，2.3当量)、Pd(PPh 3) 4(1.444克，5摩尔百分比)、及碳酸钠(6.624克，2.5当量)，接着加入无水甲苯(200毫升)和水(20毫升)，并搅拌混合10分钟，最后再加热至回流并反应18小时；待其回温后加入水(150毫升)，接着用乙酸乙酯(3×200毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/20)，得到中间体I’(15.817克，产率78％)。
4、制备中间体I”
取500毫升双颈圆底瓶并放入搅拌子与上接回流管，干燥后充入氮气；先加入中间体I’(6.071克，1.0当量)，接着分别加入溴水(2.4毫升，5.2当量)与氢溴酸(150毫升)并搅拌混合10分钟，最后再加热至回流并反应6小时；待其回温后加入水(120毫升)，接着用乙酸乙酯(3×150毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/20)，得到中间体I”(11.010克，产率63％)。
5、制备中间体I”’-1
取250毫升双颈圆底瓶并放入搅拌子与上接回流管，干燥后充入氮气；先分别加入中间体I”(9.709克，1.0当量)与氢氧化钾(1.683克，3.0当量)，接着加入1,2-二甲氧基乙烷(100毫升)并搅拌混合10分钟，最后再加热至回流并反应4小时；待其回温后加入呋喃(1.3毫升，1.8当量)，接着再加热至回流并反应12小时；待其回温后加入水(50毫升)，接着用乙酸乙酯(3×80毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/25)，得到中间体I”’-1(4.386克，产率50％)。
6、制备中间体I”’-2
取100毫升双颈圆底瓶并放入搅拌子，干燥后充入氮气；先分别加入中间体I”’-1(3.509克，1.0当量)与活性炭负载钯(5％，0.213克，2.5摩尔百分比)，接着加入乙酸乙酯(40毫升)并搅拌混合10分钟，最后充入氢气并在室温下反应8小时；加入水(30毫升)，接着用乙酸乙酯(3×30毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/25)，得到中间体I”’-2(3.306克，产率94％)。
7、制备式SP-42所示的二苯并杂环化合物
取50毫升双颈圆底瓶并放入搅拌子与上接回流管，干燥后充入氮气；先分别加入中间体I”’-2(2.638克，1.0当量)与对甲基苯磺酸(1.033克，2.0当量)，接着加入甲苯(25毫升)并搅拌混合10分钟，最后再加热至回流并反应16小时；加入水(15毫升)，接着用乙酸乙酯(3×20毫升)萃取，所得到的萃取液依序加入硫酸镁干燥、过滤及旋干；粗产物以层析纯化(乙酸乙酯/己烷，1/30)，得到化合物SP-42(2.506克，产率97％)。
元素分析：(C 60H 52N 2O 2Si)理论值：C,83.68；H,6.09；N,3.25；实测值：C,83.66；H,6.10；N,3.28；HRMS(ESI)m/z(M +)：理论值：860.3798；实测值：860.3792。
实施例12
本实施例提供一种有机电致发光器件，如图1所示，包括依次层叠设置在基板上的阳极1、空穴注入层2、空穴传输层3、发光层4、电子传输层5、电子注入层6和阴极7。
有机电致发光器件中阳极选用ITO材料；阴极7选用金属Al；
空穴注入层2材料选用PEDOT:PSS，PEDOT:PSS具有如下所示化学结构：
Figure PCTCN2019083653-appb-000035
空穴传输层3材料选用NPB，NPB具有如下所示的化学结构：
Figure PCTCN2019083653-appb-000036
电子传输层5材料选用TPBI，TPBI具有如下所示的化学结构：
Figure PCTCN2019083653-appb-000037
电子注入层6材料选用TPBI与电子注入材料LiF掺杂形成；
有机电致发光器件中发光层32的发光材料选用式SP-01所示的二苯并杂环化合物：
Figure PCTCN2019083653-appb-000038
有机致电发光器件形成如下具体结构：ITO(阳极)/PEDOT:PSS(空穴注入层，30nm)/NPB(空穴传输层，40nm)/SP-01(蓝色发光层，40nm)/TPBI(电子注入层，35nm)/TPBI：LiF(电子传输层，40nm)铝(阴极，5nm/150nm)。
发光层材料选用二苯并杂环化合物SP-01，其发光色坐标位于蓝光发光区域，能够得到蓝光发光器件。由于母核结构中存在的二苯乙烯基团，化合物SP-01具有低的LUMO能级(-1.35eV)，有利于匹配电子传输层的能级，促进电子的注入和传输。同时，二苯并杂环化合物SP-01中连接有给电子的取代基团
Figure PCTCN2019083653-appb-000039
使材料分子具有良好的空穴传输性能，其HOMO能级适于匹配相邻的空穴传输层，有利于平衡发光层中的电子和空穴，提高电子和空穴复合的几率，使OLED器件的蓝光发光效率得到提升。二苯并杂环化合物SP-01的空间构型呈蝴蝶构型，避免了材料分子发生堆叠导致的高能激子的产生，有效减少发光层内的激子湮灭，避免蓝光器件的效率滚降，防止蓝光色坐标漂移，得到发光稳定性高的蓝光器件。二苯并杂环化合物SP-01适宜的HOMO能级和LUMO能级有利于降低电子和空穴向发光层传输需要克服的势垒，使器件的工作电压降低。另一方面，SP-01所示的二苯并杂环化合物其热分解温度高、热稳定性和形态学稳定性高，成膜性能优异，作为发光层材料不易分解、结晶，进一步提升OLED器件的性能和发光效率。
作为可替代的实施方式，发光层的客体发光材料还可以选择式(SP-02)～式(SP-65)所示的任一二苯并杂环化合物。
作为可替代的实施方式，发光层的客体发光材料还可以选择具有通式(I)所示化学结构的任一其他二苯并杂环化合物。
实施例13
本实施例提供一种有机电致发光器件，与实施例12中提供有机电致发光器件的区别仅在于：发光层材料选用下述所示结构的二苯并杂环化合物：
Figure PCTCN2019083653-appb-000040
实施例14
本实施例提供一种有机电致发光器件，与实施例12中提供有机电致发光器件的区别仅在于：发光层材料选用下述所示结构的二苯并杂环化合物：
Figure PCTCN2019083653-appb-000041
实施例15
本实施例提供一种有机电致发光器件，与实施例12中提供有机电致发光器件的区别仅在于：发光层材料选用下述所示结构的二苯并杂环化合物：
Figure PCTCN2019083653-appb-000042
实施例16
本实施例提供一种有机电致发光器件，与实施例12中提供有机电致发光器件的区别仅在于：发光层材料选用下述所示结构的二苯并杂环化合物：
Figure PCTCN2019083653-appb-000043
实施例17
本实施例提供一种有机电致发光器件，与实施例12中提供有机电致发光器件的区别仅在于：发光层材料选用下述所示结构的二苯并杂环化合物：
Figure PCTCN2019083653-appb-000044
实施例18
本实施例提供一种有机电致发光器件，与实施例12中提供有机电致发光器件的区别仅在于：发光层材料选用下述所示结构的二苯并杂环化合物：
Figure PCTCN2019083653-appb-000045
实施例19
本实施例提供一种有机电致发光器件，与实施例12中提供有机电致发光器件的区别仅在于：发光层材料选用下述所示结构的二苯并杂环化合物：
Figure PCTCN2019083653-appb-000046
对比例1
本对比例提供一种有机电致发光器件，与实施例12中提供有机电致发光器件的区别仅在于：发光层材料选用下述所示结构的化合物：
Figure PCTCN2019083653-appb-000047
测试例1
1、测定二苯并杂环化合物的热分解温度(T d)
使用热重分析仪(TGA)对本专利材料进行热分解温度测试，测试范围室温至600℃，升温速率10℃/min，氮气氛围下，重量损失0.5％的温度定义为热分解温度。
2、测定二苯并杂环化合物的HOMO能级与LUMO能级
使用电化学工作站利用循环伏安法(CV)对本专利材料的HOMO与LUMO能级进行测试，以铂丝(Pt)为对电极，银/氯化银(Ag/AgCl)为参比电极。在氮气氛围下，在含有0.1M四丁基六氟磷酸铵的二氯甲烷电解液中以100mV/s的扫描速率进行测试，以二茂铁进行电位标定，设定二茂铁的电位在真空状态下的绝对HOMO能级为-4.8eV：
Figure PCTCN2019083653-appb-000048
Figure PCTCN2019083653-appb-000049
表1
Figure PCTCN2019083653-appb-000050
由表1的测试数据可知，本发明提供的二苯并杂环化合物具有高的热分解温度，在成膜后具有较高的热稳定性，材料分子不易随器件使用过程中产生的热量而分解或结晶，能够保持发光层功能稳定，避免器件崩溃，延长器件的使用寿命。同时，二苯并杂环化合物具有低的LUMO能级(-1.30至-1.57eV)，有利于电子向发光层的注入和传输，提高电子比例，由于半导体材料的空穴传输性能一般高于电子传输性能，二苯并杂环化合物有利于平衡电子和空穴，使器件的发光效率提升。
测试例2
对实施例12-实施例19，和对比例1提供的有机电致发光器件的电流、电压、亮度、发光光谱等特性采 用PR 650光谱扫描亮度计和Keithley K 2400数字源表系统同步测试。测试结果如表2所示。
表2
Figure PCTCN2019083653-appb-000051
由表2可知，本发明提供的二苯并杂环化合物作为发光层材料，有利于降低器件的工作电压、提高器件的发光效率，得到高效发光、性能稳定的蓝光发光器件。
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引伸出的显而易见的变化或变动仍处于本发明创造的保护范围之中。

Claims (12)

  1. 一种二苯并杂环化合物，其特征在于，具有如式(I)所示的结构：
    Figure PCTCN2019083653-appb-100001
    其中，R 1、R 2彼此独立地选自氢、取代或未取代的C 1-C 60的烷基、取代或未取代的C 1-C 60的烯基、取代或未取代的C 1-C 60的炔基、取代或未取代的C 3-C 60的环烷基、取代或未取代的C 3-C 60的环烯基、取代或未取代的C 3-C 60的环炔基、取代或未取代的C 1-C 60的烷氧基、取代或未取代的C 1-C 60的烯氧基、取代或未取代的C 1-C 60的炔氧基、取代或未取代的C 1-C 60的烷基硫基、取代或未取代的C 1-C 60的烯基硫基、取代或未取代的C 1-C 60的炔基硫基、取代或未取代的C 1-C 60的酯基，或者取代或未取代的C 1-C 60的酰胺基；
    Y 1-Y 10彼此独立地选自氢、卤素、氰基、取代或未取代的C 1-C 60的烷基、取代或未取代的C 1-C 60的烯基、取代或未取代的C 1-C 60的炔基、取代或未取代的C 1-C 60的烷胺基、取代或未取代的C 1-C 60的烯胺基、取代或未取代的C 1-C 60的炔胺基、取代或未取代的C 1-C 60的烷氧基、取代或未取代的C 1-C 60的烯氧基、取代或未取代的C 1-C 60的炔氧基、取代或未取代的C 1-C 60的硫代烷氧基、取代或未取代的C 1-C 60的硫代烯氧基、取代或未取代的C 1-C 60的硫代炔氧基、取代或未取代的C 1-C 60的烷硼基、取代或未取代的C 1-C 60的烯硼基、取代或未取代的C 1-C 60的炔硼基、取代或未取代的C 1-C 60的酯基、取代或未取代的C 1-C 60的酰胺基、取代或未取代的C 4-C 60的芳基、取代或未取代的C 3-C 60的杂芳基、取代或未取代的C 4-C 60的芳氧基、取代或未取代的C 4-C 60的芳香胺基、取代或未取代的C 4-C 60的硫代芳氧基、取代或未取代的C 4-C 60的芳硼基；或者Y 1-Y 10中任意相邻的两个基团结合形成环A，所述环A选自3元到7元的饱和或部分不饱和的碳环、3元到7元的饱和或部分不饱和的杂环、C 4-C 60的稠环芳基或C 3-C 30的稠环杂芳基。
  2. 根据权利要求1所述的二苯并杂环化合物，其特征在于，
    所述R 1、R 2彼此独立地选自取代或未取代的C 1-C 10的烷基、取代或未取代的C 1-C 10的烯基、取代或未取代的C 1-C 10的炔基、取代或未取代的C 1-C 10的烷氧基、取代或未取代的C 1-C 10的烷基硫基；
    所述Y 1-Y 10彼此独立地选自氢、取代或未取代的C 4-C 30的单环芳基、取代或未取代的C 3-C 30的稠环芳基、取代或未取代的C 3-C 30的单环杂芳基、取代或未取代的C 3-C 30的稠环杂芳基、取代或未取代的C 4-C 30的芳香胺基。
  3. 根据权利要求1或2所述的二苯并杂环化合物，其特征在于，所述Y 1-Y 10彼此独立地选自氢、取代或未取代的下述基团：
    苯基、联苯基、三联苯基、戊搭烯基、茚基、萘基、薁基、庚搭烯基、金刚烷基、碗烯基、三亚苯基、引达省基、苊基、芴基、螺-二芴基、苯并芴基、二苯并芴基、非那烯基、菲基、蒽基、荧蒽基、苯并菲基、芘基、屈基、并四苯基、苉基、苝基、戊芬基、并五苯基、玉红省基、蔻基、卵苯基、吡啶基、吡嗪基、嘧啶基、哒嗪基、三嗪基、噻吩基、呋喃基、喹啉基、咔唑基、吡喃基、噻喃基、酞嗪基、吩嗪基、吡咯基、吡唑基、咪唑基、噁唑基、噻唑基、吲哚基、吲哚并咔唑基、菲啶基、吖啶基、呸啶基、蝶啶基、喹唑啉基、喹喔啉基、噌啉基、菲咯琳基、咔啉基、苯并呋喃基、苯并噻吩基、二苯并呋喃基、二苯并噻吩基、苯并萘并呋喃基、二萘并呋喃基、苯并咔唑基、二苯并咔唑基、二苯并噻咯基、苯并萘并噻咯基、二萘并噻咯基、苯并咪唑基、咪唑并吡啶基、
    Figure PCTCN2019083653-appb-100002
    或者由上述基团形成的稠环基、螺环基或连环基；
    其中，p为1-5的整数，q为1-5的整数，Ar 1-Ar 5彼此独立的选自氢、C 1-C 6的烷氧基、C 1-C 6的烷基硫基、苯基、联苯基、三联苯基、戊搭烯基、茚基、萘基、薁基、庚搭烯基、金刚烷基、碗烯基、三亚苯基、引达省基、苊基、芴基、螺-二芴基、苯并芴基、二苯并芴基、非那烯基、菲基、蒽基、荧蒽基、苯并菲基、芘基、屈基、并四苯基、苉基、苝基、戊芬基、并五苯基、玉红省基、蔻基、卵苯基、吡啶基、吡嗪基、嘧啶基、 哒嗪基、三嗪基、噻吩基、呋喃基、喹啉基、咔唑基、吡喃基、噻喃基、酞嗪基、吩嗪基、吡咯基、吡唑基、咪唑基、噁唑基、噻唑基、吲哚基、吲哚并咔唑基、菲啶基、吖啶基、呸啶基、蝶啶基、喹唑啉基、喹喔啉基、噌啉基、菲咯琳基、咔啉基、苯并呋喃基、苯并噻吩基、二苯并呋喃基、二苯并噻吩基、苯并萘并呋喃基、二萘并呋喃基、苯并咔唑基、二苯并咔唑基、二苯并噻咯基、苯并萘并噻咯基、二萘并噻咯基、苯并咪唑基、咪唑并吡啶基，或者由上述基团形成的稠环基、螺环基或连环基。
  4. 根据权利要求1-3任意一项所述的二苯并杂环化合物，其特征在于，所述环A选自Y 9与Y 10形成的环A 1、Y 10与Y 1形成的环A 2、Y 2与Y 1形成的环A 3、Y 2与Y 3形成的环A 4、Y 4与Y 3形成的环A 5、Y 8与Y 7形成的环A 6、Y 6与Y 7形成的环A 7、Y 6与Y 5形成的环A 8，和Y 9与Y 5形成的环A 9中的至少一种；
    所述环A 1-环A 9彼此独立地选自3元到7元的饱和或部分不饱和的碳环、3元到7元的饱和或部分不饱和的杂环、联苯环、三联苯环、戊搭烯环、茚环、萘环、薁环、庚搭烯环、金刚烷环、碗烯环、三亚苯环、引达省环、苊环、芴环、螺-二芴环、苯并芴环、二苯并芴环、非那烯环、菲环、蒽环、荧蒽环、苯并菲环、芘环、屈环、并四苯环、苉环、苝环、戊芬环、并五苯环、玉红省环、蔻环、卵苯环、吡啶环、吡嗪环、嘧啶环、哒嗪环、三嗪环、噻吩环、呋喃环、喹啉环、咔唑环、吡喃环、噻喃环、酞嗪环、吩嗪环、吡咯环、吡唑环、咪唑环、噁唑环、噻唑环、吲哚环、吲哚并咔唑环、菲啶环、吖啶环、呸啶环、蝶啶环、喹唑啉环、喹喔啉环、噌啉环、菲咯琳环、咔啉环、苯并呋喃环、苯并噻吩环、二苯并呋喃环、二苯并噻吩环、苯并萘并呋喃环、二萘并呋喃环、苯并咔唑环、二苯并咔唑环、二苯并噻咯环、苯并萘并噻咯环、二萘并噻咯环、苯并咪唑环、咪唑并吡啶环，或者由上述基团形成的稠环、螺环或连环。
  5. 根据权利要求1-4任一项所述的二苯并杂环化合物，其特征在于，具有如下所示结构：
    Figure PCTCN2019083653-appb-100003
    Figure PCTCN2019083653-appb-100004
    Figure PCTCN2019083653-appb-100005
    Figure PCTCN2019083653-appb-100006
    Figure PCTCN2019083653-appb-100007
    Figure PCTCN2019083653-appb-100008
  6. 一种权利要求1-5任一项所述的二苯并杂环化合物的制备方法，其特征在于，
    所述式(I)所示二苯并杂环化合物的合成步骤如下所示：
    以式(A)所示的化合物为起始原料，在催化剂作用下经卤化反应，得到中间体1，中间体1与三苯磷反应，生成中间体2；中间体2与式(B)所示化合物发生维悌希反应，得到中间体3；中间体3与式(C)所示化合物发生缩合反应，得到中间体4；中间体4与Y 1-Y 8中至少一种的化合物、Y 1-Y 8的至少一种的硼酸化物，或形成Y 1-Y 8中任意相邻基团的环状化合物反应，生成式(I’)所示的中间体；
    Y 9、Y 10分别为氢时，式(I’)所示的中间体即为所述式(I)所示二苯并杂环化合物；Y 9、Y 10中的至少一个不为氢时，式(I’)所示的中间体发生卤化反应，得到式(I”)所示的中间体，式(I”)所示的中间体发生卤化反应，与Y 9-Y 10中至少一种的化合物或形成Y 9、Y 10的环状化合物反应，得到式(I)所示二苯并杂环化合物；
    其中，X 1-X 4彼此独立地选自卤素，R 3-R 10彼此独立地选自卤素或氢；
    所述式(I)所示二苯并杂环化合物的合成路线如下所示：
    Figure PCTCN2019083653-appb-100009
  7. 一种权利要求1-5任一项所述的二苯并杂环化合物作为有机电致发光材料的应用。
  8. 一种权利要求1-5任一项所述的二苯并杂环化合物在蓝光发光器件中的应用。
  9. 一种有机电致发光器件，其特征在于，所述有机电致发光器件的至少有一个功能层中含有权利要求1-5任一项所述的二苯并杂环化合物。
  10. 根据权利要求9所述的有机电致发光器件，其特征在于，所述功能层为发光层。
  11. 根据权利要求9所述的有机电致发光器件，其特征在于，所述发光层材料包括主体材料和客体发光染料，所述客体发光材料为所述二苯并杂环化合物。
  12. 一种显示装置，其特征在于，包括权利要求9-11任一项所述的有机电致发光器件。
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