Heterocyclic compound, organic electroluminescent element, and electronic device

Abstract

The invention relates to a heterocyclic compound, an organic electroluminescent element and an electronic device. The heterocyclic compound has a structure as shown in a formula (1), # imgabs0 #, wherein R1, R2, R3, R4, R5, R6, R7 and R8 are the same or different; in the formula (I), each independently selected from the group consisting of a structure represented by # imgabs 1 #, hydrogen, deuterium, halogen, a cyano group, a substituted or unsubstituted C1-C10 alkyl group, a substituted or unsubstituted C3-C10 cycloalkyl group, a substituted or unsubstituted C1-C10 alkoxy group, a substituted or unsubstituted C2-C10 alkenyl group, a substituted or unsubstituted C2-C10 alkynyl group, a substituted or unsubstituted C6-C60 aryl group, and a substituted or unsubstituted C3-C60 heteroaryl group, in the formula (1), a substituted or unsubstituted C6-C60 carbocyclic group, a substituted or unsubstituted C3-C60 heterocyclic group, and at least one of R1, R2, R3, R4, R5, R6, R7 and R8 is selected from a structure represented by a formula (2).

Description

Technical Field

[0001] The present invention belongs to the technical field of organic electroluminescence, and more specifically, relates to a heterocyclic compound, an organic electroluminescent element, and an electronic device. Background Art

[0002] Organic semiconductor materials have diversity in synthesis, relatively low manufacturing costs, and excellent optical and electrical properties. Organic light-emitting diodes (OLEDs) have great potential in the applications of optoelectronic devices (such as flat panel displays and lighting).

[0003] Classified from the device structure, according to the structure of the light-emitting layer, the OLED device structure is divided into various types, such as including a single light-emitting layer, a multi-doped light-emitting layer, a multi-layer light-emitting layer, a stacked layer, and other structures. In the stacked device, the performance of the device is improved by adding a charge generation layer to the light-emitting unit. However, there is a lack of high-performance materials for the charge generation layer that can be used in the stacked device, and the selection space is limited when designing the device. Summary of the Invention

[0004] An object of the present invention is to provide a heterocyclic compound, which can be used as an N-type charge generation layer material to prepare an organic electroluminescent element and is a high-performance organic electroluminescent material.

[0005] The technical solution adopted by the present invention to solve its technical problems is:

[0006] A heterocyclic compound having the structure shown in formula (1),

[0007]

[0008] wherein R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 are the same as or different from each other and are each independently selected from the structure shown in formula (2), hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted C6-C60 carbocyclic group, substituted or unsubstituted C3-C60 heterocyclic group, R 1 、R 2 、R 3 、R 4, R 5 , R 6 , R 7 , R 8 At least one of them is selected from the structure shown in formula (2);

[0009] In, * represents the connection position with phenanthro[4,5-bcd]furan,

[0010] L 1 , L 2 are the same as or different from each other, and are each independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene, and a substituted or unsubstituted C3-C30 heteroarylene;

[0011] Ar 1 is selected from a substituted or unsubstituted n-bipyridyl group, n is an integer between 1 and 3, and when n is 1, Ar 1 is a pyridyl group;

[0012] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 When there are multiple s, multiple are independent of each other, the same as or different from each other, multiple Ls 1 are independent of each other, the same as or different from each other, multiple Ls 2 are independent of each other, the same as or different from each other;

[0013] In the "substituted or unsubstituted", the substituents in the case of substitution are selected from deuterium, halogen, cyano, C1-C10 alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C2-C10 alkenyl, C2-C10 alkynyl, C6-C60 aryl, C3-C60 heteroaryl, C6-C60 carbocyclic group, and C3-C60 heterocyclic group;

[0014] The heteroatoms in the heterocyclic group, heteroaryl group, and heteroarylene group are selected from one or more combinations of N, O, S, Si, and P;

[0015] R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 Two adjacent ones among them form a ring or do not form a ring.

[0016] Preferably, in one embodiment of the present invention, the R 1 and R 2 and R 3 and R 4 and R 5 and R 6 and R 7 and R 8 one of them is selected from the rest are each independently selected from the structure shown in formula (2), hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted C6-C60 carbocyclic group, substituted or unsubstituted C3-C60 heterocyclic group.

[0017] Furthermore, in an alternative embodiment of the present invention, the heterocyclic compound has the structure shown in formula (3):

[0018]

[0019] wherein, R 1 and R 2 and R 3 and R 5 and R 6 and R 7 and R 8 are the same or different and are each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted C6-C60 carbocyclic group, substituted or unsubstituted C3-C60 heterocyclic group,

[0020] L 1 and L 2 are the same as or different from each other and are each independently selected from a single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene;

[0021] Preferably, in one embodiment of the present invention, the L 1 and L 2 are not both single bonds at the same time;

[0022] Preferably, in one embodiment of the present invention, the L 1, L 2 One of them is selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, and the other is selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, a substituted or unsubstituted C3-C30 heteroarylene group, provided that L 1 , L 2 are not both single bonds at the same time;

[0023] More preferably, in one embodiment of the present invention, the L 1 , L 2 are each independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, and L 1 , L 2 are not both single bonds at the same time.

[0024] Furthermore, in an alternative embodiment of the present invention, R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 are each independently selected from hydrogen, deuterium, halogen, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, phenyl, biphenyl, naphthyl, anthracenyl, phenanthryl, fluoranthenyl, pyrenyl, perylenyl, triphenylenyl, pyridyl, bipyridyl, terpyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, pyrrolyl, furyl, thienyl, indenyl, indolyl, benzofuryl, benzothienyl, dibenzofuryl, dibenzothienyl, carbazolyl, carbolinyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirobifluorenyl, phenanthrolinyl, benzoquinolinyl, benzoisoquinolinyl, imidazolyl, benzimidazolyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, pyrazolyl, benzopyrazolyl, phthalazinyl.

[0025] Furthermore, in an alternative embodiment of the present invention, the L 1 , L 2Same as or different from each other, and each independently selected from a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted phenylnaphthylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted anthrylene, a substituted or unsubstituted phenanthrylene, a substituted or unsubstituted fluoranthenylene, a substituted or unsubstituted pyrenylene, a substituted or unsubstituted perylenylene, a substituted or unsubstituted terphenylenylene, a substituted or unsubstituted pyridinylene, a substituted or unsubstituted bipyridinylene, a substituted or unsubstituted terpyridinylene, a substituted or unsubstituted pyrimidinylene, a substituted or unsubstituted pyridazinylene, a substituted or unsubstituted pyrazinylene, a substituted or unsubstituted triazinylene, a substituted or unsubstituted quinolinylene, a substituted or unsubstituted isoquinolinylene, a substituted or unsubstituted quinazolinylene, a substituted or unsubstituted quinoxalinylene, a substituted or unsubstituted pyrrolylene, a substituted or unsubstituted furanylene, a substituted or unsubstituted thiophenylene, a substituted or unsubstituted indenylene, a substituted or unsubstituted indolylene, a substituted or unsubstituted benzofuranylene, a substituted or unsubstituted benzothiophenylene, a substituted or unsubstituted dibenzofuranylene, a substituted or unsubstituted dibenzothiophenylene, a substituted or unsubstituted carbazolyl, a substituted or unsubstituted carbolinyl, a substituted or unsubstituted 9,9-dimethylfluorenyl, a substituted or unsubstituted 9,9-diphenylfluorenyl, a substituted or unsubstituted spirobifluorenyl, a substituted or unsubstituted phenanthrolinyl, a substituted or unsubstituted benzoquinolinyl, a substituted or unsubstituted benzoisoquinolinyl, a substituted or unsubstituted imidazolyl, a substituted or unsubstituted benzimidazolyl, a substituted or unsubstituted oxazolyl, a substituted or unsubstituted benzoxazolyl, a substituted or unsubstituted thiazolyl, a substituted or unsubstituted benzothiazolyl, a substituted or unsubstituted pyrazolyl, a substituted or unsubstituted benzopyrazolyl, a substituted or unsubstituted phthalazinyl;

[0026] More preferably, in an alternative embodiment of the present invention, the L 1 and L 2 are the same as or different from each other, and each independently selected from a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted phenylnaphthylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted anthrylene, a substituted or unsubstituted phenanthrylene, a substituted or unsubstituted fluoranthenylene, a substituted or unsubstituted pyrenylene, a substituted or unsubstituted perylenylene, a substituted or unsubstituted terphenylenylene, and L 1 and L 2 are not both single bonds at the same time.

[0027] Furthermore, in an alternative embodiment of the present invention, the L 1 and L 2 are each independently selected from a single bond and a substituted or unsubstituted group as follows:

[0028]

[0029]

[0030] Preferably, the heterocyclic compound is selected from any one of the compounds shown by the following No. 1 to No. 188:

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043] Application of the heterocyclic compound according to the present invention as a material for an organic electroluminescent element.

[0044] The present invention also provides a preparation, and the preparation contains a heterocyclic compound having the structure shown above and at least one solvent.

[0045] The solvent is not particularly limited, and unsaturated hydrocarbon solvents well-known to those skilled in the art such as toluene, xylene, mesitylene, tetralin, decalin, dicyclohexane, n-butylbenzene, sec-butylbenzene, tert-butylbenzene, etc., carbon tetrachloride, chloroform, dichloromethane, dichloroethane, chlorobutane, bromobutane, chloropentane, bromopentane, chlorohexane, bromohexane, chlorocyclohexane, bromocyclohexane and other halogenated saturated hydrocarbon solvents, chlorobenzene, dichlorobenzene, trichlorobenzene and other halogenated unsaturated hydrocarbon solvents, tetrahydrofuran, tetrahydropyran and other ether solvents, alkyl benzoates and other ester solvents can be used.

[0046] An organic electroluminescent element includes a first electrode, a second electrode, and an organic layer between the first electrode and the second electrode. The organic layer includes a light-emitting layer, and the organic layer has one or more, and at least one organic layer contains the heterocyclic compound described in the present invention.

[0047] Preferably, the organic layer includes at least two light-emitting units, and a P-type charge generation layer and an N-type charge generation layer are included between the two light-emitting units. The N-type charge generation layer contains the heterocyclic compound described in the present invention; the N-type charge generation layer containing the heterocyclic compound described in the present invention means including one N-type charge generation layer containing the heterocyclic compound described in the present invention, or multiple N-type charge generation layers containing the heterocyclic compound described in the present invention. When there are two or more layers containing the heterocyclic compound of the present invention, the heterocyclic compounds are the same or different.

[0048] An electronic device includes: a display device or a lighting device including the organic electroluminescent element described in the present invention; and a control unit for driving the above display device or lighting device.

[0049] Compared with the existing known light-emitting materials, the beneficial effect of the present invention is that this material can be used as an N-type charge generation layer material to prepare an organic electroluminescent element, with higher current efficiency and longer service life, and it is a high-performance organic electroluminescent device. Description of the Drawings

[0050] Figure 1 It is a schematic structural diagram of the organic electroluminescent element described in Application Example 1, where there are a first electrode layer 12, a hole injection layer 11, a hole transport layer 10, a light-emitting layer 9, an electron transport layer 8, an N-type charge generation layer 7, a P-type charge generation layer 6, a hole transport layer 5, a light-emitting layer 4, an electron transport layer 3, an electron injection layer 2, and a second electrode layer 1, where 200 is the first light-emitting unit and 100 is the second light-emitting unit. Detailed Description of the Invention

[0051] The technical solution of the present invention will be further specifically described below through specific embodiments. It should be understood that the implementation of the present invention is not limited to the following embodiments, and any formal modification and / or change made to the present invention will fall within the protection scope of the present invention.

[0052] In the present invention, unless otherwise specified, all parts and percentages are in weight units, and the equipment and raw materials used can be purchased from the market or are commonly used in the art. The methods in the following embodiments are all conventional methods in the art unless otherwise specified.

[0053] The reagents used in the following embodiments can be obtained from a conventional biochemical reagent store unless otherwise specified.

[0054] Term Explanation

[0055] As used in the present invention, the term "halogen group" may include fluorine, chlorine, bromine or iodine.

[0056] As used in the present invention, the term "C1-C10 alkyl" refers to a monovalent substituent derived from a straight-chain or branched-chain saturated hydrocarbon having 1 to 10 carbon atoms. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl and hexyl.

[0057] As used in the present invention, the term "C3-C10 cycloalkyl" refers to a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 10 carbon atoms. Examples of such cycloalkyls include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantyl, etc.

[0058] As used in the present invention, the term "C6-C60 heterocycloalkyl" refers to a monovalent substituent derived from a monocyclic or polycyclic group having 6 to 60 carbon atoms and containing at least one heteroatom in the ring, the heteroatom being selected from O, S, N, P, Si.

[0059] As used in the present invention, the term "alkoxy" refers to a straight-chain, branched-chain or cyclic chain. The number of carbon atoms in the alkoxy is not particularly limited herein, but the alkoxy preferably has 1 to 10 carbon atoms. Specific examples thereof include, but are not limited to, methoxy, ethoxy, n-propoxy, isopropoxy (i-propyloxy), n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n-hexyloxy, benzyloxy.

[0060] As used in the present invention, the term "cycloalkenyl" refers to an unsaturated carbocyclic ring and does not have aromaticity.

[0061] As used in the present invention, the term "heterocycloalkenyl" refers to an unsaturated heterocyclic ring and does not have aromaticity.

[0062] As used in the present invention, the term "C6-C60 aryl" refers to a monovalent substituent derived from an aromatic hydrocarbon having a single ring or a combination of two or more rings and having 6 to 60 carbon atoms. Further, such aryl may have a form in which two or more of the rings are simply side-bonded to each other or fused to each other. Examples of such aryls include, but are not limited to, phenyl, biphenyl, naphthyl, phenanthryl, anthryl, pyrenyl, triphenylenyl, fluoranthenyl, 9,9-dimethylfluorene, 9,9-diphenylfluorene, spirobifluorenyl, etc.

[0063] As used in the present invention, the term "arylene" refers to a divalent aryl group derived by removing one hydrogen atom from "aryl". For example, phenyl becomes phenylene after removing one hydrogen atom, and naphthyl becomes naphthylene after removing one hydrogen atom.

[0064] As used in the present invention, the term "heteroaryl having 3 to 60 carbon atoms" refers to a monovalent substituent derived from a monocyclic or polycyclic aromatic hydrocarbon having 3 to 60 carbon atoms. In this connection, at least one carbon atom, preferably 1 - 3 carbon atoms in the ring, is replaced by a heteroatom such as N, O, S, P, B or Si. In addition, such a heteroaryl can have a form in which two or more rings are simply side - joined to each other or fused to each other or fused to an aryl group. Examples of such heteroaryl include pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, indolizinyl, indolyl, indolopyridyl, purinyl, phenanthrolinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, thiazolyl, imidazolyl, oxazolyl, furyl, thienyl, benzofuryl, benzothienyl, benzothiazolyl, benzimidazolyl, benzoxazolyl, carbazolyl, dibenzofuryl, dibenzothienyl, etc., and the present invention is not limited thereto.

[0065] As used in the present invention, the term "heteroarylene" refers to a divalent heteroaryl group derived by removing one hydrogen atom from "heteroaryl". For example, pyridyl becomes pyridylene after removing one hydrogen atom.

[0066] As used in the present invention, the term "phenylnaphthylene" refers to a divalent group formed by substituting two positions in phenylnaphthalene. These two substitution positions can be on the benzene ring or the naphthalene ring simultaneously, or one on the benzene ring and the other on the naphthalene ring.

[0067] As used in the present invention, the term "silyl" refers to a trisubstituted silyl group, such as trimethylsilyl, triphenylsilyl, etc.

[0068] As used in the present invention, in the expression "Z group having X - Y carbon atoms" or "Z group of C(X - Y)", "having X - Y carbon atoms" means the number of carbon atoms of the Z group when it is unsubstituted, excluding the carbon atoms of the substituents when it is substituted. For example, an aryl group of C6 - C60 means that when unsubstituted, the number of carbon atoms in the aryl group is any integer from 6 to 60, that is, when unsubstituted, the number of carbon atoms can be 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20... 60.

[0069] As used in the present invention, the term "substituted" means that a hydrogen atom in a compound is replaced by another substituent. The position where substitution occurs can be the position where the hydrogen atom is replaced. That is, this position is not limited to a specific position, as long as the hydrogen at this position can be replaced by a substituent. For example, as long as there is no other record in this specification, the carbazolyl group includes any of the following groups, but is not limited thereto,

[0070]

[0071] indicating the substitution position. "Unsubstituted" means that the hydrogen atom is retained. In this case, the hydrogen atom includes protium, deuterium, and tritium.

[0072] When there are two or more substituents, the two or more substituents can be the same or different.

[0073] As used in the present invention, the term "phthalazine" includes 1,2-phthalazine, 1,3-phthalazine, 1,4-phthalazine, 1,5-phthalazine, 1,6-phthalazine, 1,7-phthalazine, 1,8-phthalazine, 2,3-phthalazine, 2,4-phthalazine...

[0074] As used in the present invention, the term "terphenyl" includes

[0075] As used in the present invention, the hydrogen atom includes protium, deuterium, and tritium. The compounds described in the present invention can contain deuterium atoms of natural origin, or deuterium atoms can be introduced by deuterating a part or all of the starting compounds. If deuterium atoms are introduced from the starting materials, the deuteration rate can be 100%, or less than 100%, or less than 95%, or less than 90%, or less than 80%. The deuteration rate can also be 1% or more, or 5% or more, or 10% or more. If the deuteration rate is not 100%, it means a mixture of deuterated compounds and non-deuterated compounds, or a mixture of fully deuterated compounds and incompletely deuterated compounds, or a mixture of fully deuterated compounds, non-deuterated compounds, and incompletely deuterated compounds.

[0076] As used in the present invention, when "substituted or unsubstituted", the substituents in the case of substitution are selected from the group consisting of deuterium, halogen, cyano, C1-C10 alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C2-C10 alkenyl, C2-C10 alkynyl, C6-C60 aryl, C3-C60 heteroaryl, C6-C60 carbocyclic group, C3-C60 heterocyclic group; Exemplarily, the substituents in the case of substitution include: phenyl, benzopyrenyl, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, phenyl, biphenyl, naphthyl, anthracenyl, phenanthryl, fluoranthenyl, pyrenyl, perylenyl, triphenylenyl, pyridyl, bipyridyl, terpyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, pyrrolyl, furyl, thienyl, indenyl, indolyl, benzofuryl, benzothienyl, dibenzofuryl, dibenzothienyl, carbazolyl, carbolinyl, 9,9-dimethylfluorene, 9,9-diphenylfluorene, spirobifluorene, phenanthrolinyl, benzoquinolinyl, benzoisoquinolinyl, imidazolyl, benzimidazolyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, pyrazolyl, benzopyrazolyl, phthalazinyl...

[0077] As used in the present invention, the aryl contains at least 6 C atoms, the heteroaryl contains at least 2 C atoms and at least one heteroatom, and "aryl" or "heteroaryl" is not limited to the case of only containing aryl or heteroaryl. The aryl may contain non-aromatic groups composed of carbon and hydrogen elements, such as sp3 hybridized C, carbonyl, etc. The heteroaryl may contain non-aromatic groups composed of carbon and hydrogen elements (such as sp3 hybridized C, N or O atoms, carbonyl, etc.). Therefore, biphenyl, fluorene, etc. should be considered within the scope of "aryl" or "heteroaryl" of the present invention, and bipyridine should be considered within the scope of "heteroaryl" of the present invention.

[0078] As used in the present invention, terms such as the first, the second, A, B, etc. are used. The above terms are only used to distinguish the components and do not limit the nature or order of the components corresponding to the terms.

[0079] Organic electroluminescent element

[0080] The structure used in the organic electroluminescent element of the present invention is a publicly known structure, which includes an anode, a cathode, and an organic layer located between the anode and the cathode. The organic layer includes a light-emitting layer, and at least one layer of the organic layer contains the compound of the present invention.

[0081] The organic layer may further include one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer, but is not limited thereto.

[0082] The light-emitting element of the present invention can emit fluorescence or phosphorescence or a combination thereof, and the light-emitting element can emit light individually or in series of multiple light-emitting units.

[0083] As simple light-emitting elements, the following can be cited, but are not limited thereto,

[0084] (1) Hole transport layer / fluorescent light-emitting layer / electron transport layer;

[0085] (2) Hole transport layer / phosphorescent light-emitting layer / electron transport layer;

[0086] (3) Hole transport layer / first fluorescent light-emitting layer / second fluorescent light-emitting layer / electron transport layer;

[0087] (4) Hole transport layer / first phosphorescent light-emitting layer / second phosphorescent light-emitting layer / electron transport layer;

[0088] (5) Hole transport layer / fluorescent light-emitting layer / spacer layer / phosphorescent light-emitting layer / electron transport layer;

[0089] (6) Hole transport layer / electron blocking layer / fluorescent light-emitting layer / electron transport layer;

[0090] (7) Hole transport layer / electron blocking layer / fluorescent light-emitting layer / hole blocking layer / electron transport layer;

[0091] (8) Hole transport layer / electron blocking layer / phosphorescent light-emitting layer / electron transport layer;

[0092] (9) Hole transport layer / electron blocking layer / phosphorescent light-emitting layer / hole blocking layer / electron transport layer;

[0093] (10) Hole injection layer / hole transport layer / phosphorescent light-emitting layer / electron transport layer / electron injection layer;

[0094] (11) Hole injection layer / hole transport layer / fluorescent light-emitting layer / electron transport layer / electron injection layer;

[0095] (12) Hole injection layer / hole transport layer / electron blocking layer / phosphorescent light-emitting layer / electron transport layer / electron injection layer;

[0096] (13) Hole injection layer / hole transport layer / electron blocking layer / fluorescent light-emitting layer / electron transport layer / electron injection layer;

[0097] Each of the above phosphorescent / fluorescent light-emitting layers can emit light of different colors.

[0098] As a tandem organic electroluminescent device, it can be an anode / first light-emitting unit / intermediate layer / second light-emitting unit / cathode. The intermediate layer is generally also referred to as a charge generation layer, an electron extraction layer, a linking layer, etc. For example, when stacking a fluorescent light-emitting layer and a phosphorescent light-emitting layer, in order to prevent excitons generated in the phosphorescent light-emitting layer from diffusing to the fluorescent light-emitting layer or to adjust the carrier balance, an intermediate layer is placed between the fluorescent light-emitting layer and the phosphorescent light-emitting layer.

[0099] When an organic light-emitting device includes a plurality of organic layers, the organic layers can be formed of the same material or different materials.

[0100] The organic electroluminescent device of the present specification can be manufactured by materials and methods known in the art, except that one or more of the organic layers are formed by using the heterocyclic compounds described above.

[0101] The organic electronic device of the present invention includes a substrate, an anode, a cathode, and an organic layer provided between the cathode and the anode.

[0102] The substrate serves as a support for the light-emitting device. As the substrate, for example, glass, quartz, plastic, etc. can be used. In addition, a flexible substrate can also be used. A flexible substrate refers to a substrate that can be bent (flexible), such as a plastic substrate formed of polycarbonate or polyvinyl chloride. The available substrates in the embodiments of the present invention are not limited to this, as long as they can support the light-emitting device.

[0103] The anode formed on the substrate preferably uses a metal, alloy, conductive compound, and a mixture thereof with a large work function (specifically, 4.0 eV or more). Specifically, for example, indium tin oxide (ITO: Indium Tin Oxide), indium tin oxide containing silicon or silicon oxide, indium zinc oxide, indium containing tungsten oxide and zinc oxide, graphene, etc. In addition, gold (Au), platinum (Pt), or nitrides of metal materials (for example, titanium nitride) can also be used. The available anode materials in the embodiments of the present invention are not limited to this, and other anode materials can also be used in the embodiments of the present invention.

[0104] The cathode preferably uses a metal, alloy, conductive compound, and a mixture thereof with a small work function (specifically, 3.8 eV or less). As specific examples of such cathode materials, elements belonging to Group 1 or Group 2 of the periodic table can be cited, that is, alkali metals such as lithium (Li) and cesium (Cs), alkaline earth metals such as magnesium (Mg), and alloys containing them (for example, MgAg, AlLi), etc. The available cathode materials in the embodiments of the present invention are not limited to this, and other cathode materials can also be used in the embodiments of the present invention.

[0105] As a cathode material, a material with a low work function is usually used to facilitate electron injection into the organic layer.

[0106] The hole injection layer is a layer that injects holes from the electrode and has the ability to transport holes. As substances with high hole injection properties, ladder compounds or polymer compounds (oligomers, dendrimers, polymers, etc.) such as molybdenum oxide, titanium oxide, vanadium oxide, rhenium oxide, ruthenium oxide, chromium oxide, zirconium oxide, hafnium oxide, tantalum oxide, silver oxide, tungsten oxide, manganese oxide, aromatic amine compounds, fluorene derivatives, etc. can also be selected. The hole injection layer materials available in the embodiments of the present invention are not limited to this, and other hole injection layer materials can also be used in the embodiments of the present invention.

[0107] The hole transport material is a layer that receives holes from the hole injection layer and transports the holes to the light-emitting layer, and the hole transport material is suitably a material with a high hole mobility that can receive holes from the anode or the hole injection layer and transfer the holes to the light-emitting layer. Aromatic amine compounds, carbazole derivatives, anthracene derivatives, etc. can be used in the hole transport layer. Polymer compounds such as poly(N-vinylcarbazole) (abbreviation: PVK), poly(4-vinyltriphenylamine) (abbreviation: PVTPA), etc. can also be used. Among them, as long as the hole transport property is higher than the electron transport property, substances other than the above can be used. It should be noted that the layer containing a substance with high hole transport property can be not only a single-layer layer, but also a layer formed by laminating two or more layers containing the above substances. The hole transport materials available in the embodiments of the present invention are not limited to this, and other hole transport materials can also be used in the embodiments of the present invention.

[0108] The light-emitting material is a material that can receive holes and electrons from the hole transport layer and the electron transport layer respectively and combine the holes and electrons to emit light in the visible light region. The light-emitting layer material contains a host material and a dopant material.

[0109] The light-emitting layer preferably contains a host material (sometimes called a matrix material) and a dopant material (sometimes called a light-emitting material, a guest material, or an emitter). The embodiments of the present invention use well-known host materials, such as amine derivatives, azine derivatives, and fused polycyclic aromatic derivatives, etc.

[0110] Amine derivatives, such as monoamine compounds, diamine compounds, triamine compounds, tetraamine compounds, and amine compounds substituted with a carbazolyl group, etc.

[0111] Azine derivatives, such as monoazine derivatives, diazine derivatives, and triazine derivatives, etc.

[0112] Fused polycyclic aromatic derivatives, preferably fused polycyclic aromatic hydrocarbons without a heterocyclic skeleton, such as naphthalene, anthracene, phenanthrene, fluoranthene, and triphenylene, etc. fused polycyclic aromatic hydrocarbons, or their derivatives.

[0113] The host material can be used alone or in combination of two or more kinds.

[0114] The light-emitting layer may contain only one kind of host material or two or more kinds of host materials.

[0115] The content of the host material is not particularly limited. For example, the content of the host material is preferably 80% by mass or more and 99.9% by mass or less, more preferably 90% by mass or more and 99.9% by mass or less, and further preferably 95% by mass or more and 99.9% by mass or less, based on the entire light-emitting layer.

[0116] As the fluorescent host, a compound having a singlet energy level higher than that of the fluorescent dopant is preferred, and examples thereof include heterocyclic compounds and fused aromatic compounds.

[0117] As the phosphorescent host, a compound having a triplet energy level higher than that of the phosphorescent dopant is preferred. For example, metal complexes, heterocyclic compounds, fused aromatic compounds, etc. can be cited. Among them, for example, indole derivatives, carbazole derivatives, pyridine derivatives, pyrimidine derivatives, triazine derivatives, quinoline derivatives, isoquinoline derivatives, quinazoline derivatives, dibenzofuran derivatives, dibenzothiophene derivatives, naphthalene derivatives, triphenylene derivatives, phenanthrene derivatives, fluoranthene derivatives, etc. are preferred.

[0118] The light-emitting layer contains a doping material, and the doping material is preferably a substance with good light-emitting properties. For example, as the doping material, a fluorescent light-emitting material that emits fluorescence or a phosphorescent light-emitting material that emits phosphorescence can be used. The fluorescent light-emitting material is a compound capable of emitting light from the singlet excited state, and the phosphorescent light-emitting material is a compound capable of emitting light from the triplet excited state.

[0119] The electron transport material is a layer that receives electrons from the electron injection layer and transports the electrons to the light-emitting layer, and the electron transport material can receive electrons from the cathode and transfer the electrons to the light-emitting layer, which is a material with a high electron mobility. A substance having an electron mobility of 10 -6 cm 2 / Vs or more is preferred. For example, metal complexes, aromatic heterocyclic compounds, aromatic hydrocarbon compounds, polymer compounds, etc. can be cited.

[0120] As long as the compound has a higher electron transport property than the hole transport property, substances other than these can be used for the electron transport layer.

[0121] The electron transport layer can be a single layer or two or more layers can be stacked. In this case, it is preferred to dispose a layer containing a substance having a larger energy gap among substances with high electron transport properties on the side closer to the light-emitting layer.

[0122] The electron transport layer may contain metals such as alkali metals, magnesium, alkaline earth metals, alloys containing two or more of them, etc.; metal compounds such as lithium 8-hydroxyquinolate (abbreviation: Liq), alkali metal compounds, alkaline earth metal compounds, etc. When metals such as alkali metals, magnesium, alkaline earth metals, or alloys containing two or more of them are contained in the electron transport layer, their content is not particularly limited, and it is preferably 0.1 to 50% by mass, more preferably 0.1 to 20% by mass, and further preferably 1 to 10% by mass.

[0123] When metal compounds such as alkali metal compounds or alkaline earth metal compounds are contained in the electron transport layer, their content is preferably 1 to 99% by mass, more preferably 10 to 90% by mass. It should be noted that the layer on the light-emitting layer side when the electron transport layer is multilayered may also be formed only of these metal compounds. The electron injection layer is a layer that injects electrons from the electrode. As the electron injection layer, alkali metals, alkaline earth metals, or their compounds such as lithium (Li), cesium (Cs), calcium (Ca), lithium fluoride (LiF), cesium fluoride (CsF), calcium fluoride (CaF2), and lithium oxide (LiOx) can be used. In addition, a material in which a substance having electron transport properties contains an alkali metal, an alkaline earth metal, or their compounds can also be used in the electron injection layer. Specifically, a material in which Alq contains magnesium (Mg) can be used. It should be noted that at this time, electron injection from the cathode can be performed more efficiently.

[0124] Alternatively, a composite material obtained by mixing an organic compound and an electron donor (donor) may be used for the electron injection layer. Since such a composite material generates electrons in the organic compound due to the electron donor, its electron injection property and electron transport property are excellent. At this time, as the organic compound, a material having excellent transport of the generated electrons is preferred. Specifically, for example, the substances constituting the electron transport layer (metal complexes, heteroaromatic compounds, etc.) described above can be used. As the electron donor, any substance that exhibits electron-donating properties to the organic compound can be used. As the electron donor, specifically, alkali metals, alkaline earth metals, and rare earth metals are preferred, and examples include lithium, cesium, magnesium, calcium, erbium, and ytterbium. In addition, as the electron donor, alkali metal oxides and alkaline earth metal oxides are preferred, and examples include lithium oxide, calcium oxide, and barium oxide. In addition, a Lewis base such as magnesium oxide can also be used. In addition, organic compounds such as tetrathiafulvalene (abbreviation: TTF) can also be used.

[0125] The hole blocking layer is a layer that blocks holes from reaching the cathode.

[0126] The electron blocking layer is a layer that blocks electrons from reaching the anode.

[0127] Depending on the materials used, the organic light-emitting device of this specification may be a top-emitting device, a bottom-emitting device, or a dual-emission device.

[0128] A charge generation layer refers to an intermediate layer located between the anode and the cathode in a tandem structure device, and is a layer that generates holes and electrons by charge separation. The charge generation layer is usually formed by a P-type layer on the cathode side and an N-type layer on the anode side, and can effectively separate charges and efficiently transport carriers.

[0129] In one embodiment of the present invention, the formation method of each layer is not particularly limited. Formation methods based on vacuum evaporation, spin coating, etc., which are well-known in the art, can be used. Each layer such as the light-emitting layer can be formed by a well-known method such as vacuum evaporation, molecular beam epitaxy (MBE method), or a coating method such as dip coating, spin coating, casting, bar coating, roll coating, etc. of a solution dissolved in a solvent.

[0130] In one embodiment of the present invention, the film thickness of each layer is not particularly limited, and generally several nanometers to dozens of nanometers can be used. In order to suppress defects such as pinholes, reduce the driving voltage, and improve the luminous efficiency, a range of several nm to 1 μm is usually preferred.

[0131] Those skilled in the art can synthesize the compounds of the present invention by referring to the synthesis of the following compounds and well-known synthesis methods. An example of a general synthesis formula of the present invention is as follows:

[0132]

[0133] In the above general formula, X 1 -X 5 is a halogen, which may be the same or different from each other, and L 1 , L 2 are linking groups, and their specific structures can be selected from L 1 , L 2 in Formula (1). can be replaced with -B(OH) 2 .

[0134] Those skilled in the art make selections according to the selectivity of the reaction. The above general formula of the present invention is only one exemplary one, and those skilled in the art can adjust the connection mode of the linking groups L 1 , L 2 in the above general formula according to the conventional synthesis means in the art. For example, L 2 , L 1 are sequentially connected to terpyridine, and then reacted with halogen-substituted phenanthro[4,5-bcd]furan to obtain the compound of the present application, or L 2 is connected to terpyridine, L 1 is connected to phenanthro[4,5-bcd]furan, and finally the compound of the present application is obtained through a coupling reaction.

[0135] Synthesis Example

[0136] Example 1: Synthesis of Compound 1

[0137] Step 1: Synthesis of Intermediate 1

[0138]

[0139] Under a nitrogen atmosphere, 7 g of 8-(4-bromophenyl)phenanthro[4,5-bcd]furan, 6.2 g of bis(pinacolato)diboron, 4 g of potassium acetate, and 0.3 g of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium were added to a four-necked reaction flask. Then, 100 ml of anhydrous dioxane was added, and the mixture was heated to reflux. After the reaction was completed, the temperature was lowered to room temperature, water was added, and the mixture was extracted with dichloromethane and dried over anhydrous sodium sulfate and then mixed with silica gel. After column chromatography (n-hexane:dichloromethane), 6 g of a solid (Intermediate 1) was obtained, with a yield of 75.3%.

[0140] LC-MS (APCI): 395.36 [M+H] +

[0141] Step 2: Synthesis of Intermediate 2

[0142]

[0143] Under a nitrogen atmosphere, 6 g of Intermediate 1 and 6.9 g of 4-bromoiodobenzene were dissolved in 150 ml of dioxane. Then, 6 g of sodium carbonate and 0.52 g of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium were added, and 60 ml of water was added and the temperature was raised to 90 °C for reaction. After the reaction was completed, the temperature was lowered to room temperature, water was added, and the mixture was extracted with dichloromethane and dried over anhydrous sodium sulfate and then mixed with silica gel. After column chromatography (n-hexane:dichloromethane), 5 g of a solid (Intermediate 2) was obtained, with a yield of 67.6%.

[0144] LC-MS (APCI): 423.28 [M+H] +

[0145] Step 3: Synthesis of Intermediate 3

[0146]

[0147] Under a nitrogen atmosphere, 5 g of Intermediate 2, 4 g of bis(pinacolato)diboron, 2.3 g of potassium acetate, and 0.45 g of [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium were added to a four-necked reaction flask. Then, 100 ml of anhydrous dioxane was added, and the mixture was heated to reflux. After the reaction was completed, the temperature was lowered to room temperature, water was added, and the mixture was extracted with dichloromethane and dried over anhydrous sodium sulfate and then mixed with silica gel. After column chromatography (n-hexane:dichloromethane), 5.2 g of a solid (Intermediate 3) was obtained, with a yield of 93.2%.

[0148] LC-MS(APCI): 471.50 [M+H] +

[0149] Step 4: Synthesis of Compound 1

[0150]

[0151] Under a nitrogen atmosphere, 6.8 g of 4'-bromo-2,2':6',2”-terpyridine, 10.23 g of Intermediate 3, 1.26 g of tetrakis(triphenylphosphine)palladium, and 6 g of potassium carbonate were added to a four-necked reaction flask. Then, 300 ml of tetrahydrofuran and 100 ml of water were added, and the mixture was heated to 75 °C for reaction. After the reaction was completed, the reaction solution was cooled to room temperature, and the crude product was obtained by filtration. The crude product was slurried with chlorobenzene to obtain Compound 1 as a white solid (8.2 g, 67%).

[0152] LC-MS(APCI): 576.45 [M+H] +

[0153] 1 H NMR(400MHz, CD 2 Cl 2 ) δ 8.86(s, 2H), 8.65–8.61(m, 4H), 8.04(s, 1H), 8.01–7.99(d, 2H), 7.91–7.88(m, 5H), 7.85–7.80(m, 5H), 7.79–7.74(m, 2H), 7.65–7.63(m, 2H), 7.31–7.27(m, 2H).

[0154] Example 2: Synthesis of Compound 2

[0155] Step 1: Synthesis of Intermediate 2-1

[0156]

[0157] Under a nitrogen atmosphere, 4'-(4-bromo-1-naphthyl)-2,2':6',2'-terpyridine (9.03 g, 0.021 mol), bis(pinacolato)diboron (6.28 g, 0.024 mol), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (0.45 g, 0.62 mmol), and potassium acetate (4.04 g, 0.041 mol) were added to 125 ml of 1,4-dioxane and refluxed for 5 hours. After the reaction solution was cooled to room temperature, it was filtered through diatomaceous earth and then suction filtered. The filtrate was concentrated to dryness, and the solid was slurried with methanol to obtain the solid of Intermediate 2-1 (8.1 g, yield 81%).

[0158] LC-MS(APCI): 486.49 [M+H]+

[0159] Step 2: Synthesis of Compound 2

[0160]

[0161]

[0162] Under a nitrogen atmosphere, intermediate 2-1 (5.0 g, 0.010 mol), 8-(4-bromophenyl)phenanthro[4,5-bcd]furan (3.60 g, 0.011 mol), tetrakis(triphenylphosphine)palladium (0.35 g, 0.31 mmol), and potassium carbonate (2.85 g, 0.021 mol) were added to 50 ml of toluene, 25 ml of ethanol, and 20 ml of water, and the mixture was refluxed for 3 hours. After the reaction solution was cooled to room temperature, suction filtration was carried out to obtain a crude solid, and the solid was slurried with tetrahydrofuran. A pale yellow solid, namely Compound 2 (5.6 g, yield 62%), was thus obtained.

[0163] LC-MS (APCI): 626.45 [M+H] +

[0164] 1 H NMR (400 MHz, CD 2 Cl 2 ) δ 8.77 (dt, 2H), 8.74–8.68 (m, 4H), 8.23–8.20 (m, 1H), 8.18 (s, 1H), 8.13–8.07 (m, 2H), 8.02–7.87 (m, 7H), 7.84–7.68 (m, 6H), 7.61–7.53 (m, 2H), 7.39 (ddd, 2H).

[0165] Example 3: Synthesis of Compound 10

[0166] Step 1: Synthesis of Intermediate 10-1

[0167]

[0168] Under a nitrogen atmosphere, 4'-(4-bromophenyl)-2,2':6',2”-terpyridine (10.0 g, 25.75 mmol), 4-chloro-1-naphthaleneboronic acid (6.90 g, 33.43 mmol), potassium carbonate (10.7 g, 77.25 mmol), and 1,1-bis(diphenylphosphino)ferrocene dichloropalladium (0.94 g, 1.28 mmol) were added to a four-necked reaction flask. 200 ml of tetrahydrofuran and 100 ml of water were added, and the temperature was raised to reflux for reaction. The reaction was complete after 5 h. After the reaction was completed, the reaction solution was cooled to room temperature, filtered with suction and concentrated, and slurried with 100 ml of n-hexane to obtain intermediate 10-1 (13.0 g, 27.66 mmol).

[0169] LC-MS(APCI): 470.35[M+H] +

[0170] Step 2: Synthesis of intermediate 10-2

[0171]

[0172] Under a nitrogen atmosphere, intermediate 10-1 (13.0 g, 27.66 mmol), potassium acetate (10.8 g, 110.64 mmol), bis(pinacolato)diboron (10.5 g, 41.49 mmol), and 1,1-bis(diphenylphosphino)ferrocene dichloropalladium (1.63 g, 2.22 mmol) were added to a four-necked reaction flask. 300 ml of anhydrous 1,4-dioxane was added, and the temperature was raised to strong reflux for reaction for 12 h. The reaction solution was cooled and the temperature was lowered, filtered with suction and concentrated. Column chromatography (volume ratio of n-hexane:dichloromethane = 4:1) was used for elution to obtain intermediate 10-2 (16.0 g, 28.49 mmol).

[0173] LC-MS(APCI): 562.52[M+H] +

[0174] Step 3: Synthesis of compound 10

[0175]

[0176] Step 3: Under a nitrogen atmosphere, intermediate 10-2 (15.0 g, 26.71 mmol), 8-bromophenanthro[4,5-bcd]furan (7.96 g, 29.38 mmol), bis(triphenylphosphine)palladium dichloride (0.70 g, 0.75 mmol), and potassium carbonate (6.20 g, 44.86 mmol) were placed in a four-necked reaction flask. Then 300 ml of tetrahydrofuran and 100 ml of water were added, and the temperature was raised to reflux for reaction for 4 h. The temperature was lowered to room temperature, and compound 10 (8.00 g, 12.79 mmol) was obtained by filtration with suction.

[0177] LC-MS (APCI): 626.52 [M+H] +

[0178] 1 H-NMR (400 MHz, CD 2 Cl 2 ) δ 8.83 (s, 2H), 8.71–8.63 (m, 4H), 8.10–8.02 (m, 4H), 7.90–7.80 (m, 4H), 7.77–7.72 (m, 2H), 7.72–7.59 (m, 6H), 7.43 (ddd, J=8.4, 6.7, 1.3 Hz, 1H), 7.37–7.25 (m, 4H).

[0179] Example 4: Synthesis of Compound 26

[0180] Step 1: Synthesis of Intermediate 26-3

[0181]

[0182] Under a nitrogen atmosphere, 5 g of raw material 26-1, 6.7 g of raw material 26-2, 5.1 g of potassium carbonate, and 0.27 g of Pd(dppf)Cl 2 (2%) were added to a four-necked reaction flask, and then THF:water (120 ml:40 ml) was added. The system was heated to reflux, and after reacting for 3 h, a sample was taken for TLC and sent for LC-MS. After the results were confirmed, the heating was stopped, and the temperature was cooled to room temperature. The precipitated solid was filtered. The solid was washed with 20 ml of ethanol and then with 20 ml of n-hexane, and dried to obtain Intermediate 26-3 (6.8 g, yield 94.1%).

[0183] LC-MS (APCI): 393.26 [M+H] +

[0184] Step 2: Synthesis of Compound 26

[0185]

[0186] Under a nitrogen atmosphere, 6.16 g of Intermediate 26-3, 7.51 g of Intermediate 26-4, 4.34 g of potassium carbonate, 0.287 g of (dba) 2 Pd (2%), and 0.299 g of Xpos (4%) were added to a four-necked reaction flask, and then THF:water (300 ml:100 ml) was added. The system was heated to reflux, and after reacting for 3 h, a sample was taken for TLC and sent for LC-MS. After the results were confirmed, the heating was stopped, and the temperature was cooled to room temperature. The precipitated solid was filtered and purified to obtain Compound 26 (6.25 g, yield 61.7%).

[0187] LC-MS (APCI): 666.44 [M+H] +

[0188] 1 HNMR (400 MHz, CD 2 Cl 2 ) δ 8.96 (s, 2H), 8.68–8.63 (m, 4H), 8.27 (s, 1H), 8.15–7.13 (d, 2H), 7.90–7.76 (m, 7H), 7.75–7.65 (m, 5H), 7.51–7.49 (d, 1H), 7.42–7.40 (d, 1H), 7.34–7.29 (m, 3H), 7.13 - 7.09 (m, 1H).

[0189] The following application examples further illustrate the application of the heterocyclic compounds described in the present invention in the preparation of organic electroluminescent devices.

[0190] Application Example 1:

[0191] An organic electroluminescent device, the structure is as Figure 1 shown, including a first electrode layer 12, a hole injection layer 11, a hole transport layer 10, a light-emitting layer 9, an electron transport layer 8, an N-type charge generation layer 7, a P-type charge generation layer 6, a hole transport layer 5, a light-emitting layer 4, an electron transport layer 3, an electron injection layer 2, and a second electrode layer 1 which are stacked. Among them, 200 is the first light-emitting unit and 100 is the second light-emitting unit. The first light-emitting unit 200 includes a hole injection layer 11, a hole transport layer 10, a light-emitting layer 9, and an electron transport layer 8. The second light-emitting unit 100 includes a hole transport layer 5, a light-emitting layer 4, an electron transport layer 3, and an electron injection layer 2.

[0192] The specific device structure is as follows:

[0193] ITO (100 nm) / NPD:F4-TCNQ (10%)(10 nm) / NPD (120 nm) / BH:BD (3%)(20 nm) / TmPyPB (10 nm) / Bphen:Li (2%)(10 nm) / NPD:F4-TCNQ (10%)(20 nm) / NPD (20 nm) / BH:BD (3%)(20 nm) / Alq 3 (10 nm) / LiF (0.5 nm) / Al (200 nm).

[0194] Device preparation process:

[0195] The bottom-emitting glass substrate used in this embodiment is purchased from Guangdong Xinyi Display Technology Co., Ltd., and 100 nm ITO is used as the first electrode layer 12. First, the bottom-emitting glass substrate is successively cleaned with ITO cleaning agent, deionized water, and isopropyl alcohol, and then the bottom-emitting glass substrate is baked at 180 °C for 30 minutes to dry it.

[0196] Then the bottom-emitting glass substrate is placed in the evaporation chamber, and each organic layer is successively deposited on the ITO anode by thermal vacuum evaporation at a rate of 0.2 - 2 Å / s under a vacuum of about 10 -8 Torr. Among them, F4-TCNQ (mass content 10%) is incorporated into NPD to form a thickness of 10 nm as the hole injection layer. NPD is formed into a thickness of 120 nm as the hole transport layer. On the anthracene host ADN (9,10-di(naphtha-2-yl-)anthracene), a pyrene dopant 1,6-bis(diphenylamino)pyrene with a mass content of 3% is doped to form a blue light-emitting layer with a thickness of 20 nm. TmPyPB is formed into a thickness of 10 nm as the first electron transport layer. In BPhen (4,7-Diphenyl-1,10-phenanthroline), Li with a mass content of 2% is doped to form an N-type charge generation layer 7 with a thickness of 10 nm. On NPD, F4-TCNQ with a mass content of 10% is doped to form a P-type charge generation layer with a thickness of 20 nm. NPD is formed into a thickness of 20 nm as the hole transport layer. On the anthracene host ADN (9,10-di(naphtha-2-yl-)anthracene), a pyrene dopant 1,6-bis(diphenylamino)pyrene with a mass content of 3% is doped to form a blue light-emitting layer with a thickness of 20 nm. Alq 3 (Tris-(8-hydroxyquinolinato)aluminum) is formed into a thickness of 10 nm as the second electron transport layer. LiF is formed into a thickness of 0.5 nm as the electron injection layer. Al is formed into a thickness of 200 nm as the cathode.

[0197] Finally, the device is transferred back to the glove box and encapsulated with a glass cover and a desiccant to complete the device, denoted as organic electronic component 1.

[0198]

[0199] Comparative structure 1

[0200] Bphen(4,7-Diphenyl-1,10-phenanthroline)

[0201]

[0202] Comparative structure 2

[0203] The synthesis method of compound L is as follows:

[0204] 1. Synthesis of intermediate L-1

[0205]

[0206] Under a nitrogen atmosphere, 2-(4-bromophenyl)-4,6-diphenyl-1,3,5-triazine (25 g, 64.60 mmol), bis(pinacolato)diboron (18 g, 71.06 mmol), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (II) (944 mg, 1.292 mmol), and potassium acetate (12.66 g, 129.2 mmol) were added to 500 ml of 1,4-dioxane, and the temperature was raised to reflux for 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature, extracted with dichloromethane, dried over anhydrous sodium sulfate, and the solvent was removed. Purification was carried out by silica gel chromatography (development solvent volume ratio: n-hexane:ethyl acetate = 1:1) to obtain 25 g of intermediate L-1 (yield 89%).

[0207] LC-MS (APCI): 436.35 [M+H] +

[0208] 2. Synthesis of intermediate L-2

[0209]

[0210] Under a nitrogen atmosphere, intermediate L-1 (24.56 g, 56.46 mmol), 1-bromo-4-iodonaphthalene (20.62 g, 62.10 mmol), tetrakis(triphenylphosphine)palladium (0) (1.31 g, 1.13 mmol), and potassium carbonate (115.58 g, 112.92 mmol) were added to 350 ml of toluene, 150 ml of ethanol, and 150 ml of water, and the temperature was raised to reflux for 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature, extracted with dichloromethane, dried over anhydrous sodium sulfate, and the solvent was removed. Purification was carried out by silica gel chromatography (development solvent volume ratio: n-hexane:ethyl acetate = 2:3) to obtain 21.5 g of intermediate L-2 (yield 74%).

[0211] LC-MS (APCI): 514.33 [M+H] +

[0212] 3. Synthesis of intermediate L-3

[0213]

[0214] Under a nitrogen atmosphere, the intermediate L-2 (11.5 g, 22.37 mmol), bis(pinacolato)diboron (8.49 g, 33.56 mmol), [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium (490 mg, 0.67 mmol), and potassium acetate (4.38 g, 44.74 mmol) were added to 200 ml of 1,4-dioxane, and the temperature was raised to reflux for 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature, extracted with dichloromethane, and dried over anhydrous sodium sulfate, and then the solvent was removed. Purification by silica gel chromatography (development solvent volume ratio: n-hexane:ethyl acetate = 1:4) gave 11 g of intermediate L-3 (yield 87%).

[0215] LC-MS (APCI): 562.55 [M+H] +

[0216] 4. Synthesis of Compound L

[0217]

[0218] Under a nitrogen atmosphere, the intermediate L-3 (10.0 g, 17.82 mmol), 8-bromophenanthro[4,5-bcd]furan (5.07 g, 18.71 mmol), tetrakis(triphenylphosphine)palladium (617 mg, 0.53 mmol), and potassium carbonate (7.37 g, 53.46 mmol) were added to 200 ml of tetrahydrofuran and 70 ml of water, and the temperature was raised to reflux for 4 hours. After the reaction was completed, the reaction solution was cooled to room temperature, extracted with dichloromethane, and dried over anhydrous sodium sulfate, and then the solvent was removed. Purification by silica gel chromatography (development solvent volume ratio: n-hexane:dichloromethane = 1:4) gave 10 g of compound L (yield 90%).

[0219] LC-MS (APCI): 626.52 [M+H] +

[0220] 1 H-NMR (400 MHz, CD 2 Cl 2 ) δ 9.03–8.97 (m, 2H), 8.90–8.81 (m, 4H), 8.14 (d, 2H), 7.98–7.85 (m, 4H), 7.83–7.58 (m, 12H), 7.52 (ddd, 1H), 7.46–7.34 (m, 2H).

[0221] Examples and Comparative Examples

[0222] Replace the Bphen material with Compound 1 prepared in Example 1 of the present invention to prepare the N-type charge generation layer 7, and fabricate the organic electronic device 2 by the same method.

[0223] Replace the Bphen material with Compound 2 prepared in Example 2 of the present invention to prepare the N-type charge generation layer 7, and fabricate the organic electronic device 3 by the same method.

[0224] Replace the Bphen material with Compound 10 prepared in Example 3 of the present invention to prepare the N-type charge generation layer 7, and fabricate the organic electronic device 4 by the same method.

[0225] Replace the Bphen material with Compound 26 prepared in Example 4 of the present invention to prepare the N-type charge generation layer 7, and fabricate the organic electronic device 5 by the same method.

[0226] Replace the Bphen material with Compound L of Comparative Structure 2 of the present invention to prepare the N-type charge generation layer 7, and fabricate the organic electronic device 6 by the same method.

[0227] Evaluation of Organic Electroluminescent Devices

[0228] Lifetime test method: Apply a voltage to the obtained organic electroluminescent device to make the current density reach 30 mA / cm 2 , and measure the time until the luminance becomes 95% of the initial luminance (LT95 (unit: hours)).

[0229] The current efficiency is tested at a current density of 15 mA / cm 2 .

[0230] The driving voltage is tested at a current density of 15 mA / cm 2 . The test results are shown in Table 1.

[0231] Table 1

[0232] Driving voltage, V Current efficiency, cd / A LT95, h Organic electronic component 1 7.07 17.53 58 Organic electronic component 2 6.95 17.76 109 Organic electronic component 3 6.99 17.85 122 Organic electronic component 4 6.99 17.86 115 Organic electronic component 5 6.98 17.75 84 Organic electronic component 6 8.61 18.02 10

[0233] Compared with the organic electroluminescent device 1 prepared from the Bphen material, the organic electroluminescent devices 2-5 prepared from the compounds of the present application have a lower driving voltage, a higher current efficiency, and a longer service life. Compared with the organic electronic device 6, the organic electroluminescent devices 2-5 prepared from the compounds of the present application have a significantly lower driving voltage and a significantly improved service life. Therefore, when the compounds of the present invention are used as organic electroluminescent materials, the obtained organic electroluminescent devices can exhibit more balanced and superior performance and are suitable for preparing high-performance organic electroluminescent devices.

Claims

1. A heterocyclic compound, characterized in that, the heterocyclic compound has the structure shown in formula (1), Among them, R 1 and R 2 and R 3 and R 4 and R 5 and R 6 and R 7 and R 8 are the same as or different from each other and are each independently selected from the structures shown, hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted C6-C60 carbocyclic group, substituted or unsubstituted C3-C60 heterocyclic group, provided that at least one of R 1 and R 2 and R 3 and R 4 and R 5 and R 6 and R 7 and R 8 is selected from the structure shown in formula (2); In ,"*" indicates the connection position with phenanthro[4,5-bcd]furan, L 1 and L 2 are the same as or different from each other and are each independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group; Ar 1 selected from substituted or unsubstituted n - bipyridyl groups, where n is an integer between 1 and 3, and when n is 1, Ar 1 is a pyridyl group; R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 There are multiple When there are multiple are each independent, the same as or different from each other, and multiple Ls 1 are each independent, the same as or different from each other, and multiple Ls 2 are each independent, the same as or different from each other; the substituents in the "substituted or unsubstituted" when substituted are selected from deuterium, halogen, cyano, C1-C10 alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C2-C10 alkenyl, C2-C10 alkynyl, C6-C60 aryl, C3-C60 heteroaryl, C6-C60 carbocyclic group, C3-C60 heterocyclic group; the heteroatoms in the heterocyclic group, heteroaryl group, and heteroarylene group are selected from one or more combinations of N, O, S, Si, and P; R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Any two adjacent ones among them form a ring or do not form a ring.

2. A heterocyclic compound according to claim 1, characterized in that, the heterocyclic compound has the structure shown in formula (3): Among them, R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 are the same or different and each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C1-C10 alkoxy, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C2-C10 alkynyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted C6-C60 carbocyclic group, substituted or unsubstituted C3-C60 heterocyclic group. L 1 and L 2 are the same as or different from each other and are each independently selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group.

3. A heterocyclic compound according to claim 1, characterized in that, Said R 1 , R 2 , R 3 , R 5 , R 6 , R 7 , R 8 are each independently selected from hydrogen, deuterium, halogen, cyano, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, phenyl, biphenyl, naphthyl, anthracenyl, phenanthryl, fluoranthenyl, pyrenyl, perylenyl, triphenylenyl, pyridyl, bipyridyl, terpyridyl, pyrimidinyl, pyridazinyl, pyrazinyl, triazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, pyrrolyl, furyl, thienyl, indenyl, indolyl, benzofuryl, benzothienyl, dibenzofuryl, dibenzothienyl, carbazolyl, carbolinyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, spirobifluorenyl, phenanthrolinyl, benzoquinolinyl, benzoisoquinolinyl, imidazolyl, benzimidazolyl, oxazolyl, benzoxazolyl, thiazolyl, benzothiazolyl, pyrazolyl, benzopyrazolyl, phthalazinyl.

4. A heterocyclic compound according to claim 1, characterized in that, The L 1 and L 2 are the same as or different from each other and are each independently selected from a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted phenylnaphthyl, a substituted or unsubstituted biphenylene, a substituted or unsubstituted naphthylene, a substituted or unsubstituted anthrylene, a substituted or unsubstituted phenanthrylene, a substituted or unsubstituted fluoranthenylene, a substituted or unsubstituted pyrenylene, a substituted or unsubstituted perylenylene, a substituted or unsubstituted terphenylene, a substituted or unsubstituted pyridinyl, a substituted or unsubstituted bipyridinyl, a substituted or unsubstituted terpyridinyl, a substituted or unsubstituted pyrimidinyl, a substituted or unsubstituted pyridazinyl, a substituted or unsubstituted pyrazinyl, a substituted or unsubstituted triazinyl, a substituted or unsubstituted quinolinyl, a substituted or unsubstituted isoquinolinyl, a substituted or unsubstituted quinazolinyl, a substituted or unsubstituted quinoxalinyl, a substituted or unsubstituted pyrrolyl, a substituted or unsubstituted furyl, a substituted or unsubstituted thienyl, a substituted or unsubstituted indenyl, a substituted or unsubstituted indolyl, a substituted or unsubstituted benzofuranyl, a substituted or unsubstituted benzothienyl, a substituted or unsubstituted dibenzofuranyl, a substituted or unsubstituted dibenzothienyl, a substituted or unsubstituted carbazolyl, a substituted or unsubstituted carbolinyl, a substituted or unsubstituted 9,9-dimethylfluorenyl, a substituted or unsubstituted 9,9-diphenylfluorenyl, a substituted or unsubstituted spirobifluorenyl, a substituted or unsubstituted phenanthrolinyl, a substituted or unsubstituted benzoquinolinyl, a substituted or unsubstituted benzoisoquinolinyl, a substituted or unsubstituted imidazolyl, a substituted or unsubstituted benzimidazolyl, a substituted or unsubstituted oxazolyl, a substituted or unsubstituted benzoxazolyl, a substituted or unsubstituted thiazolyl, a substituted or unsubstituted benzothiazolyl, a substituted or unsubstituted pyrazolyl, a substituted or unsubstituted benzopyrazolyl, and a substituted or unsubstituted phthalazinyl.

5. A heterocyclic compound according to claim 1, characterized in that, The said L 1 , L 2 are independently selected from a single bond, a substituted or unsubstituted group as follows:

6. A heterocyclic compound according to claim 1, characterized in that, the heterocyclic compound is selected from any one of the compounds shown in No. 1 to No. 205 below:

7. Use of a heterocyclic compound according to any one of claims 1-6 as a material for an organic electroluminescent element.

8. An organic electroluminescent element, comprising a first electrode, a second electrode, and an organic layer between the first electrode and the second electrode, the organic layer comprising a light-emitting layer, characterized in that: the organic layer has one or more, and at least one organic layer contains the heterocyclic compound according to any one of claims 1-6.

9. An organic electroluminescent element according to claim 8, characterized in that: the organic layer includes at least two light-emitting units, and an N-type charge generation layer is included between the two light-emitting units, and the N-type charge generation layer contains the heterocyclic compound according to any one of claims 1-6.

10. An electronic device, comprising: one or more of a display, a monitor, and a lighting device, including the organic electroluminescent element according to claim 8 or 9; and a control unit for driving the above display device.

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