WO2016192329A1 - 一种芳杂环化合物及其制备方法和有机电致发光器件 - Google Patents

一种芳杂环化合物及其制备方法和有机电致发光器件 Download PDF

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WO2016192329A1
WO2016192329A1 PCT/CN2015/095266 CN2015095266W WO2016192329A1 WO 2016192329 A1 WO2016192329 A1 WO 2016192329A1 CN 2015095266 W CN2015095266 W CN 2015095266W WO 2016192329 A1 WO2016192329 A1 WO 2016192329A1
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carbon atoms
group
substituted
unsubstituted
independently selected
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高春吉
崔敦洙
王贺
李文军
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吉林奥来德光电材料股份有限公司
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Definitions

  • the invention relates to the technical field of organic light-emitting materials, in particular to an aromatic heterocyclic compound and a preparation method thereof.
  • a luminescent material refers to a substance that emits light under various forms of energy excitation. Many substances in nature, including inorganic compounds and organic compounds, can emit more or less. Luminescent materials are a fine high-tech industry widely used in industry, medicine, transportation and military. The luminescent material can be classified into an inorganic luminescent material and an organic luminescent material according to its composition.
  • organic light-emitting materials can be divided into: organic small molecule luminescent materials, organic polymer luminescent materials and organic complex luminescent materials.
  • organic small molecule luminescent materials there are many kinds of organic small molecule luminescent materials, and they mostly have conjugated heterocyclic rings and various chromophores, and the structure is easy to adjust, and is changed by introducing an unsaturated group such as an olefin bond or a benzene ring and various chromophores. Its conjugation length changes the photoelectric properties of the compound.
  • an organic electroluminescent device generally means composed of two opposed electrodes and at least one organic light-emitting compound interposed between the two electrodes. Charge is injected into the organic layer formed between the anode and the cathode to form electron and hole pairs, causing light emission of an organic compound having fluorescent or phosphorescent properties. It is a new type of flat display device with many advantages such as energy saving, fast response, stable color, strong environmental adaptability, no radiation, light weight and thin thickness. And with the rapid development of optoelectronic communication and multimedia in recent years, organic optoelectronic materials have become the core of the modern social information and electronics industry. Therefore, with the rapid development of the field, higher requirements have been placed on the performance of organic light-emitting materials.
  • the technical problem to be solved by the present invention is to provide an aromatic heterocyclic compound and a preparation method thereof, and an organic electroluminescent device, particularly to a benzo[g]pyridazine-containing aromatic heterocyclic compound.
  • the aromatic heterocyclic compound provided by the invention has better performance and can improve the luminous efficiency and the service life of the light-emitting device.
  • the present invention provides an aromatic heterocyclic compound having the structure represented by the formula (I):
  • L 1 , L 2 , L 3 , L 4 are independently selected from 0 or 1;
  • Q 1 and Q 2 are independently selected from nitrogen, oxygen, sulfur, an aryl group having 6 to 30 carbon atoms or a heterocyclic group having 1 to 30 carbon atoms;
  • R 1 and R 2 are independently selected from a hydrogen atom, a cyano group, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substitution or
  • the unsubstituted carbon atom group is an aromatic amine group of 7 to 30, a substituted or unsubstituted aralkyloxy group having 7 to 30 carbon atoms, and a substituted or unsubstituted aralkyl fluorenyl group having 7 to 30 carbon atoms. Or an alkyl group having 1 to 30 carbon atoms;
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 are independently selected from a hydrogen atom, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms.
  • the substituted or unsubstituted aromatic amine group has 7 to 30 carbon atoms.
  • the aromatic heterocyclic compound has the following structure:
  • Z 1 to Z 16 are independently selected from CH, C or N;
  • L 3 and L 4 are independently selected from 0 or 1;
  • R 1 and R 2 are independently selected from a hydrogen atom, a cyano group, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substitution or
  • the unsubstituted carbon atom group is an aromatic amine group of 7 to 30, a substituted or unsubstituted aralkyloxy group having 7 to 30 carbon atoms or a substituted or unsubstituted aralkyl fluorenyl group having 7 to 30 carbon atoms. Or an alkyl group having 1 to 30 carbon atoms;
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 are independently selected from a hydrogen atom, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 50 carbon atoms. a substituted or unsubstituted aralkylfluorenyl group having 7 to 50 carbon atoms, an aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, or a substituted or unsubstituted An aromatic amine group having 7 to 30 carbon atoms.
  • the aromatic heterocyclic compound has the following structure:
  • Z 1 to Z 8 are independently selected from C, CH or N; L 3 and L 4 are independently 0 or 1;
  • Q 1 and Q 2 are independently selected from nitrogen, oxygen, sulfur, an aryl group having 6 to 30 carbon atoms or a heterocyclic group having 1 to 30 carbon atoms;
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 are independently selected from a hydrogen atom, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms.
  • R 2 , R 1 ' and R 2 ' are independently selected from an aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms or a carbon number of 1 to 30. alkyl.
  • the aromatic heterocyclic compound has the following structure:
  • Z 1 ⁇ Z 16 are independently selected from C, CH or N; L 3 and L 4 are independently 0 or 1;
  • Q 1 and Q 2 are independently selected from nitrogen, oxygen, sulfur, an aryl group having 6 to 30 carbon atoms or a heterocyclic group having 1 to 30 carbon atoms;
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 are independently selected from a hydrogen atom, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms.
  • the substituted or unsubstituted aromatic amine group has 7 to 30 carbon atoms.
  • -Ar 1 , -Ar 2 , -Ar 3 and -Ar 4 are independently selected from the structures represented by the following formulas (1) to (35):
  • X and Y are independently selected from a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, and a substitution.
  • an unsubstituted alkenyl group having 2 to 30 carbon atoms a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms,
  • Ar 1 and Ar 2 are independently selected from substituted or unsubstituted carbon atoms 7 to 50.
  • the L 1 and L 2 are not 0 at the same time.
  • the invention provides a preparation method of an aromatic heterocyclic compound, comprising:
  • the compound represented by the formula (V) is reacted with a compound represented by the formula (VI) and a compound represented by the formula (VII) to obtain an aromatic heterocyclic compound represented by the formula (I);
  • X' is a halogen atom, and Y' and Y 1 ' are independently selected from B(OH) 2 or H;
  • L 1 , L 2 , L 3 , L 4 are independently selected from 0 or 1;
  • Q 1 and Q 2 are independently selected from nitrogen, oxygen, sulfur, an aryl group having 6 to 30 carbon atoms or a heterocyclic group having 1 to 30 carbon atoms;
  • R 1 and R 2 are independently selected from a hydrogen atom, a cyano group, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substitution or
  • the unsubstituted carbon atom group is an aromatic amine group of 7 to 30, a substituted or unsubstituted aralkyloxy group having 7 to 30 carbon atoms, and a substituted or unsubstituted aralkyl fluorenyl group having 7 to 30 carbon atoms. Or an alkyl group having 1 to 30 carbon atoms;
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 are independently selected from a hydrogen atom, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms.
  • the substituted or unsubstituted aromatic amine group has 7 to 30 carbon atoms.
  • the present invention provides an organic electroluminescent device comprising the aromatic heterocyclic compound described in any one of the above aspects or the aromatic heterocyclic compound prepared by the production method described in the above technical scheme.
  • the organic layer comprises the aromatic heterocyclic compound according to any one of the above aspects or the above technical solution
  • the aromatic heterocyclic compound prepared by the preparation method is not limited to any one of the above aspects or the above technical solution.
  • the present invention provides an organic photoelectric material, characterized by comprising the aromatic heterocyclic compound according to any one of the above aspects or the aromatic heterocyclic compound prepared by the preparation method described in the above technical scheme;
  • the organic optoelectronic material includes an organic solar cell, an electronic paper, an organic photoreceptor, or an organic transistor.
  • the present invention provides a benzo[g]pyridazine-containing aromatic heterocyclic compound having the structure of formula (I), wherein L 1 , L 2 , L 3 , L 4 are independently selected from 0 or 1; Q 1 and Q 2 are independently selected from nitrogen, oxygen, sulfur, an aryl group having 6 to 30 carbon atoms or a heterocyclic group having 1 to 30 carbon atoms; and R 1 and R 2 are independently selected from a hydrogen atom, A cyano group, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, and a substituted or unsubstituted aromatic group having 7 to 30 carbon atoms.
  • L 1 , L 2 , L 3 , L 4 are independently selected from 0 or 1
  • Q 1 and Q 2 are independently selected from nitrogen, oxygen, sulfur, an aryl group having 6 to 30 carbon atoms or a heterocyclic
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 are independently selected from a hydrogen atom, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms.
  • the aromatic heterocyclic compound having the structure represented by the formula (I) provided by the present invention is introduced into Q 1 , Q 2 , Ar 1 , Ar 2 , Ar in a benzo[g]pyridazine compound.
  • the organic electroluminescent device produced by the aromatic heterocyclic compound shown in I) has high luminous efficiency and service life, as well as higher brightness and excellent heat resistance. Further, the novel aromatic heterocyclic compound provided by the present invention is simple in preparation and easy to industrialize. The experimental results show that the aromatic heterocyclic compound provided by the invention and the prepared organic electroluminescent device have good optical properties, and can improve the luminous efficiency and the service life of the light-emitting device.
  • the present invention provides an aromatic heterocyclic compound having the structure represented by the formula (I):
  • L 1 , L 2 , L 3 , L 4 are independently selected from 0 or 1, more preferably L 1 and L 2 are not 0;
  • Q 1 and Q 2 are independently selected from nitrogen, oxygen, sulfur, an aryl group having 6 to 30 carbon atoms or a heterocyclic group having 1 to 30 carbon atoms, more preferably selected from nitrogen, oxygen, sulfur, and carbon atoms.
  • the number is 6 to 24 aryl groups or a heterocyclic group having 1 to 24 carbon atoms, more preferably selected from nitrogen, oxygen, sulfur, an aryl group having 6 to 14 carbon atoms or a carbon number of 1 to 14.
  • Heterocyclic group is independently selected from nitrogen, oxygen, sulfur, an aryl group having 6 to 30 carbon atoms or a heterocyclic group having 1 to 30 carbon atoms, more preferably selected from nitrogen, oxygen, sulfur, and carbon atoms.
  • the aromatic heterocyclic compound is more specifically preferably represented by any one of the structures (II-1) to (II-9) on Q 1 and Q 2 :
  • Z 1 to Z 16 are each independently selected from C, CH or N; L 3 and L 4 are independently selected from 0 or 1;
  • R 1 and R 2 are independently selected from a hydrogen atom, a cyano group, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms.
  • a substituted or unsubstituted aromatic amine group having 7 to 30 carbon atoms a substituted or unsubstituted aralkyloxy group having 7 to 30 carbon atoms or a substituted or unsubstituted carbon atom having 7 to 30 carbon atoms
  • An aralkyl fluorenyl group or an alkyl group having 1 to 30 carbon atoms more preferably a hydrogen atom, a cyano group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted carbon number a 5- to 30-membered heterocyclic group, a substituted or unsubstituted aromatic amine group having 7 to 25 carbon atoms, a substituted or unsubstituted aralkyloxy group having 7 to 25 carbon atoms or a substituted or unsubstituted one.
  • the aralkyl fluorenyl group having 7 to 25 carbon atoms or an alkyl group having 1 to 25 carbon atoms more preferably selected from a hydrogen atom, a cyano group, a substituted or unsubstituted aryl group having 10 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 8 to 20 carbon atoms, a substituted or unsubstituted aromatic amino group having 10 to 20 carbon atoms, a substituted or unsubstituted carbon atom 10 to 20 aralkyl group or a substituted carbon atoms aryl is unsubstituted alkylmercapto group having 10 to 20 carbon atoms or an alkyl group having 2 to 20.
  • the aromatic heterocyclic compound is more specifically preferably represented by any one of the structures (III-1) to (III-7) on R 1 and R 2 :
  • Z 1 to Z 8 are independently selected from C, CH or N; L 3 and L 4 are independently 0 or 1;
  • Q 1 and Q 2 are independently selected from nitrogen, oxygen, sulfur, an aryl group having 6 to 30 carbon atoms or a heterocyclic group having 1 to 30 carbon atoms, more preferably from nitrogen, oxygen, sulfur, and carbon atoms. It is an aryl group of 7 to 25 or a heterocyclic group having 2 to 25 carbon atoms, more preferably an aryl group having 10 to 20 carbon atoms or a heterocyclic number of 5 to 20 carbon atoms, nitrogen or oxygen, sulfur. base;
  • R 2 , R 1 ' and R 2 ' are independently selected from an aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms or a carbon number of 1 to 30.
  • the alkyl group is more preferably an aryl group having 7 to 30 carbon atoms, a substituted or unsubstituted heterocyclic group having 7 to 30 carbon atoms or an alkyl group having 7 to 25 carbon atoms, more preferably a carbon atom.
  • the number is 10 to 20, an aryl group, a substituted or unsubstituted heterocyclic group having 10 to 20 carbon atoms or an alkyl group having 10 to 20 carbon atoms.
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 are independently selected from a hydrogen atom, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms.
  • the substituted or unsubstituted aromatic amine group having 7 to 30 carbon atoms more preferably a hydrogen atom, a substituted or unsubstituted aralkyl group having 10 to 30 carbon atoms, or a substituted or unsubstituted carbon atom It is a 10 to 30 aralkyloxy group, a substituted or unsubstituted aralkyl fluorenyl group having 10 to 30 carbon atoms, an aryl group having 8 to 30 carbon atoms, and a substituted or unsubstituted carbon atom number of 7 to 30.
  • Carbon atoms, a substituted or unsubstituted 10 to 25 carbon atoms, a heterocyclic group, or a substituted or unsubstituted aromatic amine is 15 to 20.
  • the aromatic heterocyclic compound when R 1 and R 2 are each selected from a hydrogen atom, is more specifically preferably represented by any one of the formulae (IV-1) to (IV-10) on Q 1 and Q 2 :
  • Z 1 ⁇ Z 16 are independently selected from C, CH or N; L 3 and L 4 are independently 0 or 1;
  • Q 1 and Q 2 are independently selected from nitrogen, oxygen, sulfur, an aryl group having 6 to 30 carbon atoms or a heterocyclic group having 1 to 30 carbon atoms, more preferably from nitrogen, oxygen, sulfur, and carbon atoms. It is an aryl group of 7 to 25 or a heterocyclic group having 2 to 25 carbon atoms, more preferably an aryl group having 10 to 20 carbon atoms or a heterocyclic number of 5 to 20 carbon atoms, nitrogen or oxygen, sulfur. base;
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 are independently selected from a hydrogen atom, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms.
  • the substituted or unsubstituted aromatic amine group having 7 to 30 carbon atoms more preferably a hydrogen atom, a substituted or unsubstituted aralkyl group having 10 to 30 carbon atoms, or a substituted or unsubstituted carbon atom It is a 10 to 30 aralkyloxy group, a substituted or unsubstituted aralkyl fluorenyl group having 10 to 30 carbon atoms, an aryl group having 8 to 30 carbon atoms, and a substituted or unsubstituted carbon atom number of 7 to 30.
  • Carbon atoms, a substituted or unsubstituted 10 to 25 carbon atoms, a heterocyclic group, or a substituted or unsubstituted aromatic amine is 15 to 20.
  • Ar 1 and Ar 2 are independently selected from substituted or unsubstituted.
  • the amine group, Ar 1 and Ar 2 are more preferably selected from a substituted or unsubstituted aryl group having 15 to 20 carbon atoms, a substituted or unsubstituted heterocyclic group having 10 to 25 carbon atoms, or a substituted or unsubstituted group.
  • the aromatic heterocyclic compound is more particularly preferably represented by any one of the formulae (1) to (35) on Ar 1 to Ar 4 :
  • X and Y are independently selected from a hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, and a substitution.
  • the number is an aromatic amine group of 15 to 20.
  • the substituted group means a substituent which is preferably selected from the group consisting of halogen, a C1-C30 alkyl group, a C2-C30 alkenyl group, a C2-C30 alkynyl group, a hydroxyl group, and a C1-C30 group.
  • the aromatic heterocyclic compound provided by the invention introduces Q 1 , Q 2 , Ar 1 , Ar 2 , Ar 3 and Ar 4 groups in the benzo[g]pyridazine compound, thereby improving electron concentration and skill; and changing benzene And [g] the kinds of R 1 and R 2 of the pyridazine can improve the properties of the aromatic heterocyclic compound, so that the organic electroluminescent device comprising the aromatic heterocyclic compound represented by the formula (I) disclosed in the present invention has a comparative advantage. High luminous efficiency and longevity, as well as higher brightness and excellent heat resistance. The experimental results show that the aromatic heterocyclic compound provided by the invention and the prepared organic electroluminescent device have good optical properties, and can improve the luminous efficiency and the service life of the light-emitting device.
  • the invention also provides a preparation method of an aromatic heterocyclic compound, comprising:
  • the compound represented by the formula (V) is reacted with a compound represented by the formula (VI) and a compound represented by the formula (VII) to obtain an aromatic heterocyclic compound represented by the formula (I);
  • X' is a halogen atom, and Y' and Y 1 ' are independently selected from B(OH) 2 or H;
  • L 1 , L 2 , L 3 , L 4 are independently selected from 0 or 1;
  • Q 1 and Q 2 are independently selected from nitrogen, oxygen, sulfur, an aryl group having 6 to 30 carbon atoms or a heterocyclic group having 1 to 30 carbon atoms;
  • R 1 and R 2 are independently selected from a hydrogen atom, a cyano group, a substituted or unsubstituted aryl group having 6 to 50 carbon atoms, a substituted or unsubstituted heterocyclic group having 5 to 50 carbon atoms, a substitution or
  • the unsubstituted carbon atom group is an aromatic amine group of 7 to 30, a substituted or unsubstituted aralkyloxy group having 7 to 30 carbon atoms, and a substituted or unsubstituted aralkyl fluorenyl group having 7 to 30 carbon atoms. Or an alkyl group having 1 to 30 carbon atoms;
  • Ar 1 , Ar 2 , Ar 3 and Ar 4 are independently selected from a hydrogen atom, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms, a substituted or unsubstituted aralkyl group having 7 to 50 carbon atoms.
  • the substituted or unsubstituted aromatic amine group has 7 to 30 carbon atoms.
  • L 1 , L 2 , L 3 , L 4 , Q 1 , Q 2 , Ar 1 , Ar 2 , Ar 3 , Ar 4 , R 1 and R 2 are all the same as described above, and are not described herein again.
  • the raw material used in the present invention is not particularly limited in its source, and is commercially available or can be produced according to a production method well known to those skilled in the art.
  • the purity of the raw material used in the present invention is not particularly limited, and may be purely known to those skilled in the art for the purity of such a reaction, and the present invention is preferably of analytical grade and above.
  • the compound represented by the formula (V) in the present invention is preferably produced by the following method:
  • Q 1 or Q 2 is a C6-C30 aryl group or a C1-C30 heterocyclic group
  • Y' or Y 1 ' is B(OH) 2
  • a compound represented by the formula (V) and a formula ( The compound shown by VI) or the compound of the formula (VII) is subjected to a CC coupling reaction under the action of a catalyst, and the reaction conditions are not particularly limited as long as it is a reaction condition well known to those skilled in the art.
  • the compound represented by the formula (VI) is preferably produced by the following method:
  • X" is a halogen atom.
  • the compound of the formula (VII) is preferably prepared by the following method:
  • X" is a halogen atom.
  • the compound represented by the formula (IV) is subjected to a reduction reaction to obtain a compound represented by the formula (I).
  • the present invention also provides an organic electroluminescent device comprising the aromatic heterocyclic compound according to any one of the above aspects or the aromatic heterocyclic compound prepared by any one of the preparation methods.
  • the other conditions of the organic electroluminescent device of the present invention are not particularly limited, and the organic electroluminescent device is well known to those skilled in the art.
  • the present invention preferably includes a first electrode, a second electrode, and is disposed in the first An organic layer between the electrode and the second electrode; the organic layer comprising the above aromatic heterocyclic compound.
  • the organic layer preferably includes a hole injection layer, a hole transport layer, and both hole injection and The hole transporting skill layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transporting layer, the electron injecting layer, and one or more layers having both electron transport and electron injecting skill layers, more preferably including sequentially Hole injection layer, hole transport layer, electron blocking layer, light emitting layer, hole blocking layer, electron transport layer and electron injecting layer or sequentially provided with both hole injection and hole transporting skill layer, electron blocking layer
  • the light-emitting layer and the hole blocking layer have both an electron transport and an electron injection skill layer.
  • the organic material layer of the present invention includes a hole injection layer, a hole transport layer, or both a hole injection and a hole transporting skill layer
  • the hole injection layer, the hole transport layer, or both the hole injection layer and the hole injection layer At least one of the hole transporting skill layers includes a hole injecting substance, a hole transporting substance, or a substance having both hole injection and hole transporting skills.
  • the organic layer of the present invention has a single layer structure
  • the organic layer is a light emitting layer
  • the organic layer includes a light emitting layer
  • the light emitting layer preferably includes a phosphorescent body and a fluorescent body.
  • a phosphorescent dopant material and a fluorescent dopant are those represented by formula (I) Heterocyclic compound.
  • the luminescent layer may also preferably be a red, yellow or cyan luminescent layer, which is the host or dopant of the red, yellow or cyan luminescent layer.
  • the aromatic heterocyclic compound represented by the formula (I) can provide high efficiency, high brightness, high resolution and long when used in a cyan main body or cyan doping. Lifetime organic light-emitting devices.
  • the electron transport layer may include an aromatic heterocyclic compound and/or a metal compound represented by the formula (I).
  • the metal compound is a substance well known to those skilled in the art for electron transport, and is not particularly limited.
  • the organic layer simultaneously includes a light-emitting layer and an electron transport layer
  • the light-emitting layer and the electron transport layer may include an aromatic heterocyclic compound represented by the formula (I) having the same or different structure.
  • the organic electroluminescent device provided by the present invention is prepared by a method for preparing an organic electronic device by using the aromatic heterocyclic compound represented by the formula (I) and a conventional material, and is not particularly limited.
  • the present invention preferably utilizes thin film evaporation and electron beam evaporation. Or a method such as physical vapor deposition, a metal and a conductive oxide and an alloy thereof are vapor-deposited on the substrate to form an anode, and then an organic layer and an evaporation cathode are formed thereon to obtain an organic electroluminescence device.
  • the organic layer may include a multilayer structure of the hole injection layer, the hole transport layer, the light-emitting layer, the hole blocking layer, and the electron transport layer described above, and the multilayer structure may be subjected to the above-described thin film evaporation and electron beam evaporation. Or vapor deposition by physical vapor deposition, etc., or a variety of polymer materials solvent engineering can be used instead of evaporation methods, such as spin-coating, tape-casting, and doctor-blading. ), screen-printing, inkjet printing, or thermal imaging (Thermal-Imaging) reduces the number of layers.
  • the organic electroluminescent device provided by the present invention can also be classified into front side light emitting, back light emitting or double side light emitting according to materials used.
  • the present invention also provides an organic photoelectric material, comprising the aromatic heterocyclic compound according to any one of the above aspects, or the aromatic heterocyclic compound prepared by the preparation method according to any one of the technical solutions;
  • the organic photoelectric material comprises Organic solar cells, electronic paper, organic photoreceptors or organic transistors.
  • the aromatic heterocyclic compound provided by the present invention can be applied to an organic solar cell (OSC) in addition to an organic light emitting device (OLED) such as an OLED for illumination or a flexible OLED.
  • OSC organic solar cell
  • OLED organic light emitting device
  • e-paper electronic paper
  • OPC organic photoreceptor
  • OTFT organic thin film transistor
  • Example 1 According to the above synthesis method of the intermediate A-1 of Example 1, the compounds shown in Table 1 were prepared in the same molar ratio, and Table 1 is a summary of the reaction materials, the produced substances and the yields of Example 2 of the present invention.
  • Table 2 is a summary of the reaction materials, produced materials and yields of Example 4 of the present invention.
  • Phenylboronic acid (24.4 g, 0.20 mol), 2,3-dibromo-5-chloroquinoline (27.3 g, 0.10 mol), tetrakistriphenylphosphine palladium (7.0 g, 3%) was added to the reaction flask and added Toluene 600 mL, sodium carbonate aqueous solution (2N, 250 mL) was protected with nitrogen, and the oil was reacted at 90 ° C overnight.
  • Example 3 According to the synthesis method of the intermediate A-9 of the above Example 5, the compound shown in Table 3 was prepared in the same molar ratio, and Table 3 is a summary of the reaction material, the produced material and the yield of Example 6 of the present invention.
  • Example 4 According to the above synthesis method of the intermediate A-13 of Example 7, the compounds shown in Table 4 were prepared in the same molar ratio, and Table 4 is a summary of the reaction materials, the resulting substances and the yields of Example 8 of the present invention.
  • Example 5 According to the synthesis method of the intermediate B-1 of the above Example 9, the compounds shown in Table 5 were prepared in the same molar ratio, and Table 5 is a summary of the reaction materials, the starting materials and the yields of Example 10 of the present invention.
  • B-1 (10 g, 41.3 mmol) compound was dissolved in 300 ml of THF, and the temperature was lowered to 0 ° C.
  • the mixture was added to LTMP (synthesis of LTMP: in 500 ml of THF, 0.13 mol of BuLi, 0.14 mol of 2 was dissolved at 0 ° C, 2,6,6-tetramethylpiperidine).
  • Table 6 is a summary of the reaction materials, produced materials and yields of Example 12 of the present invention.
  • the C-1 (10 g, 47.6 mmol) prepared in Example 11 was weighed, added to the reaction flask, 200 ml of acetonitrile was added, and 30 g of phosphorus oxychloride was added dropwise to the reaction flask, and the temperature was slowly raised after the addition was completed.
  • the reaction time was 5 hours at 60 °C.
  • Example 7 According to the synthesis method of the intermediate D-1 of the above Example 13, the compounds shown in Table 7 were prepared in the same molar ratio, and Table 7 is a summary of the reaction materials, the starting materials and the yields of Example 14 of the present invention.
  • Example 8 According to the synthesis method of the intermediate E-1 of the above Example 15, the compounds shown in Table 8 were prepared in the same molar ratio, and Table 8 is a summary of the reaction materials, the produced substances and the yields of Example 16 of the present invention.
  • Example 16 The E-2 obtained in Example 16 was analyzed by nuclear magnetic resonance, and the results were as follows:
  • Example 9 is the reaction material of Example 17 of the present invention. , product formation and yield summary.
  • Example 17 The F-1 obtained in Example 17 was analyzed by NMR, and the results were as follows: 1 H NMR (500 MHz, Chloroform) ⁇ 9.89 (s, 1H), 8.97 (s, 2H), 8.71 (s, 4H) , 8.26 (s, 2H), 7.90 (s, 4H), 7.65 - 7.42 (m, 5H).
  • the compound shown in Table 10 was prepared by using the compounds D10 to D13 prepared in Example 14 as the starting materials, and Table 10 is the reaction material of Example 18 of the present invention. , product formation and yield summary.
  • Example 18 The G-1 obtained in Example 18 was analyzed by NMR, and the results were as follows: 1H NMR (500 MHz, Chloroform) ⁇ 8.97 (s, 1H), 8.71 (s, 1H), 8.03 (s, 1H) , 7.90 (s, 1H), 7.59 (s, 1H), 7.47 (s, 1H), 7.32 (s, 1H).
  • Example 21 The H-3 obtained in Example 21 was analyzed by NMR, and the results were as follows: 1 H NMR (500 MHz, Chloroform) ⁇ 8.90 (s, 2H), 8.39 (s, 4H), 8.00 (s, 2H) , 7.68 (s, 2H), 7.06 (s, 4H).
  • Example 22 The H-4 obtained in Example 22 was analyzed by NMR, and the results were as follows: 1 H NMR (500 MHz, Chloroform) ⁇ 8.98 (s, 2H), 8.88 (s, 4H), 7.84 (s, 2H) , 7.47 (s, 2H), 7.43 (s, 4H).
  • Will Fisher's coating thickness is The ITO glass substrate was washed twice in distilled water, ultrasonically washed for 30 minutes, then washed sequentially in the order of isopropanol, acetone, and methanol for 30 minutes, repeatedly washed twice with distilled water, ultrasonically washed for 10 minutes, dried, and transferred to plasma. In the body washing machine, the substrate was washed for 5 minutes and sent to a vapor deposition machine.
  • the organic light-emitting device using the aromatic heterocyclic compound of the invention can obtain the experimental effect of good luminous efficiency and longevity, and thus can be applied to the OLED industry with high practicality.
  • the organic electroluminescent device of the invention is also suitable for light source, display panel, logo, etc. of flat panel display, planar illuminator, illuminating OLED illuminator for illumination, flexible illuminator, copier, printer, LCD backlight or measuring machine. .

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Abstract

一种如式（I）的含苯并[g]酞嗪的芳杂环化合物、其制备方法和包含该化合物的有机电致发光器件。式（I）化合物是在苯并[g]酞嗪化合物中引入Q 1、Q 2、Ar 1、Ar 2、Ar 3与Ar 4基团，可提高电子密集度及技能，改善芳杂环化合物的性能。制备方法简单，易于产业化。包含该化合物的有机电致发光器件具有较高发光效率和使用寿命，以及更高的亮度和优秀的耐热性。

Description

一种芳杂环化合物及其制备方法和有机电致发光器件
本申请要求于2015年06月02日提交中国专利局、申请号为201510295908.4、发明名称为“一种芳杂环化合物及其制备方法和有机电致发光器件”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
本发明涉及有机发光材料技术领域，尤其涉及一种芳杂环化合物及其制备方法。
背景技术
发光材料是指各种形式能量激发下能发光的物质。自然界中的许多物质，包括无机化合物和有机化合物，或多或少均可以发光。发光材料是一种精细高技术产业，广泛应用在工业、医学、交通及军事领域。发光材料按其组分可分为无机发光材料和有机发光材料。
而在众多发光材料中，由于有机化合物的种类繁多，可调性好，色彩丰富，色纯度高，分子设计相对比较灵活，并且在发光机理、物理化学性能上，或是在应用上都有各自的特点。因而，有机材料的研究日益受到人们的重视，这其中根据不同的分子结构，有机发光材料可分为：有机小分子发光材料、有机高分子发光材料和有机配合物发光材料。而这其中有机小分子发光材料种类繁多，它们多带有共轭杂环及各种生色团，结构易于调整，通过引入烯键、苯环等不饱和基团及各种生色团来改变其共轭长度，从而使化合物光电性质发生变化。因而，得到了众多的科研工作者一方面致力于小分子的研究，如恶二唑及其化合物类，三唑及其化合物类，罗丹明及其化合物类，香豆素类化合物，1,8-萘酰亚胺类化合物，吡唑啉化合物，三苯胺类化合物，卟啉类化合物，咔唑、吡嗪、噻唑类化合物，苝类化合物等。它们广泛应用于光学电子器件、DNA诊断、光化学传感器、染料、荧光增白剂、荧光涂料、激光染料、有机电致发光器件(OLED)等方面。
这其中，有机电致发光器件通常是指由两个对置的电极和插入在该两个电极之间的至少一层有机发光化合物组成。电荷被注入到在阳极和阴极之间形成的有机层中，以形成电子和空穴对，使具有荧光或磷光特性的有机化合物产生了光发射。它是一种新型的平面显示器件，具有节能、响应速度快、颜色稳定、环境适应性强、无辐射、质量轻、厚度薄等诸多优点。而且随着近几年光电通讯和多媒体领域的迅速发展，有机光电子材料已成为现代社会信息和电子产业的核心。因此，随着领域的高速发展，对有机发光材料在性能上也提出了更高的要求。
有鉴于此，如何找到一种具有更好性能的有机发光材料，提高发光器件的发光效率和使用寿命，一直是本领域研究人员亟待解决的问题。
发明内容
有鉴于此，本发明要解决的技术问题在于提供一种芳杂环化合物及其制备方法，以及有机电致发光器件，尤其是针对一种含苯并[g]酞嗪的芳杂环化合物。本发明提供的芳杂环化合物，具有更好的性能，能够提高发光器件的发光效率和使用寿命。
本发明提供了一种芳杂环化合物，具有式(I)所示结构：
Figure PCTCN2015095266-appb-000001
其中，
L1、L2、L3、L4独立地选自0或1；
Q1和Q2独立地选自氮、氧、硫、碳原子数是6～30的芳基或碳原子数是1～30的杂环基；
R1和R2独立地选自氢原子、氰基、取代或未取代的碳原子数是6～50的芳基、取代或未取代的碳原子数是5～50的杂环基、取代或未取代的碳原子数是7～30的芳香族胺基、取代或未取代的碳原子数是7～30的芳烷氧基、取代或未取代的碳原子数是7～30的芳烷巯基或碳原子数是1～30的烷基；
Ar1、Ar2、Ar3和Ar4独立地选自氢原子、取代或未取代的碳原子数是7～50的芳烷基、取代或未取代的碳原子数是7～50的芳烷氧基、取代或未取代的碳原子数是7～50的芳烷巯基、碳原子数是6～50的芳基、取代或未取代的碳原子数是5～50的杂环基、或者是取代或未取代的碳原子数是7～30的芳香族胺基。
优选的，所述芳杂环化合物具有以下结构：
Figure PCTCN2015095266-appb-000002
Figure PCTCN2015095266-appb-000003
其中，
Z1～Z16独立地选自CH、C或N；
L3和L4独立地选自0或1；
R1和R2独立地选自氢原子、氰基、取代或未取代的碳原子数是6～50的芳基、取代或未取代的碳原子数是5～50的杂环基、取代或未取代的碳原子数是7～30的芳香族胺基、取代或未取代的碳原子数是7～30的芳烷氧基或取代、未取代的碳原子数是7～30的芳烷巯基或碳原子数是1～30的烷基；
Ar1、Ar2、Ar3和Ar4独立地选自氢原子、取代或未取代的碳原子数7～50的芳烷基、取代或未取代的碳原子数7～50的芳烷氧基、取代或未取代的碳原子数7～50的芳烷巯基、碳原子数6～50的芳基、取代或未取代的碳原子数5～50的杂环基、或者是取代或未取代的碳原子数7～30的芳香族胺基。
优选的，所述芳杂环化合物具有以下结构：
Figure PCTCN2015095266-appb-000004
Figure PCTCN2015095266-appb-000005
Figure PCTCN2015095266-appb-000006
其中，
Z1～Z8独立地选自C、CH或N；L3与L4独立地为0或1；
Q1和Q2独立地选自氮、氧、硫、碳原子数是6～30的芳基或碳原子数是1～30的杂环基；
Ar1、Ar2、Ar3和Ar4独立地选自氢原子、取代或未取代的碳原子数是7～50的芳烷基、取代或未取代的碳原子数是7～50的芳烷氧基、取代或未取代的碳原子数是7～50的芳烷巯基、碳原子数是6～50的芳基、取代或未取代的碳原子数是5～50的杂环基、或者是取代或未取代的碳原子数是7～30的芳香族胺基；
R2、R1′和R2′独立地选自碳原子数是6～50的芳基、取代或未取代的碳原子数是5～50的杂环基或碳原子数是1～30的烷基。
优选的，所述芳杂环化合物具有以下结构：
Figure PCTCN2015095266-appb-000007
Figure PCTCN2015095266-appb-000008
Figure PCTCN2015095266-appb-000009
其中，
Z1～Z16独立地选自C、CH或N；L3与L4独立地为0或1；
Q1和Q2独立地选自氮、氧、硫、碳原子数是6～30的芳基或碳原子数是1～30的杂环基；
Ar1、Ar2、Ar3和Ar4独立地选自氢原子、取代或未取代的碳原子数是7～50的芳烷基、取代或未取代的碳原子数是7～50的芳烷氧基、取代或未取代的碳原子数是7～50的芳烷巯基、碳原子数是6～50的芳基、取代或未取代的碳原子数是5～50的杂环基、或者是取代或未取代的碳原子数是7～30的芳香族胺基。
优选的，所述芳杂环化合物中，-Ar1、-Ar2、-Ar3和-Ar4独立地选自以下式(1)～式(35)所示结构：
Figure PCTCN2015095266-appb-000010
Figure PCTCN2015095266-appb-000011
其中，
X和Y独立地选自氢原子、卤素原子、氰基、取代或未取代的碳原子数是1～30的烷基、取代或未取代的碳原子数是1～30的烷氧基、取代或未取代的碳原子数是2～30的烯基、取代或未取代的碳原子数是7～30的芳烷基、取代或未取代的碳原子数是7～30的芳烷氧基、取代或未取代的碳原子数是6～30的芳基、取代或未取代的碳原子数是6～30的芳氧基、取 代或未取代的碳原子数是5～30的杂环基、或者是取代或未取代的碳原子数是7～30的芳香族胺基。
优选的，所述Q1和Q2均为苯基，以及R1和R2均为氰基或苯基时，Ar1和Ar2独立地选自取代或未取代的碳原子数7～50的芳基、取代或未取代的碳原子数5～50的杂环基、或者是取代或未取代的碳原子数7～30的芳香族胺基；
所述L1与L2不同时为0。
本发明提供了一种芳杂环化合物的制备方法，包括：
将式(V)所示的化合物与式(VI)所示的化合物和式(VII)所示的化合物进行反应，得到式(I)所示的芳杂环化合物；
Figure PCTCN2015095266-appb-000012
其中，
X′为卤原子，Y′与Y1′独立地选自B(OH)2或H；
L1、L2、L3、L4独立地选自0或1；
Q1和Q2独立地选自氮、氧、硫、碳原子数是6～30的芳基或碳原子数是1～30的杂环基；
R1和R2独立地选自氢原子、氰基、取代或未取代的碳原子数是6～50的芳基、取代或未取代的碳原子数是5～50的杂环基、取代或未取代的碳原子数是7～30的芳香族胺基、取代或未取代的碳原子数是7～30的芳烷氧基、取代或未取代的碳原子数是7～30的芳烷巯基或碳原子数是1～30的烷基；
Ar1、Ar2、Ar3和Ar4独立地选自氢原子、取代或未取代的碳原子数是7～50的芳烷基、取代或未取代的碳原子数是7～50的芳烷氧基、取代或未取代的碳原子数是7～50的芳烷巯基、碳原子数是6～50的芳基、取代或未取代的碳原子数是5～50的杂环基、或者是取代或未取代的碳原子数是7～30的芳香族胺基。
本发明提供了一种有机电致发光器件，包括上述任意一项技术方案所述的芳杂环化合物或上述技术方案所述的制备方法制备的芳杂环化合物。
优选的，包括第一电极、第二电极和设置于所述第一电极与第二电极之间的有机物层；
所述有机物层包含上述任意一项技术方案所述的芳杂环化合物或上述技术方案所述 的制备方法制备的芳杂环化合物。
本发明提供了一种有机光电材料，其特征在于，包括上述任意一项技术方案所述的芳杂环化合物或上述技术方案所述的制备方法制备的芳杂环化合物；
所述有机光电材料包括有机太阳电池、电子纸、有机感光体或有机晶体管。
本发明提供了一种含苯并[g]酞嗪的芳杂环化合物，具有式(Ⅰ)所示结构，其中，L1、L2、L3、L4独立地选自0或1；Q1和Q2独立地选自氮、氧、硫、碳原子数是6～30的芳基或碳原子数是1～30的杂环基；R1和R2独立地选自氢原子、氰基、取代或未取代的碳原子数是6～50的芳基、取代或未取代的碳原子数是5～50的杂环基、取代或未取代的碳原子数是7～30的芳香族胺基、取代或未取代的碳原子数是7～30的芳烷氧基、取代或未取代的碳原子数是7～30的芳烷巯基或碳原子数是1～30的烷基；Ar1、Ar2、Ar3和Ar4独立地选自氢原子、取代或未取代的碳原子数是7～50的芳烷基、取代或未取代的碳原子数是7～50的芳烷氧基、取代或未取代的碳原子数是7～50的芳烷巯基、碳原子数是6～50的芳基、取代或未取代的碳原子数是5～50的杂环基、或者是取代或未取代的碳原子数是7～30的芳香族胺基。与现有技术相比，本发明提供的具有式(I)所示结构的芳杂环化合物，是在苯并[g]酞嗪化合物中引入Q1、Q2、Ar1、Ar2、Ar3与Ar4基团，可提高电子密集度及技能；而且改变苯并[g]酞嗪的R1和R2的种类可以改善芳杂环化合物的性能，使得本发明所公开的包含式(I)所示的芳杂环化合物制造的有机电致发光器件具有较高发光效率和使用寿命，以及更高的亮度和优秀的耐热性。此外，本发明提供的新的芳杂环化合物的制法简单，易于产业化。实验结果表明，本发明提供的芳杂环化合物以及制备的有机电致发光器件，具有良好的光学性能，能够提高发光器件的发光效率和使用寿命。
具体实施方式
下面对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅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作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。
为了进一步理解本发明，下面结合实施例对本发明优选实施方案进行描述，但是应当理解，这些描述只是为进一步说明本发明的特征和优点，而不是对本发明权利要求的限制。
本发明提供了一种芳杂环化合物，具有式(I)所示结构：
Figure PCTCN2015095266-appb-000013
其中，
L1、L2、L3、L4独立地选自0或1，更优选为L1与L2不同时为0；
Q1和Q2独立地选自氮、氧、硫、碳原子数是6～30的芳基或碳原子数是1～30的杂环基，更优选选自氮、氧、硫、碳原子数是6～24的芳基或碳原子数是1～24的杂环基，更优选选自氮、氧、硫、碳原子数是6～14的芳基或碳原子数是1～14的杂环基。
所述芳杂环化合物在Q1和Q2上更具体优选如式(II-1)～式(II-9)任意一结构所示：
Figure PCTCN2015095266-appb-000014
Figure PCTCN2015095266-appb-000015
其中，Z1～Z16各自独立地选自C、CH或N；L3和L4独立地选自0或1；
本发明中R1和R2独立地选自氢原子、氰基、取代或未取代的碳原子数是6～50的芳基、取代或未取代的碳原子数是5～50的杂环基、取代或未取代的碳原子数是7～30的芳香族胺基、取代或未取代的碳原子数是7～30的芳烷氧基或取代、未取代的碳原子数是7～30的芳烷巯基或碳原子数是1～30的烷基，更优选的选自氢原子、氰基、取代或未取代的碳原子数是6～30的芳基、取代或未取代的碳原子数是5～30的杂环基、取代或未取代的碳原子数是7～25的芳香族胺基、取代或未取代的碳原子数是7～25的芳烷氧基或取代、未取代的碳原子数是7～25的芳烷巯基或碳原子数是1～25的烷基，更优选的选自氢原子、氰基、取代或未取代的碳原子数是10～20的芳基、取代或未取代的碳原子数是8～20的杂环基、取代或未取代的碳原子数是10～20的芳香族胺基、取代或未取代的碳原子数是10～20的芳烷氧基或取代、未取代的碳原子数是10～20的芳烷巯基或碳原子数是2～20的烷基。
所述芳杂环化合物在R1和R2上更具体优选如式(III-1)～式(III-7)任意一结构所示：
Figure PCTCN2015095266-appb-000016
Figure PCTCN2015095266-appb-000017
Figure PCTCN2015095266-appb-000018
其中，
Z1～Z8独立地选自C、CH或N；L3与L4独立地为0或1；
Q1和Q2独立地选自氮、氧、硫、碳原子数是6～30的芳基或碳原子数是1～30的杂环基，更优选自氮、氧、硫、碳原子数是7～25的芳基或碳原子数是2～25的杂环基，更优选自氮、氧、硫、碳原子数是10～20的芳基或碳原子数是5～20的杂环基；
R2、R1′和R2′独立地选自碳原子数是6～50的芳基、取代或未取代的碳原子数是5～50的杂环基或碳原子数是1～30的烷基，更优选自碳原子数是7～30的芳基、取代或未取代的碳原子数是7～30的杂环基或碳原子数是7～25的烷基，更优选自碳原子数是10～20的芳基、取代或未取代的碳原子数是10～20的杂环基或碳原子数是10～20的烷基。
Ar1、Ar2、Ar3和Ar4独立地选自氢原子、取代或未取代的碳原子数是7～50的芳烷基、取代或未取代的碳原子数是7～50的芳烷氧基、取代或未取代的碳原子数是7～50的芳烷巯基、碳原子数是6～50的芳基、取代或未取代的碳原子数是5～50的杂环基、或者是取代或未取代的碳原子数是7～30的芳香族胺基，更优选选自氢原子、取代或未取代的碳原子数是10～30的芳烷基、取代或未取代的碳原子数是10～30的芳烷氧基、取代或未取代的碳原子数是10～30的芳烷巯基、碳原子数是8～30的芳基、取代或未取代的碳原子数是7～30的杂环基、或者是取代或未取代的碳原子数是10～25的芳香族胺基，更优选选自氢原子、取代或未取代的碳原子数是15～25的芳烷基、取代或未取代的碳原子数是15～25的芳烷氧基、取代或未取代的碳原子数是15～25的芳烷巯基、碳原子数是15～25的芳基、取代或未取代的碳原子数是10～25的杂环基、或者是取代或未取代的碳原子数是15～20的芳香族胺基。
所述芳杂环化合物，当R1和R2均选自氢原子时，在Q1和Q2上更具体优选如式(IV-1)～式(IV-10)任意一结构所示：
Figure PCTCN2015095266-appb-000019
Figure PCTCN2015095266-appb-000020
Figure PCTCN2015095266-appb-000021
其中，
Z1～Z16独立地选自C、CH或N；L3与L4独立地为0或1；
Q1和Q2独立地选自氮、氧、硫、碳原子数是6～30的芳基或碳原子数是1～30的杂环基，更优选自氮、氧、硫、碳原子数是7～25的芳基或碳原子数是2～25的杂环基，更优选自氮、氧、硫、碳原子数是10～20的芳基或碳原子数是5～20的杂环基；
Ar1、Ar2、Ar3和Ar4独立地选自氢原子、取代或未取代的碳原子数是7～50的芳烷基、取代或未取代的碳原子数是7～50的芳烷氧基、取代或未取代的碳原子数是7～50的芳烷巯基、碳原子数是6～50的芳基、取代或未取代的碳原子数是5～50的杂环基、或者是取代或未取代的碳原子数是7～30的芳香族胺基，更优选选自氢原子、取代或未取代的碳原子数是10～30的芳烷基、取代或未取代的碳原子数是10～30的芳烷氧基、取代或未取代的碳原子数是10～30的芳烷巯基、碳原子数是8～30的芳基、取代或未取代的碳原子数是7～30的杂环基、或者是取代或未取代的碳原子数是10～25的芳香族胺基，更优选选自氢原子、取代或未取代的碳原子数是15～25的芳烷基、取代或未取代的碳原子数是15～25的芳烷氧基、取代或未取代的碳原子数是15～25的芳烷巯基、碳原子数是15～25的芳基、取代或未取代的碳原子数是10～25的杂环基、或者是取代或未取代的碳原子数是15～20的芳香族胺基。
在某些特定实施例中，当所述Q1和Q2均为苯基，以及R1和R2均为氰基或苯基时，Ar1和Ar2独立地选自取代或未取代的碳原子数7～50的芳基、取代或未取代的碳原子数5～50的杂环基、或者是取代或未取代的碳原子数7～30的芳香族胺基，Ar1和Ar2更优选选自取代或未取代的碳原子数10～30的芳基、取代或未取代的碳原子数7～30的杂环基、或者是取代或未取代的碳原子数10～25的芳香族胺基，Ar1和Ar2更优选选自取代或未取代的碳原子数15～20的芳基、取代或未取代的碳原子数10～25的杂环基、或者是取代或未取代的碳原子数15～20的芳香族胺基。
所述芳杂环化合物在Ar1～Ar4上更具体优选如式(1)～式(35)任意一结构所示：
Figure PCTCN2015095266-appb-000022
Figure PCTCN2015095266-appb-000023
其中，
X和Y独立地选自氢原子、卤素原子、氰基、取代或未取代的碳原子数是1～30的烷基、取代或未取代的碳原子数是1～30的烷氧基、取代或未取代的碳原子数是2～30的烯基、取代或未取代的碳原子数是7～30的芳烷基、取代或未取代的碳原子数是7～30的芳烷氧基、取代或未取代的碳原子数是6～30的芳基、取代或未取代的碳原子数是6～30的芳氧基、取代或未取代的碳原子数是5～30的杂环基、或者是取代或未取代的碳原子数是7～30的芳香族胺基，更优选自氢原子、卤素原子、氰基、取代或未取代的碳原子数是2～25的烷基、取代或未取代的碳原子数是2～25的烷氧基、取代或未取代的碳原子数是3～25的烯基、取代或未取代的碳原子数是10～25的芳烷基、取代或未取代的碳原子数是10～25的芳烷氧基、取代或未取代的碳原子数是8～25的芳基、取代或未取代的碳原子数是8～25的芳氧基、取代或未取代的碳原子数是7～25的杂环基、或者是取代或未取代的碳原子数是10～25的芳香族胺基，更优选自氢原子、卤素原子、氰基、取代或未取代的碳原子数是5～20的烷基、取代或未取代的碳原子数是5～20的烷氧基、取代或未取代的碳原子数是5～20的烯基、取代或未取代的碳原子数是15～20的芳烷基、取代或未取代的碳原子数是15～20的芳烷氧基、取代或未取代的碳原子数是10～20的芳基、取代或未取代的碳原子数是10～20的芳氧基、取代或未取代的碳原子数是10～20的杂环基、或者是取代或未取代的碳原子数是15～20的芳香族胺基。
本发明中，上述取代的芳基、取代的杂环基、取代的芳香族胺基、取代的芳烷氧基、取代的芳烷巯基、取代的芳烷基、取代的烯基、取代的芳氧基中，所述取代的是指含有取代基的，所述取代基优选选自卤素、C1～C30的烷基、C2～C30的烯基、C2～C30的炔基、羟基、C1～C30的烷氧基、氨基、硝基、巯基、硫醚基、亚胺基、氰基、酰胺基、膦酸根、 膦、羧基、硫代羰基、磺酰基、氨磺酰基、羰基、醛基、酯基、乙酰基、乙酰氧基、氨基甲酰基、氧代基(＝O)、卤代烷基、取代的氨酰基和氨基烷基、环烷基(可为单环、稠合多环或非稠合多环)、杂环基(可为单环、稠合多环或非稠合多环)、单环或稠合或非稠合多环芳基(如苯基、萘基、吡咯基、吲哚基、呋喃基、噻吩基、咪唑基、噁唑基、异噁唑基、噻唑基、三唑基、四唑基、吡唑基、喹啉基、异喹啉基、吖啶基、吡嗪基、哒嗪基、嘧啶基、苯并咪唑基、苯并噻吩基或苯并呋喃基)、氨基、-O-C1～C20的烷基、O-芳基、芳基、芳基-C1～C20的烷基、-CO2CH3、-CONH2、-OCH2CONH2、-NH2、-SO2NH2、-OCHF2、-CF3、-OCF3。这些取代基可任选地进一步被选自上述基团的取代基取代。本发明中，所述取代基更优选选自以下式36～65中的任一取代基：
Figure PCTCN2015095266-appb-000024
本发明提供的芳杂环化合物在苯并[g]酞嗪化合物中引入Q1、Q2、Ar1、Ar2、Ar3与Ar4基团，可提高电子密集度及技能；而且改变苯并[g]酞嗪的R1和R2的种类可以改善芳杂环化合物的性能，使得本发明所公开的包含式(I)所示的芳杂环化合物制造的有机电致发光器件具有较高发光效率和使用寿命，以及更高的亮度和优秀的耐热性。实验结果表明，本发明提供的芳杂环化合物以及制备的有机电致发光器件，具有良好的光学性能，能够提高发光器件的发光效率和使用寿命。
本发明还提供一种芳杂环化合物的制备方法，包括：
将式(V)所示的化合物与式(VI)所示的化合物和式(VII)所示的化合物进行反应，得到式(I)所示的芳杂环化合物；
Figure PCTCN2015095266-appb-000025
其中，
X′为卤原子，Y′与Y1′独立地选自B(OH)2或H；
L1、L2、L3、L4独立地选自0或1；
Q1和Q2独立地选自氮、氧、硫、碳原子数是6～30的芳基或碳原子数是1～30的杂环基；
R1和R2独立地选自氢原子、氰基、取代或未取代的碳原子数是6～50的芳基、取代或未取代的碳原子数是5～50的杂环基、取代或未取代的碳原子数是7～30的芳香族胺基、取代或未取代的碳原子数是7～30的芳烷氧基、取代或未取代的碳原子数是7～30的芳烷巯基或碳原子数是1～30的烷基；
Ar1、Ar2、Ar3和Ar4独立地选自氢原子、取代或未取代的碳原子数是7～50的芳烷基、取代或未取代的碳原子数是7～50的芳烷氧基、取代或未取代的碳原子数是7～50的芳烷巯基、碳原子数是6～50的芳基、取代或未取代的碳原子数是5～50的杂环基、或者是取代或未取代的碳原子数是7～30的芳香族胺基。
其中，所述L1、L2、L3、L4、Q1、Q2、Ar1、Ar2、Ar3、Ar4、R1与R2均同上所述，在此不再赘述。
本发明所用原料，对其来源没有特别限制，在市场上购买的或是按照本领域技术人员熟知的制备方法制备得到即可。
本发明所用原料的纯度没有特别限制，以本领域技术人员熟知的用于此类反应的纯度即可，本发明优选为分析纯及以上级别。
本发明中所述式(V)所示的化合物优选按照以下方法进行制备：
Figure PCTCN2015095266-appb-000026
按照本发明，当Q1或Q2为C6～C30的芳基或C1～C30的杂环基；Y′或Y1′为B(OH)2，式(V)所示的化合物与式(VI)所示的化合物或式(VII)所示的化合物在催化剂作用下进行C-C耦合反应，所述反应条件为本领域技术人员熟知的反应条件即可，并无特殊的限制。
当所述Q1或Q2为N、O或S时，Y′或Y1′为H，此时，式(V)所示的化合物与式(VI)所示的化合物或式(VII)所示的化合物进行置换反应；所述置换反应的条件为本领域技术人员熟知的置换反应条件即可，并无特殊的限制。
上述反应式中，所述R1、X‘均同上所述，在此不再赘述。
本发明中，当Y＇为B(OH)2时，所述式(VI)所示的化合物优选按照以下方法制备：
Figure PCTCN2015095266-appb-000027
X＂为卤素原子。
当Y1′为B(OH)2时，式(VII)所示的化合物，优选按照以下方法制备：
Figure PCTCN2015095266-appb-000028
X＂为卤素原子。
在本发明中，当所述L1与L2同时为0时，将式(IV)所示的化合物经过还原反应后，即可得到式(I)所示的化合物。
从上述制备过程中，可以看出本发明提供的芳杂环化合物制备方法简单，易于产业化。
本发明还提供一种有机电致发光器件，包括上述任意一项技术方案所述的芳杂环化合物或任意一项制备方法制备的芳杂环化合物。
本发明对所述有机电致发光器件的其他条件没有特别限制，以本领域技术人员熟知的有机电致发光器件即可，本发明优选包括第一电极、第二电极和设置于所述第一电极与第二电极之间的有机物层；所述有机物层包含上述的芳杂环化合物。
按照本发明，所述有机物层优选包括空穴注入层、空穴传输层、既具备空穴注入又具 备空穴传输技能层、电子阻挡层、发光层、空穴阻挡层、电子传输层、电子注入层与既具备电子传输又具备电子注入技能层中的一层或多层，更优选包括依次设置的空穴注入层、空穴传输层、电子阻挡层、发光层、空穴阻挡层、电子传输层与电子注入层或依次设置的既具备空穴注入又具备空穴传输技能层、电子阻挡层、发光层、空穴阻挡层与既具备电子传输又具备电子注入技能层。
当本发明有机物层包含空穴注入层、空穴传输层或既具备空穴注入又具备空穴传输技能层时，优选所述空穴注入层、空穴传输层或既具备空穴注入又具备空穴传输技能层中至少一层包含空穴注入物质、空穴传输物质或既具备空穴注入又具备空穴传输技能的物质。
当本发明有机物层为单层结构时，所述有机物层为发光层，当所述有机物层为多层结构时，所述有机物层包括发光层；所述发光层中优选包括磷光主体、荧光主体、磷光掺杂材料与荧光掺杂中的一种或多种；所述磷光主体、荧光主体、磷光掺杂材料与荧光掺杂材料中的一种或多种为式(I)所示的芳杂环化合物。
所述发光层还可优选为红色、黄色或青色发光层，所述芳杂环化合物为红色、黄色或青色发光层的主体或掺杂物质。如，当所述发光层为青色发光层时，所述式(I)所示的芳杂环化合物使用在青色主体或青色掺杂用途时，可提供高效率、高亮度、高分辨率及长寿命的有机发光器件。
当所述有机物层包括电子传输层时，所述电子传输层可包括式(I)所示的芳杂环化合物和/或金属化合物。所述金属化合物为本领域技术人员熟知的用于电子传输的物质即可，并无特殊的限制。
当所述有机物层同时包括发光层与电子传输层时，所述发光层与电子传输层可包括结构相同或不相同的式(I)所示的芳杂环化合物。
本发明提供的有机电致发光器件利用式(I)所示的芳杂环化合物及常规材料制成有机电子器件的方法制备，并无特殊的限制，本发明优选利用薄膜蒸镀、电子束蒸发或物理气相沉积等方法在基板上蒸镀金属及具有导电性的氧化物及它们的合金形成阳极，然后在其上形成有机物层及蒸镀阴极，得到有机电致发光器件。
所述有机物层可以同时包括上述的空穴注入层、空穴传输层、发光层、空穴阻挡层及电子传输层的多层结构，并且这些多层结构可按照上述薄膜蒸镀、电子束蒸发或物理气相沉积等方法蒸镀，也可使用多样的高分子材料溶剂工程替代蒸镀方法，如旋转涂膜(spin-coating)、薄带成型(tape-casting)、刮片法(doctor-blading)、丝网印刷(Screen-Printing)、喷墨印刷或热成像(Thermal-Imaging)等方法减少层数制造。
本发明提供的有机电致发光器件按照使用的材料也可分为前面发光、背面发光或两面发光。
本发明还提供了一种有机光电材料，包括上述任意一项技术方案所述的芳杂环化合物，或任意一项技术方案所述的制备方法制备的芳杂环化合物；所述有机光电材料包括有机太阳电池、电子纸、有机感光体或有机晶体管。
基于上述有机电致发光器件同样的原理应用，本发明所提供的芳杂环化合物除了在有机发光器件(OLED)，如照明用OLED、柔性OLED中，还可以应用在有机太阳电池(OSC)、电子纸(e-paper)、有机感光体(OPC)或有机薄膜晶体管(OTFT)上。
为了进一步说明本发明，下面结合实施例对本发明提供的芳杂环化合物及其制备方法以及有机电致发光器件进行详细描述。
实施例1
中间体2-氯-5-苯基吡嗪(A-1)的合成：
Figure PCTCN2015095266-appb-000029
将2-溴-5-氯吡嗪(21.3g，0.11mol)，苯硼酸(12.2g，0.10mol)，四三苯基磷钯0.5g，加入到1000mL反应瓶中，加入甲苯400mL，碳酸钠水溶液(2N，150mL)氮气保护，油浴80℃反应24小时。后处理过程：反应体系降温，静置30分钟分液，保留有机层，旋干甲苯，固体加入少量二氯甲烷溶解，过柱分离，用石油醚：二氯甲烷＝1：1(体积比)冲柱，得固体(A-1)(10.7g，y＝56％)。
实施例2
中间体A-2～A-5的合成：
按照上述实施例1中间体A-1的合成方法，用相同摩尔量比制备得到表1所示的化合物，表1是本发明实施例2反应物质、生成物质及产率汇总。
表1实施例2反应物质、生成物质及产率汇总
Figure PCTCN2015095266-appb-000030
实施例3
中间体5-氯-N,N-二苯基吡嗪-2-胺(A-6)的合成：
Figure PCTCN2015095266-appb-000031
将二苯胺(16.9g，0.10mol)和叔丁醇钠(28g，0.30mol)，甲苯400mL加入到反应瓶中，搅拌30分钟，氮气保护，然后加入2-溴-5-氯吡嗪(23.2g，0.12mol)、三(二亚卞基丙酮)二钯1.5g，最后加入三叔丁基膦4g，升温到100℃反应24小时。后处理过程：体系降温，加入水终止反应，过滤，滤液分液，旋干甲苯，加入少量二氯甲烷溶解固体，石油醚:二氯甲烷＝3:1(体积比)过柱分离，得固体(A-6)(14.1g，y＝50％)。
实施例4
中间体A-7和A-8的合成
按照上述实施例3中间体A-6的合成方法，用相同摩尔量比制备得到表2所示化合物，
表2是本发明实施例4反应物质、生成物质及产率汇总。
表2本发明实施例4反应物质、生成物质及产率汇总
Figure PCTCN2015095266-appb-000032
实施例5
中间体5-氯-2,3-二苯基吡嗪(A-9)的合成：
Figure PCTCN2015095266-appb-000033
将苯硼酸(24.4g，0.20mol)，2,3-二溴-5-氯喹啉(27.3g，0.10mol)，四三苯基膦钯(7.0g，3％)加入到反应瓶中，加入甲苯600mL，碳酸钠水溶液(2N,250mL)氮气保护，油浴90℃反应，过夜。后处理过程：体系降温，分液，旋干甲苯，剩余物用二氯甲烷全溶，再加入等量的石油醚，过硅胶漏斗，并用二氯甲烷：石油醚＝1：2(体积比)冲洗，直到无产品点流出，收集滤液，并旋干溶剂，得深色固体(A-9)(21.3g，y＝80％)。
实施例6
中间体A-10～A-12的合成
按照上述实施例5中间体A-9的合成方法，用相同摩尔量比制备得到表3所示化合物，表3是本发明实施例6反应物质、生成物质及产率汇总。
表3本发明实施例6反应物质、生成物质及产率汇总
Figure PCTCN2015095266-appb-000034
实施例7
中间体5-(4-吡啶基)嘧啶-2-基硼酸(A-13)的合成：
Figure PCTCN2015095266-appb-000035
取5-(4-吡啶基)-2-溴嘧啶(10g，42.4mmol)加入到三口瓶中，加入THF100mL，氮气保护，-78℃搅拌30分钟，然后加入正丁基锂(2.5M)21mL，反应1小时，再加入硼酸三异丙酯14g，低温反应1小时，逐渐恢复室温。后处理过程，体系中加入2M盐酸使溶液PH值为4-5，静置分液，水层用乙酸乙酯萃取一遍，合并有机层，旋干，得白色固体(A-13)(6.8g，y＝80％)。
实施例8
中间体A-14～A-18的合成
按照上述实施例7中间体A-13的合成方法，用相同摩尔量比制备得到表4所示化合物，表4是本发明实施例8反应物质、生成物质及产率汇总。
表4本发明实施例8反应物质、生成物质及产率汇总
Figure PCTCN2015095266-appb-000036
实施例9
中间体2-(吡嗪-2-羰基)苯甲酸甲酯(B-1)的合成：
Figure PCTCN2015095266-appb-000037
将2-溴吡嗪(15.9g，0.1mol)溶于300ml无水乙醚中，干冰浴-78℃，氮气保护，加入44ml的BuLi(2.5M)，搅拌反应1小时，再加入邻苯二甲酸二甲酯(19.4g，0.1mol)，反应2小时，后逐渐升到室温，加入水中止反应，后处理过程：体系分液，分去水层，水层用乙酸乙酯萃取一遍，合并有机层并旋干有机溶剂，用二氯甲烷:石油醚＝9:1过柱分离，得白色固体(B-1)(13.3g，Y＝55％)。
实施例10
中间体B-2～B-14的合成
按照上述实施例9中间体B-1的合成方法，用相同摩尔量比制备得到表5所示化合物，表5是本发明实施例10反应物质、生成物质及产率汇总。
表5本发明实施例10反应物质、生成物质及产率汇总
Figure PCTCN2015095266-appb-000038
Figure PCTCN2015095266-appb-000039
Figure PCTCN2015095266-appb-000040
实施例11
中间体苯并[g]喹喔啉-5,10-二酮(C-1)的合成：
Figure PCTCN2015095266-appb-000041
将实施例9制备的
B-1(10g，41.3mmol)化合物溶解于300ml的THF中，降温到0℃，加入混合液LTMP(LTMP的合成：在500ml的THF中，保持0℃溶解0.13mol BuLi，0.14mol的2,2,6,6-四甲基哌啶)。0℃搅拌反应2小时，加入200ml水中止反应，分去水层，有机层旋干，用二氯甲烷:石油醚＝10:1过柱分离，得固体(C-1)(3.4g，y＝40％)。
实施例12
中间体C-2～C-14的合成：
按照上述实施例11中间体C-1的合成方法，用相同摩尔量比制备得到表6所示化合物，
表6是本发明实施例12反应物质、生成物质及产率汇总。
表6本发明实施例12反应物质、生成物质及产率汇总
Figure PCTCN2015095266-appb-000042
Figure PCTCN2015095266-appb-000043
Figure PCTCN2015095266-appb-000044
实施例13
中间体5,10-二氯苯并[g]喹喔啉(D-1)的合成：
Figure PCTCN2015095266-appb-000045
称取实施例11制备的C-1(10g，47.6mmol)，加入到反应瓶中，加入200ml乙腈，再称取30g三氯氧磷缓慢滴加到反应瓶中，滴加完毕后缓慢升温到60℃，反应时间为5小时。反应完毕后，加入水小心萃灭，再加放大量的碳酸钠饱合溶液调PH值7-8，再加入二氯甲烷，萃取三次，旋干得固体(D-1)(9.0g，y＝75％)。
实施例14
中间体D-2～D14的合成：
按照上述实施例13中间体D-1的合成方法，用相同摩尔量比制备得到表7所示化合物，表7是本发明实施例14反应物质、生成物质及产率汇总。
表7本发明实施例14反应物质、生成物质及产率汇总
Figure PCTCN2015095266-appb-000046
Figure PCTCN2015095266-appb-000047
Figure PCTCN2015095266-appb-000048
实施例15
5,10-二(4-吡啶基)苯并[g]喹喔啉(E-1)的合成：
Figure PCTCN2015095266-appb-000049
将实施例13制备的D-1(15.0g,60mmol)，4-硼酸吡啶(18.0g,146mmol)，四三苯基膦钯4g加入到反应瓶中，再加入甲苯300mL，碳酸钠水溶液(2N,100ml)，氮气保护，搅拌升温到110℃反应24小时。后处理过程：降温，分液，旋干甲苯。加入二氯甲烷溶解固体，过柱，石油醚：乙酸乙酯＝2：1(体积比)冲洗，得固体(E-1)(12g，y＝60％)。
利用核磁共振对实施例15中得到的5,10-二(4-吡啶基)苯并[g]喹喔啉(E-1)进行分析，得到结果为：
1H NMR(500MHz,Chloroform)δ8.97(s,1H),8.94(s,1H),8.71(s,2H),7.90(s,2H), 7.47(s,1H)。质谱：334.13。
实施例16
E-2～E-23的合成：
按照上述实施例15中间体E-1的合成方法，用相同摩尔量比制备得到表8所示化合物，表8是本发明实施例16反应物质、生成物质及产率汇总。
表8本发明实施例16反应物质、生成物质及产率汇总
Figure PCTCN2015095266-appb-000050
Figure PCTCN2015095266-appb-000051
Figure PCTCN2015095266-appb-000052
利用核磁共振对实施例16中得到的E-2进行分析，得到结果为：
1H NMR(500MHz,Chloroform)δ8.97(s,1H),8.93(s,1H),8.37(s,1H),7.47(s,1H),7.38(s,1H),7.14(s,1H),6.90(s,1H)。
实施例17
F-1～F-9的合成：
按照上述实施例15中间体E-1的合成方法，以实施例14制备的化合物D2～D9为原料，用相同摩尔量比制备得到表9所示化合物，表9是本发明实施例17反应物质、生成物质及产率汇总。
表9本发明实施例17反应物质、生成物质及产率汇总
Figure PCTCN2015095266-appb-000053
Figure PCTCN2015095266-appb-000054
Figure PCTCN2015095266-appb-000055
利用核磁共振对实施例17中得到的F-1进行分析，得到结果为：1H NMR(500MHz,Chloroform)δ9.89(s,1H),8.97(s,2H),8.71(s,4H),8.26(s,2H),7.90(s,4H),7.65–7.42(m,5H)。
实施例18
G-1～G9的合成：
按照上述实施例15中间体E-1的合成方法，以实施例14制备的化合物D10～D13为原料，用相同摩尔量比制备得到表10所示化合物，表10是本发明实施例18反应物质、生成物质及产率汇总。
表10本发明实施例18反应物质、生成物质及产率汇总
Figure PCTCN2015095266-appb-000056
Figure PCTCN2015095266-appb-000057
利用核磁共振对实施例18中得到的G-1进行分析，得到的结果为：1H NMR(500MHz,Chloroform)δ8.97(s,1H),8.71(s,1H),8.03(s,1H),7.90(s,1H),7.59(s,1H),7.47(s,1H),7.32(s,1H)。
实施例19
N,N-二苯基-10-(吡啶-4-基氧基)苯并[g]喹喔啉-5-胺(H-1)的合成：
Figure PCTCN2015095266-appb-000058
1)10-氯-N,N-二苯基苯并[g]喹喔啉-5-胺的合成：
按照A-6的合成方法，加入5,10-二氯苯并[g]喹喔啉(6.0g,24mol)，二苯胺(4.4g，24mol)，得固体10-氯-N,N-二苯基苯并[g]喹喔啉-5-胺(5.04g，y＝55％)。
2)N,N-二苯基-10-(吡啶-4-基氧基)苯并[g]喹喔啉-5-胺(H-1)的合成：
取4-羟基吡啶(10g,0.1mol)溶于100mL无水四氢呋喃中，搅拌，准确称量NaH(0.96g,0.4mol)分批次加到反应瓶中，不要太快，防止太多气泡产生，加完后溶液呈现黄色，这时再加入10-氯-N,N-二苯基苯并[g]喹喔啉-5-胺(42.0g，0.11mol)，也要分批加入，室温反应过夜。后处理过程：过滤，除去固体物质，旋干，加入二氯甲烷溶解，过柱用石油醚：乙酸乙酯＝1：5冲柱，得固体(H-1)(22.0g，y＝50％)。
利用核磁共振对实施例19中得到的H-1进行分析，得到结果为：1H NMR(500MHz,Chloroform)δ8.90(d,J＝9.3Hz,2H),8.39(s,2H),8.12(s,1H),8.00(s,1H),7.68(s,1H),7.50(s,1H),7.24(s,4H),7.08(d,J＝4.2Hz,6H),7.00(s,2H)。
实施例20
N,N-二苯基-10-(吡啶-4-基硫)苯并[g]喹喔啉-5-胺(H-2)的合成：
Figure PCTCN2015095266-appb-000059
将4-吡啶硫醇(1.1g，10m mol)，N,N-二苯基-10-(吡啶-4-基氧基)苯并[g]喹喔啉-5-胺(3.8g，10mmol)，KOH(840mg，15mmol)，mPANI/pFe3O4(2.5g，5mol％)、H2O(30mL)加热8小时。通过乙酸乙酯萃取有机相，并采用(乙酸乙酯：石油醚＝4:1)过柱分离，得白色固体(H-2)(1.83g，y＝40％)。
利用核磁共振对实施例20中得到的H-2进行分析，得到结果为：1H NMR(500MHz,Chloroform)δ8.99(s,1H),8.89(d,J＝7.2Hz,3H),8.12(s,1H),7.84(s,1H),7.55–7.40(m,4H),7.24(s,4H),7.08(s,4H),7.00(s,2H)。
实施例21
5,10-二(吡啶-4-基氧基)苯并[g]喹喔啉(H-3)的合成：
Figure PCTCN2015095266-appb-000060
参考实施例19中H-1的合成方法，投入10-氯-N,N-二苯基苯并[g]喹喔啉-5-胺(5.0g，20mmol)，4-羟基吡啶(4.0g，42mmol)，得固体(H-3)(3.4g，y＝50％)。
利用核磁共振对实施例21中得到的H-3进行分析，得到结果为：1H NMR(500MHz,Chloroform)δ8.90(s,2H),8.39(s,4H),8.00(s,2H),7.68(s,2H),7.06(s,4H)。
实施例22
5,10-二(吡啶-4-基硫)苯并[g]喹喔啉(H-4)的合成：
Figure PCTCN2015095266-appb-000061
按照实施例20中H-2的合成方法，加入4-吡啶硫醇(2.2g，20m mol)，N,N-二苯基-10-(吡啶-4-基氧基)苯并[g]喹喔啉-5-胺(2.5g，10mmol)，KOH(840mg，15mmol),mPANI/pFe3O4(2.5g,5mol％)、H2O(30mL)加热8小时。通过乙酸乙酯萃取有机相，并采用乙酸乙酯：石油醚＝4:1过柱分离，得白色固体(H-4)(1.4g，y＝35％)。
利用核磁共振对实施例22中得到的H-4进行分析，得到结果为：1H NMR(500MHz,Chloroform)δ8.98(s,2H),8.88(s,4H),7.84(s,2H),7.47(s,2H),7.43(s,4H)。
实施例23
将费希尔公司涂层厚度为
Figure PCTCN2015095266-appb-000062
的ITO玻璃基板放在蒸馏水中清洗2次，超声波洗涤30分钟，然后按异丙醇、丙酮、甲醇的顺序依次洗涤30分钟，用蒸馏水反复清洗2次，超声波洗涤10分钟，干燥，转移到等离子体清洗机里，将上述基板洗涤5分钟，送到蒸镀机里。
将已经准备好的ITO透明电极上蒸镀空穴注入层2-TNATA蒸镀
Figure PCTCN2015095266-appb-000063
空穴传输层a-NPD蒸镀
Figure PCTCN2015095266-appb-000064
青色主体ADN/掺杂5％的TPPDA蒸镀
Figure PCTCN2015095266-appb-000065
空穴阻挡层及空穴传输层TPBi或实施例E～H的物质蒸镀
Figure PCTCN2015095266-appb-000066
阴极
Figure PCTCN2015095266-appb-000067
上述过程有机物蒸镀速度是保持
Figure PCTCN2015095266-appb-000068
LiF是
Figure PCTCN2015095266-appb-000069
Al是
Figure PCTCN2015095266-appb-000070
Figure PCTCN2015095266-appb-000071
上述方法得到的有机发光器件的电子发光特性见表11。
表11实施例23中空穴阻挡层及空穴传输层物质种类与有机电致发光器件的电子发光特性
Figure PCTCN2015095266-appb-000072
从上述表11中可以看出，利用本发明的芳杂环化合物的器件的发光效率及寿命特性均有显著的提高。
本发明采用芳杂环化合物的有机发光器件，可以得到发光效率和寿命良好的实验效果，因此可应用于实用性高的OLED产业。本发明的有机电致发光器件同样适用于平面面板显示、平面发光体、照明用面发光OLED发光体、柔性发光体、复印机、打印机、LCD背光灯或计量机类的光源、显示板、标识等。
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。
对所公开的实施例的上述说明，使本领域专业技术人员能够实现或使用本发明。对这些实施例的多种修改对本领域的专业技术人员来说将是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下，在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (10)

  1. 一种芳杂环化合物，具有式(I)所示结构：
    Figure PCTCN2015095266-appb-100001
    其中，
    L1、L2、L3、L4独立地选自0或1；
    Q1和Q2独立地选自氮、氧、硫、碳原子数是6～30的芳基或碳原子数是1～30的杂环基；
    R1和R2独立地选自氢原子、氰基、取代或未取代的碳原子数是6～50的芳基、取代或未取代的碳原子数是5～50的杂环基、取代或未取代的碳原子数是7～30的芳香族胺基、取代或未取代的碳原子数是7～30的芳烷氧基、取代或未取代的碳原子数是7～30的芳烷巯基或碳原子数是1～30的烷基；
    Ar1、Ar2、Ar3和Ar4独立地选自氢原子、取代或未取代的碳原子数是7～50的芳烷基、取代或未取代的碳原子数是7～50的芳烷氧基、取代或未取代的碳原子数是7～50的芳烷巯基、碳原子数是6～50的芳基、取代或未取代的碳原子数是5～50的杂环基、或者是取代或未取代的碳原子数是7～30的芳香族胺基。
  2. 根据权利要求1所述的芳杂环化合物，其特征在于，所述芳杂环化合物具有以下结构：
    Figure PCTCN2015095266-appb-100002
    Figure PCTCN2015095266-appb-100003
    其中，
    Z1～Z16独立地选自CH、C或N；
    L3和L4独立地选自0或1；
    R1和R2独立地选自氢原子、氰基、取代或未取代的碳原子数是6～50的芳基、取代或未取代的碳原子数是5～50的杂环基、取代或未取代的碳原子数是7～30的芳香族胺基、取代或未取代的碳原子数是7～30的芳烷氧基或取代、未取代的碳原子数是7～30的芳烷巯基或碳原子数是1～30的烷基；
    Ar1、Ar2、Ar3和Ar4独立地选自氢原子、取代或未取代的碳原子数7～50的芳烷基、 取代或未取代的碳原子数7～50的芳烷氧基、取代或未取代的碳原子数7～50的芳烷巯基、碳原子数6～50的芳基、取代或未取代的碳原子数5～50的杂环基、或者是取代或未取代的碳原子数7～30的芳香族胺基。
  3. 根据权利要求1所述的芳杂环化合物，其特征在于，所述芳杂环化合物具有以下结构：
    Figure PCTCN2015095266-appb-100004
    Figure PCTCN2015095266-appb-100005
    其中，
    Z1～Z8独立地选自C、CH或N；L3与L4独立地为0或1；
    Q1和Q2独立地选自氮、氧、硫、碳原子数是6～30的芳基或碳原子数是1～30的杂环基；
    Ar1、Ar2、Ar3和Ar4独立地选自氢原子、取代或未取代的碳原子数是7～50的芳烷基、取代或未取代的碳原子数是7～50的芳烷氧基、取代或未取代的碳原子数是7～50的芳烷巯基、碳原子数是6～50的芳基、取代或未取代的碳原子数是5～50的杂环基、或者是取代或未取代的碳原子数是7～30的芳香族胺基；
    R2、R1′和R2′独立地选自碳原子数是6～50的芳基、取代或未取代的碳原子数是5～50的杂环基或碳原子数是1～30的烷基。
  4. 根据权利要求1所述的芳杂环化合物，其特征在于，所述芳杂环化合物具有以下结构：
    Figure PCTCN2015095266-appb-100006
    Figure PCTCN2015095266-appb-100007
    其中，
    Z1～Z16独立地选自C、CH或N；L3与L4独立地为0或1；
    Q1和Q2独立地选自氮、氧、硫、碳原子数是6～30的芳基或碳原子数是1～30的杂环基；
    Ar1、Ar2、Ar3和Ar4独立地选自氢原子、取代或未取代的碳原子数是7～50的芳烷基、取代或未取代的碳原子数是7～50的芳烷氧基、取代或未取代的碳原子数是7～50的芳烷巯基、碳原子数是6～50的芳基、取代或未取代的碳原子数是5～50的杂环基、或者是取代或未取代的碳原子数是7～30的芳香族胺基。
  5. 根据权利要求1～3任意一项所述的芳杂环化合物，其特征在于，所述芳杂环化合物中，-Ar1、-Ar2、-Ar3和-Ar4独立地选自以下式(1)～式(35)所示结构：
    Figure PCTCN2015095266-appb-100008
    Figure PCTCN2015095266-appb-100009
    Figure PCTCN2015095266-appb-100010
    其中，
    X和Y独立地选自氢原子、卤素原子、氰基、取代或未取代的碳原子数是1～30的烷基、取代或未取代的碳原子数是1～30的烷氧基、取代或未取代的碳原子数是2～30的烯基、取代或未取代的碳原子数是7～30的芳烷基、取代或未取代的碳原子数是7～30的芳烷氧基、取代或未取代的碳原子数是6～30的芳基、取代或未取代的碳原子数是6～30的芳氧基、取代或未取代的碳原子数是5～30的杂环基、或者是取代或未取代的碳原子数是7～30的芳香族胺基。
  6. 根据权利要求1所述的芳杂环化合物，其特征在于，所述Q1和Q2均为苯基，以及R1和R2均为氰基或苯基时，Ar1和Ar2独立地选自取代或未取代的碳原子数7～50的芳基、取代或未取代的碳原子数5～50的杂环基、或者是取代或未取代的碳原子数7～30的芳香族胺基；
    所述L1与L2不同时为0。
  7. 一种芳杂环化合物的制备方法，包括：
    将式(V)所示的化合物与式(VI)所示的化合物和式(VII)所示的化合物进行反应，得到式(I)所示的芳杂环化合物；
    Figure PCTCN2015095266-appb-100011
    Figure PCTCN2015095266-appb-100012
    其中，
    X′为卤原子，Y′与Y1′独立地选自B(OH)2或H；
    L1、L2、L3、L4独立地选自0或1；
    Q1和Q2独立地选自氮、氧、硫、碳原子数是6～30的芳基或碳原子数是1～30的杂环基；
    R1和R2独立地选自氢原子、氰基、取代或未取代的碳原子数是6～50的芳基、取代或未取代的碳原子数是5～50的杂环基、取代或未取代的碳原子数是7～30的芳香族胺基、取代或未取代的碳原子数是7～30的芳烷氧基、取代或未取代的碳原子数是7～30的芳烷巯基或碳原子数是1～30的烷基；
    Ar1、Ar2、Ar3和Ar4独立地选自氢原子、取代或未取代的碳原子数是7～50的芳烷基、取代或未取代的碳原子数是7～50的芳烷氧基、取代或未取代的碳原子数是7～50的芳烷巯基、碳原子数是6～50的芳基、取代或未取代的碳原子数是5～50的杂环基、或者是取代或未取代的碳原子数是7～30的芳香族胺基。
  8. 一种有机电致发光器件，包括权利要求1～6任意一项所述的芳杂环化合物或权利要求7所述的制备方法制备的芳杂环化合物。
  9. 根据权利要求8所述的有机电致发光器件，其特征在于，包括第一电极、第二电极和设置于所述第一电极与第二电极之间的有机物层；
    所述有机物层包含权利要求1～6任意一项所述的芳杂环化合物或权利要求7所述的制备方法制备的芳杂环化合物。
  10. 一种有机光电材料，其特征在于，包括权利要求1～6任意一项所述的芳杂环化合物或权利要求7所述的制备方法制备的芳杂环化合物；
    所述有机光电材料包括有机太阳电池、电子纸、有机感光体或有机晶体管。
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