Phenanthroline derivative, organic electroluminescent element containing phenanthroline derivative and electronic equipment

Abstract

The invention belongs to the technical field of organic electroluminescence, and particularly relates to a phenanthroline derivative, an organic electroluminescence element containing the phenanthroline derivative and electronic equipment. The phenanthroline derivative has a structure as shown in a general formula 1, # imgabs0 #, R1, R2, R3, R4, R5, R6, R7 and R8 are the same or different, and R1, R2, R3, R4, R5, R6, R7 and R8 are the same or different. The R1, R2, R3, R4, R5, R6, R7 and R8 are independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl, and at least one of R1, R2, R3, R4, R5, R6, R7 and R8 is selected from the structure shown in the general formula 2; # imgabs1 #

Description

Technical Field

[0001] The invention belongs to the technical field of organic electroluminescence, and more specifically, relates to a phenanthroline derivative, an organic electroluminescent element containing the same, and an electronic device. Background Art

[0002] Organic light emitting diode is a self-luminous display element based on organic electroluminescent materials. Unlike existing liquid crystal display elements, it does not require a backlight source and is thin, making it a technology suitable for flexible element devices (flexible light-emitting display devices). Organic semiconductor materials are diverse in synthesis, have relatively low manufacturing costs, and have excellent optical and electrical properties. Organic light-emitting diodes (OLEDs) have great potential for application in optoelectronic devices (such as flat panel displays and lighting).

[0003] From the perspective of device structure, OLED device structures are classified into various types according to the structure of the light-emitting layer, such as single light-emitting layer, multi-doped light-emitting layer, multiple light-emitting layer, stacked structure, etc. In stacked devices, 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 that can be used for the charge generation layer of stacked devices, and the choice space is limited when designing devices. In addition, the number of device layers is large, and different compounds are often used for each layer, which increases the complexity of device manufacturing. Summary of the invention

[0004] The object of the present invention is to provide a phenanthroline derivative, which can be applied to charge generation layer and electron transport layer materials, and has lower driving voltage, higher current efficiency and longer service life when used as charge generation layer or electron transport layer materials, and is suitable for preparing high-performance organic electroluminescent elements.

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

[0006] A phenanthroline derivative, the compound having a structure shown in general formula 1,

[0007]

[0008] Wherein, R1, R2, R3, R4, R5, R6, R7, and R8 are the same or different from each other, and are independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, and the structure shown in Formula 2, and at least one of R1, R2, R3, R4, R5, R6, R7, and R8 is selected from the structure shown in Formula 2

[0009] In general formula 2, "*" indicates connection with phenanthroline,

[0010] L1 is selected from a single bond, a substituted or unsubstituted C6-C60 arylene group, and a substituted or unsubstituted C3-C60 heteroarylene group;

[0011] The substituents in the "substituted or unsubstituted" are each independently selected from 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 carbocyclyl, substituted or unsubstituted C3-C60 heterocyclyl;

[0012] The heteroatom in the heterocyclic group and heteroaryl group is selected from N, O, S, Si, and P.

[0013] Preferably, the phenanthroline derivative has a structure shown in Formula 3,

[0014]

[0015] wherein R1, R2, R3, R4, R5, R6, and R7 are the same as or different from each other, 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 C2-C10 alkenyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl;

[0016] L1 is selected from a single bond, a substituted or unsubstituted C6-C60 arylene group, and a substituted or unsubstituted C3-C60 heteroarylene group.

[0017] Preferably, R1, R2, R3, R4, R5, R6, and R7 are each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted n-propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted n-butyl, substituted or unsubstituted isobutyl, substituted or unsubstituted sec-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted phenyl. , substituted or unsubstituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted peryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyridyl, substituted or unsubstituted bipyridyl, substituted or unsubstituted terpyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazoline, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted indenyl, substituted or unsubstituted indolyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted carbolyl, substituted or unsubstituted 9,9-dimethyl substituted or unsubstituted 9,9-diphenylfluorene, substituted or unsubstituted spirobifluorene, substituted or unsubstituted phenanthroline, substituted or unsubstituted benzoquinolyl, substituted or unsubstituted benzisoquinolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted benzothiazolyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted benzopyrazolyl, substituted or unsubstituted naphthyridinyl.

[0018] Preferably, L1 is selected from a single bond, a substituted or unsubstituted C6-C60 arylene group; R1, R2, R3, R4, R5, R6, and R7 are the same as or different from each other, 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 C2-C10 alkenyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; R8 is the structure shown in Formula 2.

[0019] Preferably, L1 is selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted phenylene naphthyl group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracene group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted fluoranthenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted perylene group, and a substituted or unsubstituted terphenylene group.

[0020] Preferably, L1 is selected from a single bond,

[0021]

[0022] The invention discloses an application of the phenanthroline derivative as an organic electroluminescent element material.

[0023] The present invention also provides a preparation, which comprises at least one of the above-mentioned phenanthroline derivatives and at least one solvent.

[0024] The present invention also provides an organic electroluminescent element, comprising: a first electrode; a second electrode arranged to face the first electrode; and one or more organic material layers arranged between the first electrode and the second electrode and comprising a light-emitting layer, wherein the one or more layers of the organic material layer contain the phenanthroline derivative.

[0025] Preferably, the organic layer comprises an electron transport layer, and the electron transport layer comprises the phenanthroline derivative

[0026] Preferably, the organic layer comprises at least two light-emitting units, an N-type charge generation layer is included between the two light-emitting units, and the N-type charge generation layer comprises the phenanthroline derivative described in the present invention.

[0027] The present invention further provides an electronic device, wherein the electronic device is provided with the organic electroluminescent element.

[0028] In general, the above technical scheme conceived by the present invention can achieve the following beneficial effects compared with the prior art: when the phenanthroline derivative of the present invention is used as an organic electroluminescent element, it has a lower driving voltage, a higher current efficiency and a longer service life, and is suitable for preparing high-performance organic electroluminescent elements. BRIEF DESCRIPTION OF THE DRAWINGS

[0029] Figure 11 is a schematic diagram of the structure of the organic electroluminescent element described in Application Example 1, wherein the first electrode layer 12, the hole injection layer 11, the hole transport layer 10, the light-emitting layer 9, the electron transport layer 8, the N-type charge generation layer 7, the P-type charge generation layer 6, the hole transport layer 5, the light-emitting layer 4, the electron transport layer 3, the electron injection layer 2 and the second electrode layer 1, wherein 200 is a first light-emitting unit and 100 is a second light-emitting unit;

[0030] Figure 2 1 is a schematic diagram of the structure of the organic electroluminescent element described in Application Example 2, wherein the first electrode layer 110 , the hole injection layer 120 , the hole transport layer 130 , the light-emitting layer 140 , the electron transport layer 150 , the electron injection layer 160 and the second electrode layer 170 . DETAILED DESCRIPTION

[0031] The technical solution of the present invention is further described in detail below through specific embodiments. It should be understood that the implementation of the present invention is not limited to the following embodiments, and any form of modification and / or change made to the present invention will fall within the protection scope of the present invention.

[0032] In the present invention, unless otherwise specified, all parts and percentages are 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 examples, unless otherwise specified, are conventional methods in the art. The reagents used in the following examples, unless otherwise specified, can be purchased from conventional biochemical reagent stores.

[0033] Explanation of terms

[0034] As used in the present invention, the term "halogen group" may include fluorine, chlorine, bromine or iodine.

[0035] As used in the present invention, the term "C1-C10 alkyl" refers to a monovalent substituent derived from a straight or branched chain saturated hydrocarbon having 1 to 10 carbon atoms, examples of which include but are not limited to methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl and hexyl.

[0036] 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 cycloalkyl include, but are not limited to, cyclopropane, cyclobutane, cyclopentane, cyclohexane, norbornyl, adamantane, and the like.

[0037] As used in the present invention, the term "C2-C10 heterocyclic group (heterocycloalkyl)" refers to a monovalent substituent derived from a monocyclic or polycyclic ring having 2 to 10 carbon atoms, and the ring contains at least one heteroatom selected from O, S, N, P, Si.

[0038] As used in the present invention, the term "alkoxy" refers to a straight chain, a branched chain or a cyclic chain. The number of carbon atoms of the alkoxy group is not particularly limited herein, but the alkoxy group 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-pentoxy, neopentoxy, isopentyloxy, n-hexyloxy, and benzyloxy.

[0039] As used herein, the term "cycloalkenyl" refers to an unsaturated carbon ring and does not have aromatic character.

[0040] As used herein, the term "heterocycloalkenyl" refers to an unsaturated heterocyclic ring, and does not have aromatic character.

[0041] As used in the present invention, the term "C6-C60 aryl" refers to a monovalent substituent derived from an aromatic hydrocarbon having a monocyclic ring or a combination of two or more rings and having 6 to 60 carbon atoms. Further, such an aryl may have a form in which two or more rings are simply lateral or fused to each other. Examples of such aryl groups include, but are not limited to, phenyl, biphenyl, naphthyl, phenanthrenyl, anthracenyl, pyrenyl, triphenylene, fluoranthenyl, dimethyl 9,9-dimethylfluorene, 9,9-diphenylfluorene, spirobifluorenyl, etc.

[0042] As used in the present invention, the term "arylene group" refers to a divalent aromatic group derived from an "aryl group" by removing a hydrogen atom. For example, a phenyl group is formed by removing a hydrogen atom from a naphthyl group and a naphthyl group is formed by removing a hydrogen atom from a naphthyl group. In the present invention, the arylene group includes an aromatic divalent group composed of multiple aromatic rings fused together and an aromatic divalent group composed of multiple aromatic rings connected by single bonds.

[0043] As used in the present invention, the term "C3-C60 heteroaryl group" refers to a monovalent substituent derived from a monocyclic heterocyclic or polycyclic aromatic hydrocarbon having 3 to 60 carbon atoms. In this connection, at least one carbon, preferably 1 to 3 carbons in the ring are substituted with a heteroatom such as N, O, S, P, B or Si. In addition, this heteroaryl group may have a form in which two or more rings are simply lateral to each other or fused to each other or fused to an aromatic group. Examples of such heteroaryl groups include pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, indolizinyl, indolyl, indolopyridinyl, purinyl, phenanthroline, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, thiazolyl, imidazolyl, oxazolyl, furanyl, thienyl, benzofuranyl, benzothienyl, benzothiazolyl, benzimidazolyl, benzoxazolyl, carbazolyl, dibenzofuranyl, dibenzothienyl and the like, but the present invention is not limited thereto.

[0044] As used in the present invention, the term "heteroarylene" refers to a divalent heteroaryl group derived from a "heteroaryl group" by removing a hydrogen atom. For example, a pyridyl group is obtained by removing a hydrogen atom from the pyridyl group to form a pyridylene group. The heteroarylene group includes an aromatic divalent group composed of multiple fused aromatic rings and an aromatic divalent group composed of multiple aromatic rings connected by single bonds.

[0045] As used in the present invention, the term "silyl group" refers to a trisubstituted silyl group, such as trimethylsilyl, triphenylsilyl, and the like.

[0046] As used in the present invention, the "carbon number is XY" in the expression "Z group having carbon number XY" or "Z group of C(XY)" means the carbon number of the Z group when it is unsubstituted, and does not include the carbon number of the substituent when it is substituted. For example, a C6-C60 aromatic group means that when it is unsubstituted, the carbon number of the aromatic group is any integer between 6 and 60, that is, the carbon number when unsubstituted can be 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20...60.

[0047] 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 the substitution occurs can be the position where the hydrogen atom is replaced. That is, the position is not limited to a specific position, as long as the hydrogen at the position can be replaced by a substituent. For example, carbazolyl includes any of the following groups, but is not limited thereto, as long as it is not otherwise described in this specification,

[0048] Indicates the position of substitution. "Unsubstituted" means that hydrogen atoms remain, in this case, hydrogen atoms include protium, deuterium, tritium.

[0049] When two or more substituents are present, the two or more substituents may be the same or different.

[0050] As used herein, the term "naphthyridine" includes

[0051] As used herein, the term "terphenyl" includes

[0052] As used herein, the term "benzoquinoline" includes

[0053] As used in the present invention, hydrogen atoms include protium, deuterium and tritium. The compounds of the present invention may contain deuterium atoms of natural origin, or may introduce deuterium atoms by deuterating a portion or all of the raw material compounds. If deuterium atoms are introduced from the raw materials, the deuteration rate may be 100%, or may be less than 100%, or less than 95%, or less than 90%, or less than 80%, and the deuteration rate may also be more than 1%, or more than 5%, or more than 10%. If the deuteration rate is not 100%, it means a mixture of deuterated compounds and undeuterated compounds, or a mixture of completely deuterated compounds and incompletely deuterated compounds, or a mixture of completely deuterated compounds and undeuterated compounds and incompletely deuterated compounds.

[0054] As used in the present invention, terms such as first, second, A, B, etc. are used. The above terms are only used to distinguish components, and do not limit the nature or order of the components to which the terms correspond.

[0055] Organic electroluminescent element

[0056] The structure of the organic electroluminescent element of the present invention is a disclosed structure, comprising an anode, a cathode and an organic layer located between the anode and the cathode, wherein the organic layer comprises a light-emitting layer, and at least one layer of the organic layer comprises the compound of the present invention.

[0057] 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.

[0058] The light-emitting element of the present invention may emit fluorescence or phosphorescence or a combination thereof. The light-emitting element may emit light alone or in series with multiple light-emitting units.

[0059] As simple light emitting elements, the following may be cited, but are not limited thereto:

[0060] (1) hole transport layer / fluorescent light emitting layer / electron transport layer;

[0061] (2) hole transport layer / phosphorescent light emitting layer / electron transport layer;

[0062] (3) hole transport layer / first fluorescent light-emitting layer / second fluorescent light-emitting layer / electron transport layer;

[0063] (4) hole transport layer / first phosphorescent light-emitting layer / second phosphorescent light-emitting layer / electron transport layer;

[0064] (5) hole transport layer / fluorescent emitting layer / spacer layer / phosphorescent emitting layer / electron transport layer;

[0065] (6) hole transport layer / electron blocking layer / fluorescent light emitting layer / electron transport layer;

[0066] (7) hole transport layer / electron blocking layer / fluorescent light emitting layer / hole blocking layer / electron transport layer;

[0067] (8) hole transport layer / electron blocking layer / phosphorescent light emitting layer / electron transport layer;

[0068] (9) hole transport layer / electron blocking layer / phosphorescent emitting layer / hole blocking layer / electron transport layer;

[0069] (10) hole injection layer / hole transport layer / phosphorescent light emitting layer / electron transport layer / electron injection layer;

[0070] (11) hole injection layer / hole transport layer / fluorescent light emitting layer / electron transport layer / electron injection layer;

[0071] (12) hole injection layer / hole transport layer / electron blocking layer / phosphorescent light emitting layer / electron transport layer / electron injection layer;

[0072] (13) hole injection layer / hole transport layer / electron blocking layer / fluorescent light emitting layer / electron transport layer / electron injection layer;

[0073] The phosphorescent / fluorescent light-emitting layers mentioned above can each emit light of a different color.

[0074] As a tandem type organic electroluminescent element, it can be an anode / first light-emitting unit / intermediate layer / second light-emitting unit / cathode. The intermediate layer can also be generally called a charge generation layer, an electron extraction layer, a connecting layer, etc. For example, when stacking a fluorescent light-emitting layer and a phosphorescent light-emitting layer, an intermediate layer is placed between the fluorescent light-emitting layer and the phosphorescent light-emitting layer in order to prevent the excitons generated by the phosphorescent light-emitting layer from diffusing to the fluorescent light-emitting layer or to adjust the balance of carriers.

[0075] When the organic light emitting device includes a plurality of organic layers, the organic layers may be formed of the same material or different materials.

[0076] The organic electroluminescent element of the present specification can be manufactured by using materials and methods known in the art, except that one or more of the organic layers are prepared by using the compound comprising Formula 1.

[0077] As the cathode material, a material having a low work function is generally used to facilitate electron injection into the organic layer.

[0078] The hole injection layer is a layer that injects holes from the electrode and has a capability of transporting holes.

[0079] 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 is suitably a material having high hole mobility that can receive holes from the anode or the hole injection layer and transfer the holes to the light emitting layer.

[0080] The light emitting material may be a material that receives holes and electrons from the hole transport layer and the electron transport layer, respectively, and combines the holes and electrons to emit light in the visible light region. The light emitting layer material includes a host material and a doping material.

[0081] 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 is a material having high electron mobility that can receive electrons from the cathode and transfer the electrons to the light emitting layer.

[0082] The electron injection layer is a layer that injects electrons from the electrode.

[0083] The hole blocking layer is a layer that blocks holes from reaching the cathode.

[0084] The electron blocking layer is a layer that blocks electrons from reaching the anode.

[0085] The organic light emitting device of the present specification may be a top-emitting device, a bottom-emitting device, or a dual-emission type device according to the materials used.

[0086] The charge generation layer refers to the middle layer between the anode and 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, which can effectively separate charges and effectively transport carriers.

[0087] In a specific embodiment of the present invention, the phenanthroline derivative is selected from any one of the compounds represented by the following chemical formulas No. 1-103:

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098] Those skilled in the art can synthesize the compounds of the present invention by referring to the synthesis of the following compounds and known synthesis methods. For example, Formula 1 and Formula 2 can be obtained by Suzuki coupling reaction.

[0099] Synthesis Example

[0100] Example

[0101] Synthesis Example 1: Synthesis of 2J01

[0102] Synthesis of intermediate 1-1:

[0103]

[0104] Under nitrogen atmosphere, 1,6-dibromopyrene (20.0 g, 55.6 mmol), 9-phenanthrene boronic acid (14.2 g, 63.8 mmol), tetrakistriphenylphosphine palladium (642 mg, 0.55 mmol) and potassium carbonate (15.3 g, 111.2 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, and dried with anhydrous sodium sulfate to remove the solvent. Purification by silica gel chromatography (developing solvent: n-hexane: ethyl acetate = 100: 1) gave a total of 10.0 g (yield 39%) of intermediate 1.

[0105] LC-MS (APCI): 457.21 (M+H + ).Calcd for C 304 H 19 Br

[0106] Synthesis of intermediate 1-2

[0107]

[0108] Under nitrogen atmosphere, intermediate 2 (9.5 g, 20.78 mmol), biboronic acid pinacol ester (7.88 g, 31.2 mmol), 1,1'-bis(diphenylphosphino)ferrocene palladium dichloride (304 mg, 0.416 mmol) and potassium acetate (4.1 g, 41.56 mmol) were added to 300 ml of 1,4-dioxane and heated to reflux for 3 hours. After the reaction was completed, the reaction solution was cooled to room temperature, extracted with dichloromethane, and dried with anhydrous sodium sulfate to remove the solvent. Purification by silica gel chromatography (volume ratio of developing solvent: n-hexane: ethyl acetate = 1:1) gave a total of 10.3 g (yield 98%) of intermediate 2.

[0109] LC-MS (APCI): 505.37 (M+H + ).Calcd for C 36 H 31 BO2

[0110] Synthesis of 2J01

[0111]

[0112] Under nitrogen atmosphere, intermediate 2 (8.2 g, 16.25 mmol), 2-bromo-1,10-phenanthroline (4.0 g, 16.47 mmol), tetrakistriphenylphosphine palladium (185 mg, 0.16 mmol) and potassium carbonate (4.49 g, 32.5 mmol) were added to 350 ml of tetrahydrofuran and 150 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 with anhydrous sodium sulfate to remove the solvent. Purification by silica gel chromatography (volume ratio of developing solvent: n-hexane: dichloromethane = 1:4) gave 2J01, a total of 8.5 g (yield 94%).

[0113] LC-MS (APCI): 557.40 (M+H + ).Calcd for C 42 H 24 N2

[0114] 1 H NMR (400MHz, CD2Cl2) (ppm) δ = 9.19 (dt, 1H), 8.89 (dd, 2H), 8.59 (d, 1H), 8.50 (d, 1H), 8.42–8.29 ( m,4H),8.26–8.10(m,3H),8.03–7.91(m,5H),7.84–7.76(m,2H),7.79–7.65(m,3H),7.44(dt,2H)

[0115] Synthesis Example 2: Synthesis of 2J03

[0116] Synthesis of intermediate 2-1

[0117]

[0118] Under nitrogen atmosphere, 1,6-bis(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)pyrene (10.0 g, 22.017 mmol), 9-bromophenanthrene (5.7 g, 22.017 mmol), potassium carbonate (6.1 g, 44.035 mmol) and tetrakis(triphenylphosphine)palladium (0.51 g, 0.440 mmol), XantPhos (i.e. 4,5-bis(diphenylphosphine)-9,9-dimethylxanthene) (1.27 g, 2.202 mmol) were put into a four-necked bottle, 100 mL of tetrahydrofuran and 33 mL of deionized water were added, the temperature was raised to reflux of the reaction system, and then the mixture was stirred for 4 h. When the reaction was completed, the heating was stopped. The mixture was passed through a chromatography column with a volume ratio of n-hexane: dichloromethane = 3:1 to obtain 9.0 g of intermediate 2-1.

[0119] LC-MS (APCI): 505.23 (M+H + )Calcd for:C 36 H 29 BO2

[0120] Synthesis of 2J03

[0121]

[0122] Under nitrogen atmosphere, 4,4,5,5-tetramethyl-2-(6-(phenanthrene-9-yl)pyrene-1-yl)-1,3,2-dioxaborane (9.0 g, 17.850 mmol), 2-(4-bromophenyl)-1,10-phenanthroline (6.0 g, 17.850 mmol), potassium carbonate (4.9 g, 35.698 mmol) and bis(triphenylphosphine)palladium chloride (II) (0.25 g, 0.357 mmol) were placed in a four-necked bottle, 100 mL of tetrahydrofuran and 33 mL of deionized water were added, and the temperature was raised to reflux of the reaction system, and then the mixture was stirred for 8 h. The heating was stopped when the reaction was completed. The mixture was passed through a chromatography column with n-hexane: dichloromethane = 3:1 to obtain 7.0 g of yellow solid 2J03.

[0123] LC-MS (APCI): 633.23 (M+H + ).Calcd for:C 48 H 28 N2

[0124] 1H NMR(400MHz,CD2Cl2)δ9.16(dd,1H),8.83–8.77(m,2H),8.51–8.48(m,2H),8.36(d,1H),8.32(d,1H),8.29–8.21(m,3H),8.18(d,1H),8.14 (d,1H),8.05(d,2H),7.92(dd,1H),7.89–7.86(m,2H),7.84(d,3H),7.79(d,1H),7.72–7.66(m,2H),7.65–7.60(m,3H),7.36–7.30(m,2H).

[0125] The following application examples further illustrate the application of the phenanthroline derivatives of the present invention in the preparation of organic electroluminescent elements.

[0126] Application Example 1:

[0127] An organic electroluminescent element, such as Figure 1 As shown, it includes a stacked 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, wherein 200 is a first light-emitting unit, 100 is a 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, and 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.

[0128] The specific device structure is:

[0129] ITO(100nm) / NPD:F4-TCNQ(10%)(10nm) / NPD(120nm) / BH:BD(3%)(20nm) / TmPyPB(10nm) / Bphen:Li(2%)( 10nm) / NPD:F4-TCNQ(10%)(20nm) / NPD(20nm) / BH:BD(3%)(20nm) / Alq3(10nm) / LiF(0.5nm) / Al(200nm).

[0130] Device preparation process:

[0131] The bottom-emitting glass substrate used in this embodiment was purchased from Guangdong Xinli Display Technology Co., Ltd., and 100 nm ITO was used as the first electrode layer 12. First, the bottom-emitting glass substrate was cleaned with ITO cleaning agent, deionized water, and isopropyl alcohol in sequence, and then the bottom-emitting glass substrate was baked at 180 degrees Celsius for 30 minutes to dry it.

[0132] Then put the bottom luminescent glass substrate into the evaporation chamber and place it in a vacuum chamber of about 10 -8 Each organic layer is deposited on the ITO anode in sequence by thermal vacuum evaporation at a rate of 0.2-2 angstroms / second under the condition of torr. Among them, F4-TCNQ (mass content 10%) is doped into NPD to form a thickness of 10nm as a hole injection layer. NPD is formed to a thickness of 120nm as a hole transport layer, and the anthracene main body ADN (9,10-di(naphtha-2-yl-) anthracene) is doped with a 3% mass content of pyrene dopant 1,6-bis(diphenylamino)pyrene to form a blue light-emitting layer with a thickness of 20nm. TmPyPB is formed to a thickness of 10nm as the first electron transport layer, and BPhen (4,7-Diphenyl-1,10-phenanthroline) is doped with 2% mass content of Li to form an N-type charge generation layer 7 with a thickness of 10nm. F4-TCNQ with a mass content of 10% is doped on NPD. A P-type charge generation layer with a thickness of 20 nm is formed, NPD with a thickness of 20 nm is formed as a hole transport layer, an anthracene main body ADN (9,10-di(naphtha-2-yl-)anthracene) is doped with a pyrene dopant 1,6-bis(diphenylamino)pyrene with a mass content of 3% to form a blue light-emitting layer with a thickness of 20 nm, Alq3 (Tris-(8-hydroxyquinolinato)aluminum) is formed with a thickness of 10 nm as a second electron transport layer, LiF is formed with a thickness of 0.5 nm as an electron injection layer, and Al is formed with a thickness of 200 nm as a cathode.

[0133] Finally, the device was transferred back to the glove box and packaged with a glass cover and a moisture absorbent to complete the device, which was recorded as organic electronic element 1 (Comparative Example 1).

[0134]

[0135] Contrast structure

[0136] Bphen(4,7-Diphenyl-1,10-phenanthroline)

[0137]

[0138] Examples and Comparative Examples

[0139] The N-type charge generation layer 7 was prepared by using 2J01 prepared in Synthesis Example 1 of the present invention instead of the Bphen material, and the organic electronic element 2 was prepared by the same method.

[0140] The N-type charge generation layer 7 was prepared by using 2J03 prepared in Synthesis Example 2 of the present invention instead of Bphen material, and the organic electronic element 3 was prepared by the same method.

[0141] Comparative Example 2: The N-type charge generation layer 7 is prepared by replacing the Bphen material with the known material Ref01, and the organic electronic element 4 is prepared by the same method. Comparative Structure 1: The material Ref01 is a known material, and the structural formula is:

[0142]

[0143] Organic electroluminescent element evaluation

[0144] Life test method: Apply voltage to the obtained organic electroluminescent element so that the current density reaches 30mA / cm 2 The time until the brightness reaches 95% of the initial brightness (LT95 (unit: hour)) was measured.

[0145] Current efficiency at current density 15mA / cm 2 The driving voltage was tested at a current density of 15 mA / cm2. The test results are shown in Table 1 below.

[0146] Table 1

[0147] Driving voltage / V Current efficiency, cd / A LT95,h Organic electronic components1 7.07 17.53 58 Organic Electronic Components2 6.90 17.97 94 Organic Electronic Components3 6.88 17.83 95 Organic Electronic Components4 6.93 17.24 90

[0148] According to the test results, the organic electroluminescent elements 2 and 3 prepared by the compounds of the present application have lower driving voltage, higher current efficiency and longer service life than the organic electronic elements 1 and 4. Therefore, the compounds of the present invention are suitable for preparing high-performance organic electroluminescent elements as N-type charge generation layer materials.

[0149] The following application examples further illustrate the application of the phenanthroline derivatives described in the present invention as electron transport layers in the preparation of organic electroluminescent elements.

[0150] Application Example 2

[0151] This embodiment provides an organic electroluminescent device, such as Figure 2 As shown, it includes a first electrode layer 110 , a hole injection layer 120 , a hole transport layer 130 , a light emitting layer 140 , an electron transport layer 150 , an electron injection layer 160 and a second electrode layer 170 .

[0152] The specific device structure is:

[0153] ITO(100nm) / NPD:F4-TCNQ(10%)(10nm) / NPD(120nm) / BH:BD(3%)(20nm) / Alq3:Liq(50%)(10nm) / LiF(0.5nm) / Al(200nm).

[0154] Device preparation process:

[0155] The bottom-emitting glass substrate used in this embodiment was purchased from Guangdong Xinli Display Technology Co., Ltd., and 100 nm ITO was used as the first electrode layer 110. First, the bottom-emitting glass substrate was cleaned with ITO cleaning agent, deionized water, and isopropyl alcohol in sequence, and then the bottom-emitting glass substrate was baked at 180 degrees Celsius for 30 minutes to dry it.

[0156] Then put the bottom luminescent glass substrate into the evaporation chamber and place it in a vacuum chamber of about 10 -8 Each organic layer was deposited on the ITO anode in sequence by thermal vacuum evaporation at a rate of 0.2-2 angstroms / second under the condition of 1000 Å / s. Among them, F4-TCNQ (2,3,5,6-Tetrafluoro-tetracyanoquinodimethane) with a mass content of 10% was doped on NPD to form a thickness of 10nm as a hole injection layer, NPD was formed to a thickness of 120nm as a hole transport layer, 1,6-bis (diphenylamino) pyrene with a mass content of 3% was doped on the anthracene main body ADN (9,10-di (naphtha-2-yl-) anthracene) to form a blue light emitting layer with a thickness of 20nm, Alq3 was doped with Liq with a mass content of 50% to form an electron transport layer with a thickness of 10nm, LiF (Lithium Fluoride) was formed to a thickness of 0.5nm as an electron injection layer, and Al was formed to a thickness of 200nm as a cathode.

[0157] Finally, the device was transferred back to the glove box and encapsulated with a glass cover and a moisture absorbent to complete the device, which was recorded as organic electronic component 5.

[0158] Examples and Comparative Examples

[0159] The electron transport layer was prepared by using 2J03 prepared in Synthesis Example 2 of the present invention instead of Alq3, and the organic electronic component 6 was prepared by the same method.

[0160] Organic electroluminescent element evaluation

[0161] Life test method: Apply voltage to the obtained organic electroluminescent element so that the current density reaches 30mA / cm 2The time until the brightness reaches 95% of the initial brightness (LT95 (unit: hour)) was measured.

[0162] The driving voltage is at a current density of 15 mA / cm 2 Next test.

[0163] Current efficiency at current density 15mA / cm 2 The test results are shown in Table 2.

[0164] Table 2

[0165] Drive voltage, V Current efficiency, cd / A LT95,h Organic electronic components5 5.44 5.38 14 Organic electronic components6 3.81 7.99 44.9

[0166] Compared with the organic electronic element 5, the organic electroluminescent element 6 prepared by the compound of the present application has a lower driving voltage, a higher current efficiency and a longer service life. Therefore, the compound of the present invention is suitable for preparing high-performance organic electroluminescent elements as an electron transport layer material.

[0167] In this specification, each embodiment is described in a progressive manner, and each embodiment focuses on the differences from other embodiments. The same or similar parts between the embodiments can be referred to each other. For the device disclosed in the embodiment, since it corresponds to the method disclosed in the embodiment, the description is relatively simple, and the relevant parts can be referred to the method part.

[0168] A phenanthroline derivative provided by the present invention, an organic electroluminescent element and an electronic device comprising the same are described in detail above. Specific examples are used herein to illustrate the principle and implementation of the present invention, and the description of the above embodiments is only used to help understand the method of the present invention and its core idea. It should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, the present invention can also be improved and modified in a number of ways, and these improvements and modifications also fall within the scope of protection of the claims of the present invention.

Claims

1. A phenanthroline derivative, characterized in that The compound has a structure shown in general formula 1, Wherein, R1, R2, R3, R4, R5, R6, R7, and R8 are the same or different from each other, and are independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, and the structure shown in Formula 2, and at least one of R1, R2, R3, R4, R5, R6, R7, and R8 is selected from the structure shown in Formula 2 In general formula 2, "*" indicates connection with phenanthroline, L1 is selected from a single bond, a substituted or unsubstituted C6-C60 arylene group, and a substituted or unsubstituted C3-C60 heteroarylene group; In the "substituted or unsubstituted" mentioned above, the substituents when substituted are each independently selected from 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 carbocyclyl, substituted or unsubstituted C3-C60 heterocyclyl; The heteroatom in the heterocyclic group and heteroaryl group is selected from N, O, S, Si, and P.

2. A phenanthroline derivative according to claim 1, characterized in that, The phenanthroline derivative has a structure shown in general formula 3, Wherein, R1, R2, R3, R4, R5, R6, and R7 are the same as or different from each other and are independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C3-C10 cycloalkyl, substituted or unsubstituted C2-C10 alkenyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl; L1 is selected from a single bond, substituted or unsubstituted C6-C60 arylene, substituted or unsubstituted C3-C60 heteroarylene.

3. A phenanthroline derivative according to claim 1, characterized in that, R1, R2, R3, R4, R5, R6, and R7 are each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted n-propyl, substituted or unsubstituted isopropyl, substituted or unsubstituted n-butyl, substituted or unsubstituted isobutyl, substituted or unsubstituted sec-butyl, substituted or unsubstituted tert-butyl, substituted or unsubstituted pentyl, substituted or unsubstituted hexyl, substituted or unsubstituted heptyl, substituted or unsubstituted octyl, substituted or unsubstituted phenyl, substituted or unsubstituted substituted biphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted fluoranthenyl, substituted or unsubstituted pyrenyl, substituted or unsubstituted peryl, substituted or unsubstituted triphenylene, substituted or unsubstituted pyridyl, substituted or unsubstituted bipyridyl, substituted or unsubstituted terpyridyl, substituted or unsubstituted pyrimidyl, substituted or unsubstituted pyridazinyl, substituted or unsubstituted pyrazinyl, substituted or unsubstituted triazinyl, substituted or unsubstituted quinolyl, substituted or unsubstituted substituted or unsubstituted isoquinolyl, substituted or unsubstituted quinazoline, substituted or unsubstituted quinoxalinyl, substituted or unsubstituted pyrrolyl, substituted or unsubstituted furanyl, substituted or unsubstituted thienyl, substituted or unsubstituted indenyl, substituted or unsubstituted indolyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted benzothienyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothienyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted carbolyl, substituted or unsubstituted 9,9-dimethyl fluorene, substituted or unsubstituted 9,9-diphenylfluorene, substituted or unsubstituted spirobifluorene, substituted or unsubstituted phenanthroline, substituted or unsubstituted benzoquinolyl, substituted or unsubstituted benzisoquinolyl, substituted or unsubstituted imidazolyl, substituted or unsubstituted benzimidazolyl, substituted or unsubstituted oxazolyl, substituted or unsubstituted benzoxazolyl, substituted or unsubstituted thiazolyl, substituted or unsubstituted benzothiazolyl, substituted or unsubstituted pyrazolyl, substituted or unsubstituted benzopyrazolyl, substituted or unsubstituted naphthyridinyl.

4. A phenanthroline derivative according to claim 1, characterized in that, The L1 is selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted phenylene naphthyl group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted fluoranthenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted perylene group, and a substituted or unsubstituted terphenylene group.

5. A phenanthroline derivative according to claim 1, characterized in that, L1 is selected from a single bond, 6. A phenanthroline derivative according to claim 1, characterized in that: The phenanthroline derivative is selected from any one of the compounds shown in the following chemical formulas No. 1-103:

7. An organic electroluminescent element, characterized in that: include: a first electrode; a second electrode disposed to face the first electrode; as well as one or more organic layers disposed between the first electrode and the second electrode and including a light-emitting layer, One or more layers of the organic layer contain the phenanthroline derivative according to any one of claims 1 to 6.

8. The organic electroluminescent element according to claim 7, characterized in that: The organic layer includes an electron transport layer, and the electron transport layer includes the phenanthroline derivative according to any one of claims 1 to 6.

9. The organic electroluminescent element according to claim 7, characterized in that: The organic layer comprises at least two light-emitting units, an N-type charge generation layer is included between the two light-emitting units, and the N-type charge generation layer comprises the phenanthroline derivative according to any one of claims 1 to 6.

10. An electronic device, characterized in that: The electronic device comprises the organic electroluminescent element according to claim 9.

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