Organic compounds, mixtures, compositions and electronic devices containing nitrogen-containing heterocycles

Abstract

The application relates to a nitrogen-containing heterocyclic organic compound, a mixture, a composition and an electronic device. The nitrogen-containing heterocyclic organic compound has a structure as shown in formula (1), shows excellent electron transport properties and stability, can be used as a novel electron transport layer material in an organic electronic device, and improves the stability and service life of the device.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of organic light-emitting materials, in particular to a nitrogen-containing heterocyclic organic compound, mixture, composition and electronic device. BACKGROUND

[0002] In recent years, organic electroluminescence diodes (OLEDs) have shown great application prospects in full-color display and solid-state lighting due to their self-luminescence, wide viewing angle, wide color gamut, low energy consumption, high efficiency, fast response speed, ultra-light and ultra-thin, and easy to be flexible.

[0003] The light-emitting principle of OLED is that carriers are injected from the anode and cathode, and hole carriers from the anode side and electron carriers from the cathode side recombine in the light-emitting zone to form excitons, which emit light by radiation transition. The simplest OLED device structure is generally a sandwich structure composed of an anode, an organic light-emitting layer, and a cathode. However, due to the imbalance of hole and electron carrier transport within the organic light-emitting material, functional layers such as hole transport layer and electron transport layer need to be introduced.

[0004] The material used in the electron transport layer is usually an n-type organic material, which has a high electron mobility, so that the charge recombination zone can be moved away from the cathode to increase the probability of recombination, and has appropriate HOMO and LUMO energy levels, which reduces the potential barrier of electron injection and also has a certain hole blocking ability. In addition, according to non-patent document 1 (Org. Electron. 2009, 10, 1529), n-type organic materials not only can be used as pure electron transport materials, but also can be used as n-type host materials in the light-emitting layer, so that the light-emitting layer has more balanced carrier transport, thereby improving the performance of the device.

[0005] At present, there are still a lack of stable and excellent n-type electron transport materials. Therefore, it is urgent to develop electron transport materials with high efficiency, long service life and low manufacturing cost for application in organic electroluminescence devices. SUMMARY

[0006] Therefore, the purpose of the present application is to provide a nitrogen-containing heterocyclic organic compound with excellent electron transport properties.

[0007] The technical solution is as follows:

[0008] A nitrogen-containing heterocyclic organic compound has a structure as shown in formula (1):

[0009]

[0010] Wherein:

[0011] R1-R 11independently selected from hydrogen, deuterium, halogen, a substituted or unsubstituted aryl group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, or an organophosphorus group.

[0012] The present application also provides a mixture comprising a first organic compound H1 and a second organic compound H2, the first organic compound H1 and the second organic compound H2 being different;

[0013] The first organic compound H1 is selected from at least one of the nitrogen-containing heterocyclic organic compounds described above;

[0014] The second organic compound H2 is selected from a hole-transporting material, an electron-transporting material, an electron-injecting material, a host material, or an organic dye.

[0015] The present application also provides a composition comprising the nitrogen-containing heterocyclic organic compound described above, or the mixture described above, and at least one organic solvent.

[0016] The present application also provides an electronic device comprising an anode, a cathode, and one or more organic functional layers between the anode and the cathode, the organic functional layers comprising the nitrogen-containing heterocyclic organic compound described above, or the mixture described above, or being prepared from the composition described above.

[0017] Compared with the prior art, the present application has the following beneficial effects:

[0018] The present application provides a nitrogen-containing heterocyclic organic compound, which is based on a phenanthro[9',10':4,5]imidazo[1,2-a]pyridine containing a nitrogen-containing heterocycle containing an electron-deficient sp2 hybridized nitrogen atom, having a large conjugated structure, improving the electron cloud density, and can enhance the electron transport properties of the compound. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 The figure is a schematic diagram of the OLED device structure of the device embodiment 1 of the present application.

[0020] In the figure, 100 represents a substrate, 110 represents an anode, 120 represents a hole injection layer, 130 represents a hole transport layer, 140 represents an electron blocking layer, 150 represents a light-emitting layer, 160 represents an electron transport layer, 170 represents an electron injection layer, and 180 represents a cathode. DETAILED DESCRIPTION

[0021] The present application will be further described below in conjunction with specific embodiments. The present application can be realized in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the disclosure of the present application more thorough and comprehensive.

[0022] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used in the description herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. As used herein, the term "and / or" includes any and all combinations of one or more of the associated listed items.

[0023] In the present application, "substituted" means that a hydrogen atom in a substituent is replaced with a substituent. And the term "substituted or unsubstituted" in the present application means that the event or environment described later can but does not necessarily occur, and the description includes the case where the event or environment occurs or does not occur. For example, "substituted or unsubstituted aryl" means that a hydrogen atom on the aryl group can be further substituted or can not be substituted.

[0024] Further, when the substituent of the present application can be further substituted, it can be substituted with an alkyl group, a cycloalkyl group, an alkoxy group, a heterocyclic group, an aryl group, a heteroaryl group, a silyl group, a keto group, a carbonyl group, a carboxyl group, an ester group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, a cyano group, a carbamoyl group, a halogen formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, or a halogen.

[0025] Still further, it can be substituted with a C 1-10 alkyl group, a 3-10 membered cycloalkyl group, a C 1-10 alkoxy group, a 3-10 membered heterocyclic group, a 6-30 membered aryl group, a 5-30 membered heteroaryl group, a silyl group, a keto group, a carbonyl group, a carboxyl group, an ester group, an alkoxycarbonyl group, an aryloxycarbonyl group, an amino group, a cyano group, a carbamoyl group, a halogen formyl group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a nitro group, or a halogen.

[0026] In the present application, "alkyl" means a saturated aliphatic hydrocarbon group, including straight chain and branched chain groups. For example, C1-C 10Alkyl refers to an alkyl group containing from 1 to 10 carbon atoms. Non-limiting examples include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, sec-butyl, n-pentyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 2,2-dimethylpropyl, 1-ethylpropyl, 2-methylbutyl, 3-methylbutyl, n-hexyl, 1-ethyl-2-methylpropyl, 1,1,2-trimethylpropyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 2,2-dimethylbutyl, 1,3-dimethylbutyl, 2-ethylbutyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 2,3-dimethylbutyl. C1-C4 alkyl refers to an alkyl group containing from 1 to 4 carbon atoms. In one embodiment, C1-C4 alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, sec-butyl. Alkyl groups can be substituted or unsubstituted, and when substituted, the substituents can be substituted at any available attachment point.

[0027] "Cycloalkyl" refers to a saturated or partially unsaturated monocyclic or polycyclic cyclic hydrocarbon group. 3-10 membered cycloalkyl refers to a ring containing from 3 to 10 carbon atoms. In one embodiment, 3-10 membered monocyclic cycloalkyl is cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl, cyclohexenyl, cyclohexadienyl, cycloheptyl, cycloheptatrienyl, cyclooctyl, and the like. Polycyclic cycloalkyl includes spiro, fused, and bridged cycloalkyl groups. Cycloalkyl groups can be optionally substituted with one or more substituents.

[0028] "Heterocyclyl" refers to a saturated or partially unsaturated monocyclic or polycyclic cyclic hydrocarbon group, wherein one or more ring atoms are selected from nitrogen, oxygen, or S(O) m (wherein m is an integer from 0 to 2) heteroatom, preferably a nitrogen or oxygen heteroatom; but excluding ring members -O-O-, -O-S-, or -S-S-, the remaining ring atoms being carbon. 4-10 membered heterocyclyl refers to a ring containing from 4 to 10 ring atoms, of which 1 to 3 are heteroatoms; preferably the heterocyclyl ring contains 5 to 6 ring atoms, of which 1 to 2 are heteroatoms.

[0029] In the present application, the substituent "amino" includes primary, secondary, and tertiary amino groups. Specifically, amino includes -NR 16 R 17 wherein R 16 and R 17 are hydrogen atoms or any optional group, such as: H, substituted or unsubstituted alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aromatic group, or substituted or unsubstituted heteroaromatic group, and the like.

[0030] Alkoxy groups include -O-(alkyl) and -O-(cycloalkyl). The definitions of alkyl and cycloalkyl are as described above. In one embodiment, C1-C4 alkoxy is methoxy, ethoxy, propoxy, butoxy, cyclopropoxy, or cyclobutoxy. Alkoxy groups can be optionally substituted or unsubstituted.

[0031] "Carbonyl" means "-CO-"; "carboxyl" means -COOH; "ester" means "-COOR 17 ", and carbamoyl means "-CONR 17 R 18 ", where R 17 and R 18 are any optional groups, such as H, substituted or unsubstituted alkyl, substituted or unsubstituted branched alkyl, substituted or unsubstituted cycloalkyl, substituted or unsubstituted heterocyclyl, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, etc.

[0032] "Silyl" means -Si(alkyl)3, and the three alkyl groups attached to silicon are the same or different from each other; "halogen" means fluorine, chlorine, bromine, or iodine.

[0033] In the present application, "ring atom number" means the number of atoms among the atoms constituting a ring itself of a structural compound obtained by bonding atoms into a ring (e.g., monocyclic compound, fused ring compound, crosslinked compound, carbocyclic compound, heterocyclic compound). When the ring is substituted with a substituent, the atoms included in the substituent are not included in the ring-forming atoms. The same is true for "ring atom number" described below, unless otherwise specified. For example, the ring atom number of a benzene ring is 6, the ring atom number of a naphthalene ring is 10, and the ring atom number of a thienyl group is 5.

[0034] "Aryl, aryl group or aromatic group" means a hydrocarbon group containing at least one aromatic ring. "Heteroaryl, heteroaryl group or heteroaromatic group" means an aromatic hydrocarbon group containing at least one heteroatom. The heteroatom is preferably selected from Si, N, P, O, S and / or Ge, particularly preferably from Si, N, P, O and / or S. A fused ring aromatic group means that the rings of the aromatic group can have two or more rings, wherein two carbon atoms are shared by two adjacent rings, i.e. a fused ring. A fused heteroaromatic group means a fused ring aromatic hydrocarbon group containing at least one heteroatom. For the present application, an aromatic group or a heteroaromatic group not only includes systems of aromatic rings, but also non-aromatic ring systems. Thus, for example, systems such as pyridine, thiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, pyrazine, pyridazine, pyrimidine, triazine, carbene and the like are also considered to be aromatic groups or heteroaromatic groups. For the present application, a fused aromatic or fused heteroaromatic ring system not only includes systems of aromatic groups or heteroaromatic groups, but also, wherein a plurality of aromatic groups or heteroaromatic groups can also be interrupted by short non-aromatic units (<10% of non-H atoms, preferably <5% of non-H atoms, such as C, N or O atoms). Thus, for example, systems such as 9,9'-spirobifluorene, 9,9-dialkylfluorene, triarylamine, diaryl ether and the like are also considered to be fused aromatic ring systems.

[0035] Further, the aromatic rings in the aromatic group are selected from the group consisting of benzene, naphthalene, anthracene, phenanthrene, benzophenanthrene, pyrene, acenaphthene, fluorene, and derivatives thereof; the heteroaromatic rings in the heteroaromatic group are selected from the group consisting of triazine, pyridine, pyrimidine, imidazole, furan, thiophene, benzofuran, benzothiophene, indole, carbazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furanopyrrole, furanofuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, quinoline, isoquinoline, perylene, quinoxaline, phenanthridine, berberine, quinazoline, quinazolinone, dibenzothiophene, dibenzofuran, carbazole and derivatives thereof. Further, the aromatic rings in the aromatic group are selected from the group consisting of benzene, naphthalene or biphenyl; the heteroaromatic rings in the heteroaromatic group are selected from the group consisting of pyridine, pyrimidine, imidazole, oxazole, triazine, carbazole or diphenylamine.

[0036] In the present application, an organic phosphorus group means a group containing phosphorus in its structure.

[0037] In the present application, "*" represents a connection site.

[0038] In the present application, a connection line containing "*" interposed in a ring is understood to have the usual meaning in the art, indicating that the optional connectable positions on the ring can serve as connection sites, for example: indicates that any one of the optional connectable positions X1 to X6 on the ring serves as a connection site, indicates that any two of the optional connectable positions X1 to X6 on the ring serve as connection sites.

[0039] In the present application, the same substituent group can be selected independently from different groups when it appears multiple times. For example, if the general formula contains multiple R1, R1 can be selected independently from different groups.

[0040] The technical solution of the present application is as follows:

[0041] An organic compound containing a nitrogen-containing heterocycle has a structure as shown in formula (1):

[0042]

[0043] Wherein:

[0044] R1-R 11 are independently selected from hydrogen, deuterium, halogen, a substituted or unsubstituted aryl group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms, or an organophosphorus group.

[0045] The present application provides an organic compound containing a nitrogen-containing heterocycle, which is based on a nitrogen-containing heterocycle of phenanthrene [9', 10': 4, 5] imidazo [1, 2-a] pyridine containing an electron-deficient sp2 hybridized nitrogen atom, having a large conjugated structure, improving the electron cloud density, and can enhance the electronic transport properties of the compound.

[0046] In one embodiment, the organophosphorus group has a structure as shown in formula (2):

[0047]

[0048] Ar is a substituted or unsubstituted aryl group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms; Y is O or S; R 12 and R 13 are each independently selected from a substituted or unsubstituted aryl group having 6 to 30 ring atoms, or a substituted or unsubstituted heteroaryl group having 5 to 30 ring atoms; m is 0 or 1; n is 1 or 2; * represents a connection site.

[0049] The phosphorus-oxygen or phosphorus-sulfur group shown in formula (2) can further enhance the electron transport and injection capacity of the organic compound containing a nitrogen-containing heterocycle of the present application. At the same time, the compound after introducing the phosphorus-oxygen or phosphorus-sulfur group shown in formula (2) has a rigid structure, a higher glass transition temperature, good thermal stability and film-forming property, and has appropriate HOMO and LUMO energy levels, which can effectively improve the photoelectric performance and lifetime of OLED devices through device structure optimization. In addition, the phosphorus-oxygen or phosphorus-sulfur group also has a high triplet energy level, and is soluble in polar alcohol solvents, so that the organic compound containing a nitrogen-containing heterocycle of the present application has the potential for application in solution devices.

[0050] In one embodiment, m is 1. Further, when n is 1, Ar is selected from any one of the following groups (A-1) to (A-9):

[0051]

[0052] When n is 2, Ar is selected from any one of the following groups (A-10) to (A-18):

[0053]

[0054] wherein:

[0055] X is independently N or substituted or unsubstituted C;

[0056] the atom connected with unsubstituted C is independently selected from hydrogen atom or deuterium atom;

[0057] Z is independently selected from substituted N, substituted C, O, S or substituted Si;

[0058] the substituent of substituted C in X, the substituent of substituted N in Z, the substituent of substituted C in Z and the substituent of substituted Si in Z are independently selected from alkyl group with 1 to 10 C atoms, alkoxy group with 1 to 10 C atoms, aryl group with 6 to 20 ring atoms, heteroaryl group with 5 to 20 ring atoms.

[0059] Ar is aryl group or heteroaryl group as described above, which can increase the conjugation degree of the compound, and when applied to the functional layer of electronic devices, it is more conducive to improve the electronic transmission capacity.

[0060] In one embodiment, the substituent of substituted C in X, the substituent of substituted N in Z, the substituent of substituted C in Z and the substituent of substituted Si in Z are independently selected from phenyl group, biphenyl group, terphenyl group, naphthyl group, pyridyl group, pyrimidyl group, pyrazyl group, quinolyl group, isoquinolyl group, quinoxalyl group or quinazolyl group. The aryl group or heteroaryl group as described above, in addition to increasing the conjugation degree of the compound, when applied to the functional layer of electronic devices, it is more conducive to improve the electronic transmission capacity; also has appropriate steric hindrance, which can avoid the difficulty in reaction preparation due to excessive steric hindrance.

[0061] In one embodiment, n is 1, and Ar is selected from any one of the following groups:

[0062]

[0063] n is 2, and Ar is selected from any one of the following groups:

[0064]

[0065] Further, n is 1, and Ar is selected from any one of the following groups:

[0066]

[0067] n is 2, and Ar is selected from any one of the following groups

[0068]

[0069] In one embodiment, R 12 and R 13 are each independently selected from any one of the following groups (B-1) to (B-7):

[0070]

[0071] wherein:

[0072] X1is each independently selected from N or a substituted or unsubstituted C;

[0073] the atom connected to the unsubstituted C is independently selected from a hydrogen atom or a deuterium atom;

[0074] Y1is each independently selected from a substituted N, a substituted C, O, S or a substituted Si;

[0075] the substituent of the substituted C in X1, the substituent of the substituted N in Y1, the substituent of the substituted C in Y1and the substituent of the substituted Si in Y1are each independently selected from an alkyl group having 1 to 10 C atoms, an alkoxy group having 1 to 10 C atoms, an aryl group having 6 to 20 ring atoms, a heteroaryl group having 5 to 20 ring atoms. The use of the above-mentioned aryl or heteroaryl group can increase the conjugation degree of the compound, and when applied to a functional layer of an electronic device, it is more advantageous to improve its electron transport ability.

[0076] In one embodiment, the substituent of the substituted C in X1, the substituent of the substituted N in Y1, the substituent of the substituted C in Y1and the substituent of the substituted Si in Y1are each independently selected from a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a pyridyl group, a pyrimidyl group, a pyrazyl group, a quinolyl group, an isoquinolyl group, a quinoxalyl group or a quinazolyl group. The use of the above-mentioned aryl or heteroaryl group can increase the conjugation degree of the compound, and when applied to a functional layer of an electronic device, it is more advantageous to improve its electron transport ability; it also has appropriate steric hindrance, which can avoid difficulty in reaction and preparation due to excessive steric hindrance.

[0077] Further, R 12 and R 13 are each independently selected from any one of the following groups:

[0078]

[0079] In one embodiment, the organic phosphorus group is selected from any one of the following:

[0080]

[0081]

[0082]

[0083] The phosphorus-oxygen or phosphorus-sulfur groups described above can further enhance the electron transport and injection capability of the nitrogen-containing heterocyclic organic compounds of the present application.

[0084] In one embodiment, R1, R2, R3, R4, R9, R 10 and R 11 are independently selected from the group consisting of hydrogen, deuterium, phenyl, biphenyl, terphenyl, naphthyl, pyridyl, pyrimidyl, pyrazinyl, quinolyl, isoquinolyl, quinoxalyl, or quinazolyl, or an organic phosphorus group represented by formula (2); and at least one of R1, R2, R3, R4, R9, R 10 and R 11 is an organic phosphorus group represented by formula (2).

[0085] Further, at least one of R2, R3, R4, R9, R 10 and R 11 is an organic phosphorus group represented by formula (2), m is 1, and n is 1 or 2.

[0086] In one embodiment, one of R2, R3, R4, R9, R 10 and R 11 is an organic phosphorus group represented by formula (2). When one of R2, R3, R4, R9, R 10 and R 11 is an organic phosphorus group represented by formula (2), the remaining ones are hydrogen or phenyl.

[0087] In one embodiment, at least two of R2, R3, R4, R9, R 10 and R 11 are organic phosphorus groups represented by formula (2). When two of R2, R3, R4, R9, R 10 and R 11 are organic phosphorus groups represented by formula (2), the remaining ones are hydrogen or phenyl.

[0088] In one embodiment, R5, R6, R7, and R8 are independently selected from the group consisting of hydrogen, deuterium, phenyl, biphenyl, terphenyl, naphthyl, pyridyl, pyrimidyl, pyrazinyl, quinolyl, isoquinolyl, quinoxalyl, and quinazolyl.

[0089] Furthermore, R5, R6, R7 and R8 are each independently selected from hydrogen or deuterium.

[0090] In one embodiment, R5, R6, R7 and R8 are all hydrogen.

[0091] In one embodiment, the nitrogen-containing heterocyclic organic compound has a structure shown in any of formulas (3-1)-(3-3):

[0092]

[0093] In equations (3-1)-(3-3), R2, R3, R4, R9, and R... 10 and R 11 At least one of the compounds is selected from the organophosphorus group shown in formula (2), and m is 1, n is 1 or 2. Such compounds have excellent electron transport properties and are easy to prepare, which can meet the performance requirements of electronic devices without high costs, and have broad application prospects.

[0094] In one embodiment, R2, R3, R4, R9, and R in equations (3-1)-(3-3) 10 and R 11 One of them is an organophosphorus group selected from the one shown in formula (2). When R2, R3, R4, R9, R 10 and R 11 When one of them is an organophosphorus group as shown in formula (2), the rest are hydrogen or phenyl.

[0095] In one embodiment, R2, R3, R4, R9, and R in equations (3-1)-(3-3) 10 and R 11 It contains at least two organophosphorus groups selected from those shown in formula (2). When R2, R3, R4, R9, R 10 and R 11 When two of them are organophosphorus groups as shown in formula (2), the rest are hydrogen or phenyl.

[0096] The following lists the structures of nitrogen-containing heterocyclic organic compounds according to the present invention, but are not limited thereto:

[0097]

[0098]

[0099]

[0100]

[0101]

[0102] In one aspect, the nitrogen-containing heterocyclic organic compound according to the present application has an electron-deficient sp2 hybridized nitrogen atom in the nitrogen-containing heterocyclic ring based on phenanthro[9',10':4,5]imidazo[1,2-a]pyridine, has a large conjugated structure, and has an increased electron cloud density, which can enhance the electron transport property of the group, and can effectively improve the photoelectric performance and lifetime of the electronic device. Therefore, the nitrogen-containing heterocyclic organic compound according to the present application can be used as a functional material in a functional layer of an electronic device. The organic functional layer includes, but is not limited to, a hole injection layer (HIL), a hole transport layer (HTL), an electron transport layer (ETL), an electron injection layer (EIL), an electron blocking layer (EBL), a hole blocking layer (HBL), and an emission layer (EML).

[0103] In one embodiment, the nitrogen-containing heterocyclic organic compound according to the present application is used in an electron transport layer or an electron injection layer. Particularly preferably, the nitrogen-containing heterocyclic organic compound according to the present application is used in an electron transport layer of an electronic device.

[0104] The nitrogen-containing heterocyclic organic compound according to the present application can be used alone or in combination with an organic functional material.

[0105] In one embodiment, the present application also provides a mixture comprising: a first organic compound H1 and a second organic compound H2, the first organic compound H1 and the second organic compound H2 being different; the first organic compound H1 being selected from at least one of the nitrogen-containing heterocyclic organic compounds, and the second organic compound H2 being selected from a hole transport material, an electron transport material, an electron injection material, a host material, or an organic dye.

[0106] The nitrogen-containing heterocyclic organic compound according to the present application can be used alone or in combination with an organic functional material.

[0107] In a more preferred embodiment, the organic functional material is selected from an electron injection material. Preferably, the organic functional material is lithium quinolate.

[0108] On the other hand, the nitrogen-containing heterocyclic organic compound of the present application is soluble in polar alcohol solvents, which makes the nitrogen-containing heterocyclic organic compound of the present application potentially useful in solution-based devices.

[0109] In one embodiment, the present application also provides a composition comprising the nitrogen-containing heterocyclic organic compound of the present application or the mixture as described above, and at least one organic solvent.

[0110] Preferably, the organic solvent is selected from the group consisting of alcohols, ethers, ketones and esters. Further, the organic solvent is selected from at least one of methanol, ethanol, isopropanol, n-hexanol, n-heptanol, n-octanol, ethylene glycol, diethylene glycol, triethylene glycol dimethyl ether, hexafluoroacetylacetone, ethylene glycol diacetate and octafluoro-dimethyl adipate. That is, the solvent can be used alone or as a mixture of two or more organic solvents.

[0111] The present application also provides the use of the nitrogen-containing heterocyclic organic compound, the mixture or the composition as described above in an organic electronic device. The technical solution is as follows:

[0112] An electronic device comprising an anode, a cathode, one or more organic functional layers between the anode and the cathode, the organic functional layers comprising the nitrogen-containing heterocyclic organic compound of the present application, or the mixture as described above, or prepared from the composition of the present application.

[0113] The electronic device can be, but is not limited to, an organic light-emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light-emitting electrochemical cell (OLEEC), an organic field-effect transistor (OFET), an organic light-emitting field-effect transistor, an organic laser, an organic spintronics device, an organic sensor and an organic plasmon emitting diode (Organic Plasmon Emitting Diode), etc., and is particularly preferred to be an OLED, and the nitrogen-containing heterocyclic organic compound is used in the electron transport layer of the OLED device.

[0114] In one embodiment, the structure of the OLED is shown in Figure 1 which comprises a substrate 100, an anode 110, a hole injection layer 120, a hole transport layer 130, an electron blocking layer 140, a light-emitting layer 150, an electron transport layer 160, an electron injection layer 170 and a cathode 180, which are sequentially stacked, and the electron transport layer 160 comprises the nitrogen-containing heterocyclic organic compound of the present application.

[0115] The present application also relates to the use of the organic electronic device according to the present application in various electronic devices, including but not limited to display devices, lighting devices, light sources and sensors.

[0116] The application will now be described by way of example with reference to the accompanying drawings. The application is not limited to the examples described below which should not be taken as limiting the scope of the application as defined by the claims. It will be appreciated by those skilled in the art that modifications can be made to the embodiments described without departing from the scope of the present application as defined by the claims. Embodiments

[0118] 1. Synthesis of compounds

[0119] The synthesis route of the compounds is as follows:

[0120]

[0121] wherein the halogen is bromine or chlorine, and the actual reaction can be taken as the standard; n1, n2 and n3 are each selected from 0, 1, 2, 3 or 4; and only the reactive groups involved in the reaction, such as the halogen substituent, are shown in the synthesis route, and the substituents not shown can be freely substituted according to the definition in the present application. For example, Only the halogen substituent on the benzene ring is shown, and the groups not shown correspond to any one of R5, R6, R7 and R8 in formula (1) of the present application, and the definition is consistent with the foregoing, and will not be described again here.

[0122] and at least one of to generate the nitrogen-containing heterocyclic organic compound of the present application.

[0123] In one embodiment, the following reaction occurs:

[0124]

[0125] In another embodiment, the following reaction occurs:

[0126]

[0127] Synthesis of

[0128] Dissolve in 1,2-dichlorobenzene, add Cu(OAc)2-H2O, ZnI2 and 1,10-phenanthroline, and heat and stir at 120°C for 24 h to obtain a mixture. Dilute the mixture with dichloromethane and filter through a bed of diatomite, and collect the organic phase. Concentrate the organic phase under reduced pressure, and purify by silica gel chromatography to obtain the solid compound and analyze by GC-MS.

[0129] Synthesis of

[0130] Dissolve Pd(PPh3)4 and potassium carbonate were dissolved in dry DMF and heated at 130 °C under nitrogen atmosphere for 12 h to give a mixture. The mixture was diluted with ethyl acetate and filtered through a bed of celite to collect the organic phase. The organic phase was washed with water twice, saturated brine once, and then concentrated under reduced pressure to give a solid compound and analyzed by GC-MS.

[0131] Synthesis of:

[0132] Compound Pd(OAC)2, Ag2CO3, trimethylacetic acid were mixed in a sealed tube and heated at 140 °C for 12 h to give a mixture. The mixture was diluted with ethyl acetate and filtered through a bed of celite to collect the organic phase. The organic phase was washed with water twice, saturated brine once, and then concentrated under reduced pressure to give a solid compound and analyzed by GC-MS.

[0133] Synthesis of:

[0134] Compound bis-pinacolboronate, PdCl2(dppf) and potassium acetate were dissolved in DMF and heated at 90 °C under nitrogen atmosphere for 10 h to give a mixture. The solvent was removed from the mixture by vacuum evaporation and dichloromethane was added to the residue. The mixture was stirred and filtered to collect the organic phase. The organic phase was purified by silica gel chromatography to give a solid compound and analyzed by GC-MS.

[0135] Synthesis of:

[0136] Compound was dissolved in dry THF. The solution was cooled to -78 °C and n-BuLi was added dropwise. The mixture was stirred at -78 °C for 1 h. After the temperature was raised to -50 °C, R 12 R 13 PCl was added and the mixture was stirred at room temperature overnight. Methanol was added to quench the reaction to give a mixture. The solvent was removed from the mixture by vacuum evaporation and dichloromethane was added to the residue. The mixture was stirred and 30 wt% aqueous H2O2 was added. After the reaction was completed, the mixture was washed with saturated brine and the organic phase was collected. The organic phase was dried over anhydrous magnesium sulfate and the solvent was removed from the dried organic phase by vacuum evaporation. The residue was purified by silica gel chromatography to give a solid compound and analyzed by GC-MS.

[0137] Synthesis of:

[0138] Compound Pd(PPh3)4 and potassium carbonate were dissolved in THF and water, and heated at 80°C for 10 hours under a nitrogen atmosphere to obtain a mixture. The solvent in the mixture was removed by vacuum rotary evaporation, and the residue was added to dichloromethane, stirred, filtered, and purified by silica gel column chromatography to obtain a solid compound. Gas chromatography-mass spectrometry (GC-MS) analysis was employed.

[0139] Synthesis:

[0140] compound Pd(PPh3)4 and potassium carbonate were dissolved in THF and water, and heated at 80°C for 10 hours under a nitrogen atmosphere to obtain a mixture. The solvent in the mixture was removed by vacuum rotary evaporation, and the residue was added to dichloromethane, stirred, filtered, and purified by silica gel column chromatography to obtain a solid compound. Gas chromatography-mass spectrometry (GC-MS) analysis was employed.

[0141] Example 1: Preparation of compound M-1

[0142]

[0143] Synthesis of compound M-1a:

[0144] 2-Amino-5-chloropyridine (12.8 g, 100.0 mmol) and 2'-iodoacetophenone (24.6 g, 100.0 mmol) were dissolved in 1,2-dichlorobenzene (100 mL). Cu(OAc)₂·H₂O (2.0 g, 10.0 mmol), ZnI₂ (3.2 g, 10.0 mmol), and 1,10-phenanthroline (1.98 g, 10.0 mmol) were added. The mixture was heated and stirred at 120 °C for 24 h to obtain a mixture. The mixture was diluted with dichloromethane and filtered through a diatomaceous earth bed, and the organic phase was collected. The organic phase was concentrated under reduced pressure and purified by silica gel column chromatography to obtain solid compound M-1a (27.6 g, 78.0 mmol), with a yield of 78%. The ESI-MS (m / z) result was 354.3.

[0145] Synthesis of compound M-1b:

[0146] Compound M-la (17.7 g, 50.0 mmol), benzene boronic acid (6.1 g, 50 mmol), Pd(PPh3)4(2.9 g, 2.5 mmol) and potassium carbonate (20.7 g, 150.0 mmol) were dissolved in dry DMF (200 mL) and heated at 130 °C for 12 h under nitrogen atmosphere to give a mixture. The mixture was diluted with ethyl acetate and filtered through a bed of celite, and the organic phase was collected. The organic phase was washed with water twice, saturated brine once, and the organic phase was collected, concentrated under reduced pressure, and purified by silica gel chromatography to give solid compound M-lb (9.45 g, 31.0 mmol) with a yield of 62%. ESI-MS (m / z) was analyzed by GC-MS: 304.6.

[0147] Synthesis of compound M-lc:

[0148] Compound M-lb (6.09 g, 20 mmol) was dissolved in 100 mL of dry DMF, Pd(OAC)2(0.22 g, 1 mmol), Ag2CO3(0.28 g, 1 mmol), trimethylacetic acid (0.30 g, 3 mmol) were added, and the dehydrocyclization reaction was heated at 140 °C for 12 h in a sealed tube to give a mixture. The mixture was diluted with ethyl acetate and filtered through a bed of celite, and the organic phase was collected. The organic phase was washed with water twice, saturated brine once, and the organic phase was collected, concentrated under reduced pressure, and purified by silica gel chromatography to give solid compound M-lc (3.94 g, 13.0 mmol) with a yield of 65%. ESI-MS (m / z) was analyzed by GC-MS: 302.6.

[0149] Synthesis of compound M-lc:

[0150] Compound M-lc (3.0 g, 10.0 mmol), bis(pinacolato)diboron (2.8 g, 11 mmol), PdCl2(dppf) (0.41 g, 0.5 mmol) and potassium acetate (2.94 g, 30.0 mmol) were dissolved in DMF (100 mL) and heated at 90 °C for 10 h under nitrogen atmosphere to give a mixture. The solvent was removed from the mixture by vacuum evaporation, and dichloromethane was added to the residue, which was stirred and filtered. The solid compound M-l d (3.15 g, 8.0 mmol) was obtained by purification with silica gel chromatography with a yield of 80%. ESI-MS (m / z) was analyzed by GC-MS: 394.2.

[0151] Synthesis of compound M-lc:

[0152] Compound M-1 d (3.94 g, 10 mmol), M-1 e (3.57 g, 10 mmol), Pd(PPh3)4(0.58 g, 0.5 mmol) and potassium carbonate (4.14 g, 30.0 mmol) were dissolved in THF (50 mL) and water (50 mL) and heated at 80 °C under nitrogen atmosphere for 10 h to give a mixture. The solvent was removed from the mixture by vacuum evaporation to give a residue, dichloromethane was added to the residue and stirred, filtered and purified by silica gel column chromatography to give compound M-1 (3.81 g, 7.0 mmol) as a solid with a yield of 70%. ESI-MS (m / z) 544.2 was obtained by GC-MS analysis.

[0153] Synthesis of compound M-1

[0154] Compound M-1 d (3.94 g, 10 mmol), M-1 e (3.57 g, 10 mmol), Pd(PPh3)4(0.58 g, 0.5 mmol) and potassium carbonate (4.14 g, 30.0 mmol) were dissolved in THF (50 mL) and water (50 mL) and heated at 80 °C under nitrogen atmosphere for 10 h to give a mixture. The solvent was removed from the mixture by vacuum evaporation to give a residue, dichloromethane was added to the residue and stirred, filtered and purified by silica gel column chromatography to give compound M-1 (3.81 g, 7.0 mmol) as a solid with a yield of 70%. ESI-MS (m / z) 544.2 was obtained by GC-MS analysis.

[0155] Example 2: Preparation of compound M-11

[0156]

[0157]

[0158] Synthesis of compound M-11 a

[0159] A mixture of 2-amino-4-chloropyridine (12.8 g, 100.0 mmol), 2'-iodoacetophenone (24.6 g, 100.0 mmol), Cu(OAc)2-H2O (2.0 g, 10.0 mmol), ZnI2(3.2 g, 10.0 mmol), 1,10-phenanthroline (1.98 g, 10.0 mmol) was dissolved in 1,2-dichlorobenzene (100 mL) and heated under stirring at 120 °C for 24 h under atmospheric air. The mixture was diluted with dichloromethane and filtered through a bed of celite, and the organic phase was collected. The organic phase was then concentrated under reduced pressure and purified by silica gel chromatography to obtain compound M-11a (20.6 g, 58.0 mmol) as a solid with a yield of 58%. ESI-MS (m / z) 354.6 was obtained by GC-MS analysis.

[0160] Synthesis of compound M-11b:

[0161] A mixture of compound M-11a (17.7 g, 50.0 mmol), phenylboronic acid (6.1 g, 50 mmol), Pd(PPh3)4(2.9 g, 2.5 mmol) and potassium carbonate (20.7 g, 150.0 mmol) was dissolved in dry DMF (200 mL) and heated at 130 °C for 12 h under nitrogen atmosphere. The mixture was diluted with ethyl acetate and filtered through a bed of celite. The organic layer was washed twice with water, once with saturated brine, and then concentrated under reduced pressure and purified by silica gel chromatography to obtain compound M-11b (8.53 g, 28.0 mmol) as a solid with a yield of 56%. ESI-MS (m / z) 304.7 was obtained by GC-MS analysis.

[0162] Synthesis of compound M-11c:

[0163] Compound M-11b (6.09 g, 20 mmol) was dissolved in 100 mL of dry DMF, Pd(OAC)2(0.22 g, 1 mmol), Ag2CO3(0.28 g, 1 mmol), trimethylacetic acid (0.30 g, 3 mmol) were added and the mixture was heated at 140 °C for 12 h in a sealed tube. The mixture was diluted with ethyl acetate and filtered through a bed of celite, and the organic phase was collected. The organic phase was washed twice with water, once with saturated brine, and the organic phase was collected and then concentrated under reduced pressure and purified by silica gel chromatography to obtain compound M-11c (4.36 g, 14.4 mmol) as a solid with a yield of 72%. ESI-MS (m / z) 302.8 was obtained by GC-MS analysis.

[0164] Synthesis of compound M-11d:

[0165] Compound M-llc (3.0 g, 10.0 mmol), bis-pinacolboronate (2.8 g, 11 mmol), PdCl2(dppf) (0.41 g, 0.5 mmol) and potassium acetate (2.94 g, 30.0 mmol) were dissolved in DMF (100 mL) and heated at 90 °C under nitrogen atmosphere for 10 h to give a mixture. The solvent was removed from the mixture by rotary evaporation under vacuum. Dichloromethane was added to the residue and stirred, filtered, and purified by silica gel chromatography to give solid compound M-ll d (3.0 g, 7.6 mmol) with a yield of 76%. ESI-MS (m / z) was analyzed by GC-MS: 394.3.

[0166] Synthesis of compound M-ll e:

[0167] Compound M-llc (3.0 g, 10.0 mmol), bis-pinacolboronate (2.8 g, 11 mmol), PdCl2(dppf) (0.41 g, 0.5 mmol) and potassium acetate (2.94 g, 30.0 mmol) were dissolved in DMF (100 mL) and heated at 90 °C under nitrogen atmosphere for 10 h to give a mixture. The solvent was removed from the mixture by rotary evaporation under vacuum. Dichloromethane was added to the residue and stirred, filtered, and purified by silica gel chromatography to give solid compound M-ll d (3.0 g, 7.6 mmol) with a yield of 76%. ESI-MS (m / z) was analyzed by GC-MS: 394.3.

[0168] Synthesis of compound M-ll e:

[0169] Compound M-llc (3.0 g, 10.0 mmol), bis-pinacolboronate (2.8 g, 11 mmol), PdCl2(dppf) (0.41 g, 0.5 mmol) and potassium acetate (2.94 g, 30.0 mmol) were dissolved in DMF (100 mL) and heated at 90 °C under nitrogen atmosphere for 10 h to give a mixture. The solvent was removed from the mixture by rotary evaporation under vacuum. Dichloromethane was added to the residue and stirred, filtered, and purified by silica gel chromatography to give solid compound M-ll d (3.0 g, 7.6 mmol) with a yield of 76%. ESI-MS (m / z) was analyzed by GC-MS: 394.3.

[0170] Example 3: Preparation of compound M-19

[0171] Compound M-llc (3.0 g, 10.0 mmol), bis-pinacolboronate (2.8 g, 11 mmol), PdCl2(dppf) (0.41 g, 0.5 mmol) and potassium acetate (2.94 g, 30.0 mmol) were dissolved in DMF (100 mL) and heated at 90 °C under nitrogen atmosphere for 10 h to give a mixture. The solvent was removed from the mixture by rotary evaporation under vacuum. Dichloromethane was added to the residue and stirred, filtered, and purified by silica gel chromatography to give solid compound M-ll d (3.0 g, 7.6 mmol) with a yield of 76%. ESI-MS (m / z) was analyzed by GC-MS: 394.3.

[0172] Synthesis of compound M-19a:

[0173] Dissolve 2-aminopyridine (9.4 g, 100.0 mmol), 2'-iodoacetophenone (24.6 g, 100.0 mmol) in 1,2-dichlorobenzene (100 mL), add Cu(OAc)2-H2O (2.0 g, 10.0 mmol), ZnI2(3.2 g, 10.0 mmol), 1,10-phenanthroline (1.98 g, 10.0 mmol), heat under atmospheric air at 120 °C for 24 h to obtain a mixture. Dilute the mixture with dichloromethane and filter through a bed of celite, collect the organic phase. Concentrate the organic phase under reduced pressure, purify by silica gel chromatography column to obtain solid compound M-19a (22.4 g, 70.0 mmol) with a yield of 70%. Analyze by GC-MS to obtain ESI-MS (m / z): 320.2.

[0174] Synthesis of compound M-19b:

[0175] Dissolve compound M-19a (16.0 g, 50.0 mmol), p-chlorobenzoic acid (6.1 g, 50 mmol), Pd(PPh3)4(2.9 g, 2.5 mmol) and potassium carbonate (20.7 g, 150.0 mmol) in dry DMF (200 mL), heat under nitrogen atmosphere at 130 °C for 12 h to obtain a mixture. Dilute the mixture with ethyl acetate and filter through a bed of celite, collect the organic phase. Wash the organic phase with water twice, saturated brine once, collect the organic phase, concentrate under reduced pressure, purify by silica gel chromatography column to obtain solid compound M-19b (10.0 g, 33.0 mmol) with a yield of 66%. Analyze by GC-MS to obtain ESI-MS (m / z): 304.1.

[0176] Synthesis of compound M-19c:

[0177] Dissolve compound M-19b (6.08 g, 20 mmol) in 100 mL of dry DMF, add Pd(OAC)2(0.22 g, 1 mmol), Ag2CO3(0.28 g, 1 mmol), trimethylacetic acid (0.30 g, 3 mmol), heat under dehydrocyclization reaction at 140 °C for 12 h in a closed tube to obtain a mixture. Dilute the mixture with ethyl acetate and filter through a bed of celite, collect the organic phase. Wash the organic phase with water twice, saturated brine once, concentrate under reduced pressure, purify by silica gel chromatography column to obtain solid compound M-19c (3.81 g, 12.6 mmol) with a yield of 63%. Analyze by GC-MS to obtain ESI-MS (m / z): 302.3.

[0178] Synthesis of compound M-19d:

[0179] Compound M-19c (3.0 g, 10.0 mmol), bis-pinacolborane (2.8 g, 11 mmol), PdCl2(dppf) (0.41 g, 0.5 mmol) and potassium acetate (2.94 g, 30.0 mmol) were dissolved in DMF (100 mL) and heated at 90 °C under nitrogen atmosphere for 10 h to give a mixture. The solvent of the mixture was removed by rotary evaporation under vacuum, and dichloromethane was added to the residue and stirred, filtered, and purified by silica gel column chromatography to give compound M-19d (2.6 g, 6.6 mmol) as a solid with a yield of 66%. ESI-MS (m / z) was analyzed by GC-MS to be 394.2.

[0180] Synthesis of compound M-19:

[0181] Compound M-19d (3.94 g, 10 mmol), M-1e (3.57 g, 10 mmol), Pd(PPh3)4(0.58 g, 0.5 mmol) and potassium carbonate (4.14 g, 30.0 mmol) were dissolved in THF (50 mL) and water (50 mL) and heated at 80 °C under nitrogen atmosphere for 10 h to give a mixture. The solvent of the mixture was removed by rotary evaporation under vacuum, and dichloromethane was added to the residue and stirred, filtered, and purified by silica gel column chromatography to give compound M-19 (3.48 g, 6.4 mmol) as a solid with a yield of 64%. ESI-MS (m / z) was analyzed by GC-MS to be 544.2.

[0182] Example 4: Preparation of compound M-28

[0183]

[0184] Synthesis of compound M-28b:

[0185] Compound M-19a (16.0 g, 50.0 mmol), m-chlorobenzeneboronic acid (6.1 g, 50 mmol), Pd(PPh3)4(2.9 g, 2.5 mmol) and potassium carbonate (20.7 g, 150.0 mmol) were dissolved in dry DMF (200 mL) and heated at 130 °C under nitrogen atmosphere for 12 h to give a mixture. The mixture was diluted with ethyl acetate and filtered through a bed of celite. The organic layer was washed with water twice, saturated brine once, the organic phase was collected and concentrated under reduced pressure, and purified by silica gel column chromatography to give compound M-28b (10.2 g, 33.5 mmol) as a solid with a yield of 67%. ESI-MS (m / z) was analyzed by GC-MS to be 304.2.

[0186] Synthesis of compound M-28c:

[0187] Compound M-28b (6.08 g, 20 mmol) was dissolved in 100 mL of dry DMF, Pd(OAC)2 (0.22 g, 1 mmol), Ag2CO3 (0.28 g, 1 mmol), trimethylacetic acid (0.30 g, 3 mmol) were added, and the mixture was heated at 140 °C for 12 h in a sealed tube to give a mixture. The mixture was diluted with ethyl acetate and filtered through a bed of celite, and the organic phase was collected. The organic phase was washed twice with water, once with saturated brine, and then concentrated under reduced pressure to give a solid compound M-28c (2.54 g, 8.4 mmol) with a yield of 42%. ESI-MS (m / z) was analyzed by GC-MS to be 302.1.

[0188] Synthesis of compound M-28d:

[0189] Compound M-28c (3.0 g, 10.0 mmol), bis(pinacolato)diboron (2.8 g, 11 mmol), PdCl2(dppf) (0.41 g, 0.5 mmol) and potassium acetate (2.94 g, 30.0 mmol) were dissolved in DMF (100 mL) and heated at 90 °C for 10 h under nitrogen atmosphere to give a mixture. The solvent of the mixture was removed by vacuum evaporation, and dichloromethane was added to the residue, stirred, filtered, and purified by silica gel chromatography to give a solid compound M-28d (2.84 g, 7.2 mmol) with a yield of 72%. ESI-MS (m / z) was analyzed by GC-MS to be 394.3.

[0190] Synthesis of compound M-28:

[0191] Compound M-28d (3.94 g, 10 mmol), M-1e (3.57 g, 10 mmol), Pd(PPh3)4 (0.58 g, 0.5 mmol) and potassium carbonate (4.14 g, 30.0 mmol) were dissolved in THF (50 mL) and water (50 mL) and heated at 80 °C for 10 h under nitrogen atmosphere to give a mixture. The solvent of the mixture was removed by vacuum evaporation, and dichloromethane was added to the residue, stirred, filtered, and purified by silica gel chromatography to give a solid compound M-28 (3.70 g, 6.8 mmol) with a yield of 68%. ESI-MS (m / z) was analyzed by GC-MS to be 544.1.

[0192] Example 5: Preparation of compound M-37

[0193]

[0194] Synthesis of compound M-37b:

[0195] Compound M-19a (16.0 g, 50.0 mmol), o-chlorobenzeneboronic acid (6.1 g, 50 mmol), Pd(PPh3)4(2.9 g, 2.5 mmol) and potassium carbonate (20.7 g, 150.0 mmol) were dissolved in dry DMF (200 mL) and heated at 130 °C for 12 h under nitrogen atmosphere to give a mixture. The mixture was diluted with ethyl acetate and filtered through a bed of celite, and the organic phase was collected. The organic phase was washed with water twice, saturated brine once, concentrated under reduced pressure, and purified by silica gel chromatography to give solid compound M-37b (9.12 g, 30 mmol) with a yield of 60%. ESI-MS (m / z) was analyzed by GC-MS to be 304.3.

[0196] Synthesis of compound M-37c:

[0197] Compound M-37b (6.08 g, 20 mmol) was dissolved in 100 mL of dry DMF, Pd(OAC)2(0.22 g, 1 mmol), Ag2CO3(0.28 g, 1 mmol), trimethylacetic acid (0.30 g, 3 mmol) were added, and the mixture was heated at 140 °C for 12 h in a sealed tube to give a mixture. The mixture was diluted with ethyl acetate and filtered through a bed of celite, and the organic phase was collected. The organic phase was washed with water twice, saturated brine once, and the organic phase was collected and concentrated under reduced pressure. The residue was purified by silica gel chromatography to give solid compound M-37c (3.14 g, 10.4 mmol) with a yield of 52%. ESI-MS (m / z) was analyzed by GC-MS to be 302.1.

[0198] Synthesis of compound M-37d:

[0199] Compound M-37c (3.0 g, 10.0 mmol), bis(pinacolato)diboron (2.8 g, 11 mmol), PdCl2(dppf) (0.41 g, 0.5 mmol) and potassium acetate (2.94 g, 30.0 mmol) were dissolved in DMF (100 mL) and heated at 90 °C for 10 h under nitrogen atmosphere to give a mixture. The solvent of the mixture was removed by vacuum evaporation, and dichloromethane was added to the residue, which was stirred and filtered. The residue was purified by silica gel chromatography to give solid compound M-37d (2.80 g, 7.1 mmol) with a yield of 71%. ESI-MS (m / z) was analyzed by GC-MS to be 394.2.

[0200] Synthesis of compound M-37:

[0201] Compound M-37d (3.94 g, 10 mmol), M-le (3.57 g, 10 mmol), Pd(PPh3)4(0.58 g, 0.5 mmol) and potassium carbonate (4.14 g, 30.0 mmol) were dissolved in THF (50 mL) and water (50 mL), heated at 80 °C under nitrogen atmosphere for 10 h to give a mixture. The solvent in the mixture was removed by rotary evaporation under vacuum, dichloromethane was added to the residue, stirred, filtered, and purified by silica gel chromatography to give solid compound M-37 (3.37 g, 6.2 mmol) with a yield of 62%. ESI-MS (m / z) was analyzed by GC-MS to be 544.3.

[0202] Example 6: Preparation of compound M-46

[0203]

[0204] Synthesis of compound M-46b:

[0205] Compound M-la (17.7 g, 50.0 mmol), p-chlorobenzeneboronic acid (6.1 g, 50 mmol), Pd(PPh3)4(2.9 g, 2.5 mmol) and potassium carbonate (20.7 g, 150.0 mmol) were dissolved in dry DMF (200 mL), heated at 130 °C under nitrogen atmosphere for 12 h to give a mixture. The mixture was diluted with ethyl acetate and filtered through a bed of celite, and the organic phase was collected. The organic phase was washed with water twice, saturated brine once, the organic phase was collected, concentrated under reduced pressure, and purified by silica gel chromatography to give solid compound M-46b (9.91 g, 29 mmol) with a yield of 58%. ESI-MS (m / z) was analyzed by GC-MS to be 338.3.

[0206] Synthesis of compound M-46c:

[0207] Compound M-46b (6.77 g, 20 mmol) was dissolved in 100 mL of dry DMF, Pd(OAC)2(0.22 g, 1 mmol), Ag2CO3(0.28 g, 1 mmol), trimethylacetic acid (0.30 g, 3 mmol) were added, and the dehydrogenation cyclization reaction was heated at 140 °C in a sealed tube for 12 h to give a mixture. The mixture was diluted with ethyl acetate and filtered through a bed of celite, and the organic phase was collected. The organic phase was washed with water twice, saturated brine once, the organic phase was collected, concentrated under reduced pressure, and purified by silica gel chromatography to give solid compound M-46c (3.24 g, 9.6 mmol) with a yield of 48%. ESI-MS (m / z) was analyzed by GC-MS to be 336.8.

[0208] Synthesis of compound M-46d:

[0209] Compound M-46c (3.0 g, 10.0 mmol), bis-pinacolborane (5.6 g, 22 mmol), PdCl2(dppf) (0.41 g, 0.5 mmol) and potassium acetate (2.94 g, 30.0 mmol) were dissolved in DMF (100 mL) and heated at 90 °C under nitrogen atmosphere for 10 hours to obtain a mixture. The solvent of the mixture was removed by rotary evaporation under vacuum, dichloromethane was added to the residue and stirred, filtered, and purified by silica gel column chromatography to obtain solid compound M-46d (2.65 g, 5.1 mmol) with a yield of 51%. ESI-MS (m / z) was analyzed by GC-MS to be 520.2.

[0210] Synthesis of compound M-46:

[0211] Compound M-46d (3.94 g, 10 mmol), M-1e (3.57 g, 20 mmol), Pd(PPh3)4(0.58 g, 0.5 mmol) and potassium carbonate (4.14 g, 30.0 mmol) were dissolved in THF (50 mL) and water (50 mL) and heated at 80 °C under nitrogen atmosphere for 10 hours to obtain a mixture. The solvent of the mixture was removed by rotary evaporation under vacuum, dichloromethane was added to the residue and stirred, filtered, and purified by silica gel column chromatography to obtain solid compound M-46 (4.27 g, 5.2 mmol) with a yield of 52%. ESI-MS (m / z) was analyzed by GC-MS to be 820.3.

[0212] Example 7: Preparation of compound M-54

[0213]

[0214] Synthesis of compound M-54b:

[0215] Compound M-1a (17.7 g, 50.0 mmol), m-chlorobenzeneboronic acid (6.1 g, 50 mmol), Pd(PPh3)4(2.9 g, 2.5 mmol) and potassium carbonate (20.7 g, 150.0 mmol) were dissolved in dry DMF (200 mL) and heated at 130 °C under nitrogen atmosphere for 12 hours to obtain a mixture. The mixture was diluted with ethyl acetate and filtered through a bed of celite, and the organic phase was collected. The organic phase was washed twice with water, once with saturated brine, the organic phase was collected, concentrated under reduced pressure, and purified by silica gel column chromatography to obtain solid compound M-46b (11.2 g, 33 mmol) with a yield of 66%. ESI-MS (m / z) was analyzed by GC-MS to be 338.1.

[0216] Synthesis of compound M-54c:

[0217] Compound M-54b (6.77 g, 20 mmol) was dissolved in 100 mL of dry DMF, Pd(OAC)2(0.22 g, 1 mmol), Ag2CO3(0.28 g, 1 mmol), trimethylacetic acid (0.30 g, 3 mmol) were added, and the mixture was heated at 140 °C for 12 h in a sealed tube to give a mixture. The mixture was diluted with ethyl acetate and filtered through a bed of celite, and the organic phase was collected. The organic layer was washed twice with water, once with saturated brine, and the organic phase was collected and then concentrated under reduced pressure. The residue was purified by silica gel chromatography to give compound M-54c (2.34 g, 7.0 mmol) as a solid in 35% yield. ESI-MS (m / z) was analyzed by GC-MS: 336.5.

[0218] Synthesis of compound M-54d:

[0219] Compound M-46c (3.0 g, 10.0 mmol), bis(pinacolato)diboron (5.6 g, 22 mmol), PdCl2(dppf) (0.41 g, 0.5 mmol) and potassium acetate (2.94 g, 30.0 mmol) were dissolved in DMF (100 mL) and heated at 90 °C for 10 h under nitrogen atmosphere to give a mixture. The solvent of the mixture was removed by vacuum evaporation, and dichloromethane was added to the residue, which was stirred, filtered, and purified by silica gel chromatography to give compound M-54d (2.97 g, 5.7 mmol) as a solid in 57% yield. ESI-MS (m / z) was analyzed by GC-MS: 520.3.

[0220] Synthesis of compound M-54:

[0221] Compound M-54d (3.94 g, 10 mmol), M-1e (3.57 g, 20 mmol), Pd(PPh3)4(0.58 g, 0.5 mmol) and potassium carbonate (4.14 g, 30.0 mmol) were dissolved in THF (50 mL) and water (50 mL) and heated at 80 °C for 10 h under nitrogen atmosphere to give a mixture. The solvent of the mixture was removed by vacuum evaporation, and dichloromethane was added to the residue, which was stirred, filtered, and purified by silica gel chromatography to give compound M-54 (4.43 g, 5.4 mmol) as a solid in 54% yield. ESI-MS (m / z) was analyzed by GC-MS: 820.1.

[0222] Example 8: Preparation of compound M-62

[0223]

[0224] Synthesis of compound M-62b:

[0225] Compound M-1a (17.7 g, 50.0 mmol), o-chlorobenzeneboronic acid (6.1 g, 50 mmol), Pd(PPh3)4(2.9 g, 2.5 mmol) and potassium carbonate (20.7 g, 150.0 mmol) were dissolved in dry DMF (200 mL) and heated at 130 °C under nitrogen atmosphere for 12 h to obtain a mixture. The mixture was diluted with ethyl acetate and filtered through a bed of celite, and the organic phase was collected. The organic phase was washed with water twice, saturated brine once, and the organic phase was collected, concentrated under reduced pressure, and purified by silica gel chromatography to obtain solid compound M-46b (10.8 g, 32 mmol) with a yield of 64%. ESI-MS (m / z) was analyzed by GC-MS to be 338.1.

[0226] Synthesis of compound M-62c:

[0227] Compound M-62b (6.77 g, 20 mmol) was dissolved in 100 mL of dry DMF, Pd(OAC)2(0.22 g, 1 mmol), Ag2CO3(0.28 g, 1 mmol), trimethylacetic acid (0.30 g, 3 mmol) were added, and the mixture was heated at 140 °C in a sealed tube for 12 h to obtain a mixture. The mixture was diluted with ethyl acetate and filtered through a bed of celite, and the organic phase was collected. The organic layer was washed with water twice, saturated brine once, and the organic phase was collected, concentrated under reduced pressure, and purified by silica gel chromatography to obtain solid compound M-62c (3.23 g, 9.6 mmol) with a yield of 48%. ESI-MS (m / z) was analyzed by GC-MS to be 336.3.

[0228] Synthesis of compound M-62d:

[0229] Compound M-62c (3.0 g, 10.0 mmol), bis(pinacolato)diboron (5.6 g, 22 mmol), PdCl2(dppf) (0.41 g, 0.5 mmol) and potassium acetate (2.94 g, 30.0 mmol) were dissolved in DMF (100 mL) and heated at 90 °C under nitrogen atmosphere for 10 h to obtain a mixture. The solvent of the mixture was removed by vacuum evaporation, dichloromethane was added to the residue, stirred, filtered, and purified by silica gel chromatography to obtain solid compound M-62d (2.86 g, 5.5 mmol) with a yield of 55%. ESI-MS (m / z) was analyzed by GC-MS to be 520.2.

[0230] Synthesis of compound M-62:

[0231] Compound M-62d (3.94 g, 10 mmol), M-1e (3.57 g, 20 mmol), Pd(PPh3)4(0.58 g, 0.5 mmol) and potassium carbonate (4.14 g, 30.0 mmol) were dissolved in THF (50 mL) and water (50 mL), heated at 80°C for 10 hours under nitrogen atmosphere to obtain a mixture. The solvent in the mixture was removed by vacuum evaporation, dichloromethane was added to the residue, stirred, filtered, and purified by silica gel chromatography to obtain solid compound M-62 (4.18 g, 5.1 mmol) with a yield of 51%. ESI-MS (m / z) was obtained by gas chromatography-mass spectrometry analysis: 820.2.

[0232] 2. Preparation and performance test of organic electroluminescent device

[0233] In the device implementation, the structure of OLED is a substrate / anode / hole injection layer / hole transport layer / electron blocking layer / light-emitting layer / electron transport layer / electron injection layer / cathode arranged in layers.

[0234] In addition to the substrate, the corresponding substances and layer thicknesses of each layer are as follows: ITO (100 nm) / HATCN (10 nm) / NPB (60 nm) / TCTA (10 nm) / CBP:Ir(PPy)3(94 wt%:6 wt%, 30 nm) / the compound described in the application: Liq (40 nm, 50 wt%:50 wt%) / Liq (2 nm) / Al (100 nm).

[0235] The structural formulas of some of the functional compounds used in the OLED are as follows:

[0236]

[0237] The nitrogen-containing heterocyclic organic compounds of Examples 1-5 and Example 7 were used together with lithium 8-hydroxyquinolate as electron transport materials to prepare OLED devices 1-6 (labeled as OLED-1, OLED-2, OLED-3, OLED-4, OLED-5, OLED-6, respectively). The specific preparation process is as follows:

[0238] The transparent conductive ITO glass substrate was cleaned by ultrasonic washing with distilled water, acetone, and isopropyl alcohol and dried in an oven, and then transferred into a vacuum evaporation chamber. The vacuum degree was 2*10-5Pa. First, 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HATCN) was evaporated to form a 10 nm thick hole injection layer. Then, N,N'-diphenyl-naphthyl-9,9'-diamine (NPB) was evaporated to form a 60 nm thick hole transport layer. Then, 4,4',4"-tris(N-carbazolyl)triphenylamine (TCTA) was evaporated to form a 10 nm thick electron blocking layer. On the electron blocking layer, 94 wt% of CBP was used as a host material, and 6 wt% of green phosphorescent dopant tris(2-phenylpyridine) iridium (Ir(PPy)3) was used as a dopant material. The host material and the dopant material were co-evaporated to form a 30 nm thick light-emitting layer. Then, a 40 nm thick electron transport layer was evaporated on the light-emitting layer. The electron transport layer was a mixture of the nitrogen-containing heterocycle-containing organic compound of Examples 1-5 and 7 of the present application and 8-hydroxyquinoline lithium (Liq) in a mass ratio of 50 wt%:50 wt%. Finally, 2 nm of Liq was evaporated as an electron injection layer, and 100 nm of Al was evaporated as a cathode of the device, thereby producing OLED devices 1-6.

[0239] OLED Comparative Example: The OLED device was prepared in the same manner as the OLED devices 1-6, except that 1,3,5-tris(1-phenyl-1H-benzimidazol-2-yl)benzene (TPBi) was used instead of the nitrogen-containing heterocycle-containing organic compound of Examples 1-5 and 7 of the present application in the electron transport layer.

[0240] Evaluation of the Performance of the OLED Device: The current of the organic optoelectronic device at different voltages was measured using a Keithley 2400 digital nanovoltmeter, and the current density was obtained by dividing the current by the light-emitting area. The luminance and radiant energy density of the organic optoelectronic device at different voltages were measured using a Photo Research PR655. The current efficiency (cd / A) and external quantum efficiency (EQE) of the device were obtained based on the current density and luminance of the organic optoelectronic device at different voltages. The current efficiency and external quantum efficiency of the prepared device at a luminance of 1000 cd / m2were measured to be 8.5 cd / A and 5.4%, respectively. 2

[0241] Table 1

[0242]

[0243]

[0244] ​As can be seen from Table 1, compared with the comparative example (commonly used electron transport material TPBi), the new organic compound based on nitrogen heterocycle used in the electron transport layer of the OLED together with Liq can achieve higher device efficiency and relatively long lifetime, which indicates that it is very suitable as a stable and excellent organic electron transport material.

[0245] The technical features of the above-described embodiments can be combined in any manner. To make the description concise, all possible combinations of the technical features in the above-described embodiments are not described, but as long as the combinations of the technical features do not exist in contradiction, they shall be considered within the scope of the present disclosure.

[0246] The above-described embodiments only express several implementation manners of the present application, and the description is relatively specific and detailed, but it shall not be understood as a limitation on the patent scope of the present application. It should be pointed out that, for those skilled in the art, several modifications and improvements can be made without departing from the concept of the present application, and these shall be within the protection scope of the present application. Therefore, the patent protection scope of the present application shall be subject to the appended claims.

Claims

1. A nitrogen-containing heterocyclic organic compound characterized in that, having a structure according to any one of the following: 。 2. A mixture characterized in that, comprising: a first organic compound H1 and a second organic compound H2, the first organic compound H1 and the second organic compound H2 being different; the first organic compound H1 is selected from at least one nitrogen-containing heterocyclic organic compound according to claim 1; the second organic compound H2 is selected from a hole-transporting material, an electron-transporting material, an electron-injecting material, a host material, or an organic dye.

3. The mixture of claim 2, wherein, the second organic compound H2 is selected from an electron-injecting material.

4. The mixture according to claim 2 or 3, characterized in that, the second organic compound H2 is 8-hydroxyquinoline.

5. A composition characterized in that, comprising a nitrogen-containing heterocyclic organic compound according to claim 1, or a mixture according to any one of claims 2 to 4, and at least one organic solvent.

6. The composition of claim 5, wherein the organic solvent is selected from at least one of an alcohol, an ether, a ketone, and an ester.

7. The composition according to claim 5 or 6, wherein the organic solvent is selected from at least one of methanol, ethanol, isopropanol, n-hexanol, n-heptanol, n-octanol, ethylene glycol, diethylene glycol, triethylene glycol dimethyl ether, hexafluoroacetylacetone, ethylene glycol diacetate, and octafluoro-dimethyl adipate.

8. An electronic device comprising an anode, a cathode, one or more organic functional layers positioned between the anode and the cathode, characterized in that, the organic functional layer comprises a nitrogen-containing heterocyclic organic compound according to claim 1, or a mixture according to any one of claims 2 to 4, or is prepared from a composition according to any one of claims 5 to 7.

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