A triptycene derivative and its application

Abstract

The present invention relates to the field of display technology, and in particular to a triptycene derivative and its application. The triptycene derivative provided by the present invention has a structure as shown below: the triptycene derivative can effectively transmit electrons or holes, block electrons or holes, and has good thermal stability. Therefore, using the triptycene derivative as a hole transport layer material and an electron blocking layer material can make an organic electroluminescent device have a lower driving voltage, a higher luminous efficiency and a longer life.

Description

Technical Field

[0001] The present invention relates to the field of display technology, and in particular to a triptycene derivative and application thereof. Background Art

[0002] Organic light emitting diodes (OLEDs) are considered to be the most promising display and lighting technology by converting electrical energy into light by applying power to organic electroluminescent materials, and generally include an anode, a cathode, and an organic layer formed between the two electrodes. The organic layer of the electronic version of organic light emitting (organic EL) may include a hole injection layer, a hole transport layer, a hole auxiliary layer, a luminescent auxiliary layer, an electron blocking layer, a luminescent layer (containing a host material and a dopant material), an electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, etc. The materials used in the organic layer can be divided into hole injection materials, hole transport materials, hole auxiliary materials, luminescent auxiliary materials, electron blocking materials, luminescent materials, electron buffer materials, hole blocking materials, electron transport materials, electron injection materials, etc. depending on their functions. In the device of organic EL, holes from the anode and electrons from the cathode are injected into the luminescent layer by applying a voltage, and excitons with high energy are generated by the recombination of holes and electrons. The electrons of the organic electroluminescent material emit light by the energy when the energy moves to the excited state and returns to the ground state from the excited state.

[0003] Organic electroluminescent devices utilize triplet and singlet excitons. Compared with singlet excitons, triplet excitons have a longer lifetime and diffusion length. Therefore, phosphorescent organic electroluminescent devices generally require a hole blocking layer (HBL) to be added between the light-emitting layer (EML) and the electron transport layer (ETL), or an electron blocking layer (EBL) to be added between the light-emitting layer and the hole transport layer. The purpose of using an HBL or an EBL is to limit the recombination of injected holes and electrons and relax the excitons generated in the EML, thereby improving the luminous efficiency of the organic electroluminescent device.

[0004] In the field of organic electroluminescent materials, there is a continuous demand for organic materials that can effectively transport electrons or holes, block electrons or holes, and have good thermal stability. At the same time, there is also a continuous demand for hole transport materials (HTL) and electron blocking materials (EBL) that can reduce driving voltage and power consumption, increase luminous efficiency and service life. Summary of the invention

[0005] The purpose of the present invention is to overcome the problem that existing hole transport layer materials and electron blocking layer materials cannot obtain organic electroluminescent devices with lower driving voltage, higher luminous efficiency and longer life, and further provide an organic electroluminescent compound and its application.

[0006] The present invention also aims to solve the technical problems existing in the prior art by providing an organic electroluminescent compound with good stability.

[0007] Definitions of substituent terms in this invention:

[0008] As used herein, the term "halogen" may include fluorine, chlorine, bromine or iodine.

[0009] As used in the present invention, the term "C1-C30 alkyl" refers to a monovalent substituent derived from a straight or branched chain saturated hydrocarbon having 1 to 30 carbon atoms, examples of which include but are not limited to methyl, ethyl, propyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl and hexyl.

[0010] As used in the present invention, the term "C3-C30 cycloalkyl" refers to a group derived from a monocyclic hydrocarbon or a polycyclic hydrocarbon having 1 to 30 ring main chain carbon atoms, and the cycloalkane may include cyclopropyl, cyclobutyl, adamantyl, and the like.

[0011] In the present invention, aryl and arylene groups include monocyclic, polycyclic or condensed-ring aromatic groups, the rings may be interrupted by short non-aromatic units, and may contain spiro structures. Aryl groups include but are not limited to phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracenyl, fluorenyl, spirobifluorenyl, etc., and arylene groups include but are not limited to phenylene, biphenylene, terphenylene, naphthyl, phenanthryl, anthracenyl, fluorenyl, spirobifluorenyl, etc.

[0012] In the present invention, heteroaryl and heteroarylide include monocyclic, polycyclic or condensed ring heteroaryl, and the rings may be interrupted by short non-aromatic units, and the heteroatoms include nitrogen, oxygen and sulfur. Heteroaryl includes, but is not limited to, furanyl, phenylthio, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl, benzo thiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl, and derivatives thereof; heteroarylene includes but is not limited to furanyl, phenylene thio, pyrroleyl yl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazolyl, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl, benzofuranyl, benzothiophenylene, isobenzofuranyl, dibenzofuranyl, dibenzothiophenylene, benzimidazolyl, oxazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, acridinyl, and derivatives thereof.

[0013] As used in the present invention, the term "substituted" refers to a hydrogen atom in a compound being replaced by another substituent. The position is not limited to a specific position, as long as the hydrogen at the position can be replaced by a substituent. When two or more substituents are present, the two or more substituents may be the same or different.

[0014] As used herein, unless otherwise specified, hydrogen atoms include protium, deuterium and tritium.

[0015] In the present invention, the range of the number of carbon atoms is defined in the definition of the group, and the number of carbon atoms is any integer within the defined range. For example, C6-C30 aromatic group, the number of carbon atoms representing the aromatic group can be any integer within the range of 6-60, such as 6, 8, 10, 13, 15, 17, 20, 22, 25 or 30, etc.

[0016] In the present invention, Indicates a connection key.

[0017] The scheme adopted by the present invention is as follows:

[0018] The present invention provides a triptycene derivative having the following structure:

[0019]

[0020] Among them, R 1 -R 12 Each is independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C5-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C6-C30 arylamine;

[0021] R 13 , R 14 Each is independently selected from substituted or unsubstituted C1-C20 alkyl;

[0022] The substituents in the substituted C1-C30 alkyl, substituted C3-C30 cycloalkyl, substituted C5-C60 aryl, substituted C3-C60 heteroaryl, and substituted or unsubstituted C6-C30 aromatic amine are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C5-C12 aryl, and C3-C12 heteroaryl.

[0023] Preferably, R 1 -R 12 At least one has the following structure:

[0024]

[0025] L1 is selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted C3-C30 heteroarylene group;

[0026] n is an integer from 0 to 5;

[0027] Ar 1 -Ar 2 Each is independently selected from hydrogen, deuterium, protium, tritium, halogen, cyano, substituted or unsubstituted C6-C30 arylamine, substituted or unsubstituted C3-C30 heteroarylamine, substituted or unsubstituted C6-C30 aryl, and substituted or unsubstituted C3-C30 heteroaryl;

[0028] The substituents of the substituted C6-C30 arylene group, substituted C3-C30 heteroarylene group, substituted C6-C30 arylamine group, substituted C3-C30 heteroarylamine group, substituted C6-C30 aryl group, substituted C3-C30 heteroaryl group are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl group, C3-C30 cycloalkyl group, C5-C12 aryl group, C3-C12 heteroaryl group.

[0029] Preferably, L1 is selected from a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted terphenylene, and a substituted or unsubstituted naphthylene;

[0030] The substituents of the substituted phenylene, substituted biphenylene, substituted terphenylene and substituted naphthylene are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C5-C12 aryl and C3-C12 heteroaryl.

[0031] Preferably, R 1 -R 12 One of them has the structure shown in Formula 2, and the other is hydrogen;

[0032]

[0033] L1 is selected from phenylene, biphenylene, naphthylene;

[0034] n is 0 or 1.

[0035] Preferably, Ar 1 -Ar 2 Each is independently selected from a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group;

[0036] The substituents of the substituted C6-C30 aryl group and the substituted C3-C30 heteroaryl group are selected from one or a combination of C5-C12 aryl group and C3-C12 heteroaryl group.

[0037] Preferably, Ar 1 -Ar 2 Each is independently selected from substituted or unsubstituted A groups:

[0038] Wherein the A group is selected from one of the following groups:

[0039] phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracenyl, triphenylene, pyrenyl, phenylnaphthyl, naphthylphenyl, pyridyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, dinaphthothiophenyl, dinaphthofuranyl, dinaphthothiophenyl, dibenzofuranylphenyl, dibenzothiophenylphenyl, dibenzocarbazolyl, phenylbenzocarbazolyl, phenylcarbazolyl, dibenzocarbazolyl, dimethylfluorenyl, benzodimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, and dimethylfluorenylphenyl;

[0040] The substituent of the substituted A group is selected from one or a combination of two of hydrogen, C1-C6 alkyl, C3-C30 cycloalkyl, C5-C12 aryl, and C3-C12 heteroaryl.

[0041] Preferably, Ar 1 -Ar 2 Each is independently selected from phenyl, biphenyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, dimethylfluorenyl, diphenylfluorenyl, and dibenzocarbazolyl.

[0042] Preferably, R 1 -R 12 At least one has the following structure:

[0043]

[0044] L2 is selected from a single bond, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted C3-C30 heteroarylene group;

[0045] R T1 -R T8 each independently selected from hydrogen, deuterium, tritium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, C1-C30 alkyl in which one or more methylene groups are each substituted with -O- and / or -S- in a non-adjacent O atom and / or S atom, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, substituted or unsubstituted C4-C30 heteroaralkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C1-C30 alkoxy, and substituted or unsubstituted C6-C30 aryloxy;

[0046] R T1 -R T8 Each exists independently or two adjacent rings are connected to form ring B, and the ring B is a substituted or unsubstituted C6-C30 aromatic ring, or a substituted or unsubstituted C3-C30 heteroaromatic ring;

[0047] The substituents of the substituted or unsubstituted C6-C30 arylene group, substituted or unsubstituted C3-C30 heteroarylene group, substituted C1-C30 alkyl group, substituted C7-C30 aralkyl group, substituted C6-C30 aryl group, substituted C3-C30 heteroaryl group, substituted C4-C30 heteroaralkyl group, substituted C3-C30 cycloalkyl group, substituted C3-C30 heterocycloalkyl group, substituted C3-C30 cycloalkenyl group, substituted C1-C30 alkoxy group, substituted C6-C30 aryloxy group, substituted C6-C30 aromatic ring, substituted C3-C30 heteroaromatic ring are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl group, C3-C30 cycloalkyl group, C5-C12 aromatic group, C3-C12 heteroaromatic group.

[0048] Preferably, L2 is selected from a single bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, a substituted or unsubstituted terphenylene, a substituted or unsubstituted naphthylene;

[0049] The substituents of the substituted phenylene, substituted biphenylene, substituted terphenylene and substituted naphthylene are selected from one or a combination of two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C5-C12 aryl and C3-C12 heteroaryl.

[0050] Preferably, the formula c is selected from any one of the following c-1, c-2, c-3, c-4, c-5, c-6 and c-7,

[0051]

[0052]

[0053] Among them, R T1 -R T8 are each independently selected from hydrogen, deuterium, tritium, and substituted or unsubstituted D groups,

[0054] Wherein the D group is selected from one of the following groups:

[0055] methyl, ethyl, tert-butyl, adamantyl, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracenyl, triphenylene, phenylnaphthyl, naphthylphenyl, pyridyl, bipyridyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, benzonaphthothiophenyl, dinaphthofuranyl, dinaphthothiophenyl, dibenzofuranylphenyl, dibenzothiophenylphenyl, dimethylfluorenyl, benzodimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, and dimethylfluorenylphenyl;

[0056] The substituent of the substituted D group is selected from one or a combination of two of hydrogen, deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C5-C12 aryl, and C3-C12 heteroaryl.

[0057] Preferably, R 1 -R 12 One of them has any one of the structures of formula c-1, c-2, c-3, c-4, c-5, c-6 and c-7, and the others are hydrogen;

[0058] L2 is selected from phenylene, biphenylene, and naphthylene.

[0059] Preferably, R 1 -R 12 One of them has the structure of formula c-4, and the other is hydrogen;

[0060] Among them, R T1 , R T2 , R T7 , R T8 All are hydrogen;

[0061] L2 is selected from phenylene and naphthylene.

[0062] Preferably, R 13 , R 14 Each is independently selected from deuterium and C1-C6 alkyl.

[0063] Preferably, R 13 , R 14 Each is independently selected from deuterium, methyl and ethyl.

[0064] Preferably, the triptycene derivative is selected from the following:

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074] Where D stands for deuterium.

[0075] The present invention provides an organic electroluminescent device, which comprises a cathode, an anode and an organic layer located between the cathode and the anode, wherein the organic layer comprises the above-mentioned triptycene derivative.

[0076] Preferably, the organic layer comprises a hole transport layer, and the hole transport layer comprises the triptycene derivative described above.

[0077] Preferably, the organic layer comprises an electron blocking layer and / or an exciton blocking layer, and the electron blocking layer and / or the exciton blocking layer comprises the above-mentioned triptycene derivative.

[0078] Preferably, the organic layer comprises a light-emitting layer, and the material of the light-emitting layer comprises a host material and a guest material; the host material comprises the organic electroluminescent composition described above.

[0079] Preferably, the organic layer comprises a light-emitting layer, and the light-emitting layer comprises the triptycene derivative described above.

[0080] The present invention also provides the use of the above-mentioned triptycene derivative in the preparation of optical devices.

[0081] The organic electroluminescent device is an organic light emitting diode.

[0082] In an embodiment of an organic electroluminescent device of the present invention, the first electrode of the organic electroluminescent device is an anode, the second electrode is a cathode, the organic layer is composed of a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer stacked in sequence, and the organic electroluminescent device also includes a substrate, which is located on the surface of the anode facing away from the cathode.

[0083] Optionally, an electron blocking layer is further included between the hole transport layer and the light-emitting layer.

[0084] In the present invention, the synthesis route of any of the above-mentioned triptycene derivatives includes the following method:

[0085] 1. When n = 0,

[0086] (1) Compound Nn-A reacts with compound Nn-B to obtain intermediate Nn-1:

[0087]

[0088] Wherein Hal represents halogen;

[0089] (2) Compound Nn-1 reacts with diarylamine Nn-C to obtain compound Nn:

[0090]

[0091] 2. When n is not 0 and L1 is not a connecting key,

[0092] (1) Compound Nn-1 reacts with bipyralidone to obtain intermediate Nn-2:

[0093]

[0094] Bpin is pinacol borate.

[0095] (2) Compound Nn-2 reacts with aromatic amine Nn-D to obtain compound Nn:

[0096]

[0097] Hal 1 Represents halogen.

[0098] Beneficial effects of the present invention:

[0099] The triptycene derivative provided by the present invention is based on the structure of Formula 1, and further defines R 1 -R 14 The structure in the invention is that the triptycene derivative can effectively transport electrons or holes, block electrons or holes, and has good thermal stability. Therefore, by further modifying the triptycene mother core structure, the triptycene derivative is used as a hole transport layer material and an electron blocking layer material, so that the organic electroluminescent device has a lower driving voltage, a higher luminous efficiency and a longer life. BRIEF DESCRIPTION OF THE DRAWINGS

[0100] In order to more clearly illustrate the specific implementation methods of the present invention or the technical solutions in the prior art, the drawings required for use in the specific implementation methods or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are some implementation methods of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0101] Figure 1 A structural diagram of an organic electroluminescent device in an embodiment of the device of the present invention;

[0102] 1-substrate; 2-anode; 3-hole injection layer; 4-hole transport layer; 5-electron blocking layer; 6-light-emitting layer; 7-electron transport layer; 8-electron injection layer; 9-cathode. DETAILED DESCRIPTION

[0103] The following examples are provided for a better understanding of the present invention, but are not intended to limit the best mode of implementation, nor to limit the content and protection scope of the present invention. Any product identical or similar to the present invention obtained by anyone under the inspiration of the present invention or by combining the features of the present invention with other prior arts shall fall within the protection scope of the present invention.

[0104] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in the field can be used. If no manufacturer is specified for the reagents or instruments used, they are all conventional reagent products that can be obtained commercially.

[0105] The term "organic electroluminescent material" in the present disclosure means a material that can be used in an organic electroluminescent device and can contain at least one compound. If necessary, the organic electroluminescent material can be contained in any layer constituting the organic electroluminescent device. For example, the organic electroluminescent material can be a hole injection material, a hole transport material, a hole auxiliary material, a luminescence auxiliary material, an electron blocking material, a luminescent material (containing a host material and a dopant material), an electron buffer material, a hole blocking material, an electron transport material, an electron injection material, etc.

[0106] The term "multiple organic electroluminescent materials" in the present disclosure means one or more organic electroluminescent materials comprising a combination of at least two compounds, which may be included in any layer constituting an organic electroluminescent device. It may mean both the material contained in the organic electroluminescent device before (e.g., before vapor deposition) and the material contained in the organic electroluminescent device after (e.g., after vapor deposition). For example, a variety of organic electroluminescent materials may be a combination of at least two compounds, which may be included in at least one of the following: a hole injection layer, a hole transport layer, a hole auxiliary layer, a luminescent auxiliary layer, an electron blocking layer, a luminescent layer, an electron buffer layer, a hole blocking layer, an electron transport layer, and an electron injection layer. At least two compounds may be contained in the same layer or in different layers, and may be mixed-evaporated or co-evaporated, or may be evaporated individually.

[0107] Example 1

[0108] This embodiment provides a triptycene derivative N-1, and the preparation method of the triptycene derivative N-1 specifically comprises the following steps:

[0109]

[0110] Synthesis of N1-1: Take a 1-liter four-mouth round-bottom flask and put in a stirrer and a reflux tube. After drying, fill with nitrogen. Take 10g N1-A (48.4mmol, CAS: 781-43-1) and add it to the flask. Dissolve it with 168mL of anhydrous dichloromethane (DCM) and heat it to reflux. Dissolve 20.9g N1-B (96.9mmol, CAS: 20776-48-1) in 140mL of anhydrous tetrahydrofuran (THF) to prepare N1-B (THF) solution, and dissolve 14.2g of isoamyl nitrite in 126mL of anhydrous DCE to prepare isoamyl nitrite / DCE solution. Add N1-B / THF and isoamyl nitrite / DCE solution dropwise at the same time, and keep the content of isoamyl nitrite in the system always greater than the content of N1-B in the system. The dropping time is controlled to about 4h. After the addition was completed, the mixture was stirred and reacted for 12 hours under reflux. The target product, compound N1-1 (7 g, yield: 42%), was obtained by purification by column chromatography.

[0111] Synthesis of N-1: 7 g of the above-obtained compound N1-1 (19.33 mmol), 3.43 g of compound N1-C (20.3 mmol, CAS: 122-39-4), 354 mg of Pd2(dba)3 (0.386 mmol) (dba is distyryl acetone), 396 mg of S-Phos (0.966 mmol) (S-Phos is 2-dicyclohexylphosphine-2', 6'-dimethoxybiphenyl), 7.4 g of t-BuONa (38.6 mmol) were added to a 500 mL four-necked flask, 70 mL of toluene was added thereto, and the mixture was stirred at 110° C. for 5 hours. After the reaction was completed, the obtained solid was purified by column chromatography to obtain compound N-1 (6 g, yield: 70%).

[0112] Elemental analysis: C 34 H 27 N theoretical value: C, 90.83; H, 6.05; N, 3.12; found value: C, 90.80; H, 6.06; N, 3.14; HRMS (ESI) m / z [M+H] +: theoretical value: 449.21; found value: 450.59.

[0113] Example 2

[0114] This embodiment provides a triptycene derivative N-37, and the preparation method of the triptycene derivative N-37 specifically comprises the following steps:

[0115]

[0116] Synthesis of N37-C: 7 g of compound N37-A (21 mmol, CAS: 1268519-74-9), 5.45 g of compound N37-B (20 mmol, CAS: 28320-31-2), 354 mg of Pd2(dba)3 (0.386 mmol), 396 mg of S-Phos (0.966 mmol), 7.4 g of t-BuONa (386.44 mmol) were added to a 500 mL four-necked flask, 70 mL of toluene was added thereto, and the mixture was stirred at 110° C. for 5 hours. After the reaction was completed, the solid was purified by column chromatography to obtain compound N37-C (9 g, yield: 81.8%).

[0117] Synthesis of N-37: 9 g of the compound N37-C (17 mmol) obtained above, 6.17 g of the compound N1-1 (17.1 mmol), 269 mg of Pd2(dba)3 (0.29 mmol), 301 mg of S-Phos (0.734 mmol), and 2.82 g of t-BuONa (29.36 mmol) were added to a 500 mL four-necked flask, 90 mL of toluene was added thereto, and the mixture was stirred at 110° C. for 5 hours. After the reaction was completed, the solid obtained was purified by column chromatography to obtain compound N-37 (10 g, yield: 72%).

[0118] Elemental analysis: C 62 H 47 N theoretical value: C, 92.38; H, 5.88; N, 1.74; found value: C, 92.35; H, 5.87; N, 1.78; HRMS (ESI) m / z [M+H]+: theoretical value: 805.37; found value: 806.15.

[0119] Example 3

[0120] This embodiment provides a triptycene derivative N-71, and the preparation method of the triptycene derivative N-71 specifically comprises the following steps:

[0121]

[0122] Synthesis of N71-1: Take a 1-liter four-mouth round-bottom flask and put in a stirrer and a reflux tube. After drying, fill with nitrogen. Take 10gN1-A (48.4mmol, CAS: 781-43-1) and add it to the flask. Dissolve it with 168mL of anhydrous DCM and heat it to reflux. Dissolve 20.9g N71-B (96.9mmol, CAS: 5794-88-7) in 140mL of anhydrous THF to prepare N71-B / THF solution, and dissolve 14.2g of isoamyl nitrite in 126mL of anhydrous DCE to prepare isoamyl nitrite / DCE solution. Add N71-B / THF and isoamyl nitrite / DCE solution dropwise at the same time, and keep the content of isoamyl nitrite in the system always greater than the content of N71-B in the system. The addition time is controlled to be about 4h. After the addition is completed, stir the reaction under reflux for 12h. Purification by column chromatography gave the target product, compound N71-1 (7 g, yield: 42%).

[0123] Synthesis of N-71: 7 g of the above-obtained compound N71-1 (19.33 mmol), 3.43 g of compound N1-C (20.3 mmol, CAS: 122-39-4), 354 mg of Pd2(dba)3 (0.386 mmol), 396 mg of S-Phos (0.966 mmol), and 7.4 g of t-BuONa (38.6 mmol) were added to a 500 mL four-necked flask, 70 mL of toluene was added thereto, and the mixture was stirred at 110° C. for 5 hours. After the reaction was completed, the obtained solid was purified by column chromatography to obtain compound N-71 (6 g, yield: 70%).

[0124] Elemental analysis: C 34 H 27 N theoretical value: C, 90.83; H, 6.05; N, 3.12; found value: C, 90.81; H, 6.05; N, 3.14; HRMS (ESI) m / z [M+H]+: theoretical value: 449.21; found value: 449.07.

[0125] Example 4

[0126] This embodiment provides a triptycene derivative N-141, and the preparation method of the triptycene derivative N-141 specifically comprises the following steps:

[0127]

[0128] Synthesis of N141-b: Take a 1-liter four-necked round-bottom flask and put in a stirrer and a reflux tube. After drying, fill it with nitrogen. Take 10g N141-a (48.07mmol, CAS: 84-65-1) and add it to the flask. Cool it to -70~-80℃, and drop 144mL ethyl lithium (144.23mmol, 1.0mol / L in Diethyl ether) into the system. After 2h of dropwise addition, pour the system into 1L ammonium chloride aqueous solution, extract, and purify it by column chromatography to obtain the target product, compound N141-b (10g, yield: 78%);

[0129] Synthesis of N141-A: Add 10g N141-b (37.3mmol) obtained above into a 250mL four-necked round-bottom flask, fill with nitrogen after drying, cool the system to 0°C, and simultaneously add 15.6g triethylsilane (134.32mmol, CAS: 617-86-7) and 42.8g boron trifluoride ether solution (141.79mmol, 47%, CAS: 109-63-7) dropwise. Add after 2h, transfer to room temperature and stir to react for 2h. After the reaction is completed, add 100mL water to quench the reaction, extract, and purify by column chromatography to obtain the target product, compound N141-A (6g, yield: 69%);

[0130] Synthesis of N141-1: Take a 1-liter four-mouth round-bottom flask and put it in a stirrer and a reflux tube. After drying, fill it with nitrogen. Take 6g N141-A (25.6mmol) and add it to the flask. Dissolve it with 100mL of anhydrous DCM and heat it to reflux. Dissolve 11.08g N1-B (51.28mmol, CAS: 20776-48-1) in 84mL of anhydrous THF to prepare N1-B / THF solution, and dissolve 7.5g of isoamyl nitrite (64.1mmol, CAS: 110-46-3) in 76mL of anhydrous DCE to prepare isoamyl nitrite / DCE solution. Add N1-B / THF and isoamyl nitrite / DCE solution dropwise at the same time, and keep the content of isoamyl nitrite in the system always greater than the content of N1-B in the system. The addition time is controlled to be about 4h. After the addition is completed, stir the reaction under reflux for 12h. Purification by column chromatography gave the target product, compound N141-1 (6 g, yield: 60%).

[0131] Synthesis of N-141: 6 g of compound N141-1 (15.42 mmol), 3.98 g of compound N141-C (16.24 mmol, CAS: 32228-99-2), 282 mg of Pd2(dba)3 (0.308 mmol), 316 mg of S-Phos (0.77 mmol), and 2.96 g of t-BuONa (30.8 mmol) were added to a 250 mL four-necked flask, 60 mL of toluene was added thereto, and the mixture was stirred at 110° C. for 3 hours. After the reaction was completed, the solid was purified by column chromatography to obtain compound N-141 (6 g, yield: 71%).

[0132] Elemental analysis: C 42 H 35 N theoretical value: C, 91.10; H, 6.37; N, 2.53; found value: C, 91.05; H, 6.39; N, 2.56; HRMS (ESI) m / z [M+H] +: theoretical value: 553.28; found value: 554.17.

[0133] Example 5

[0134] This embodiment provides a triptycene derivative N-178, and the preparation method of the triptycene derivative N-178 specifically comprises the following steps:

[0135]

[0136] Synthesis of N178-D: Take a 250mL four-necked round-bottom flask and put a stirrer and a reflux tube on it, fill it with nitrogen after drying, take 10g N178-a (37.5mmol, CAS: 194-59-2) and add it to the flask, 6.76g compound N178-b (39.33mmol, CAS: 106-40-1), 685mg Pd2(dba)3 (0.75mmol), 614mg S-Phos (1.50mmol), 7.34g t-BuONa (74.9mmol) and add it to a 250mL four-necked flask, measure 100mL toluene and add it thereto, and stir the mixture at 110°C for 4 hours. After the reaction is completed, the solid obtained is purified by column chromatography to obtain compound N178-D (12g, yield: 76%).

[0137]

[0138] Synthesis of N178-2: To a 250mL three-necked flask equipped with a thermometer and a magnetic stirrer, 7g of compound N141-1 (19.4mmol), 5.9g of bis-pinacol borate (23.3mmol, CAS: 73183-34-3), 3.8g of potassium acetate (38.8mmol) and 282mg of Pd(dppf)Cl2 (0.39mmol) were added, and 70mL of 1,4-dioxane was added. Under nitrogen protection, the temperature was raised to 110°C and the reaction was reacted for 4h. 100mL of toluene was added to the reaction solution, and 100mL of water was used for extraction and separation. The organic phase was mixed and passed through a column to obtain the intermediate N178-2 (6g, yield: 76%).

[0139]

[0140] Synthesis of N-178: 6.2g of compound N178-D (14.69mmol), 6g of compound N178-2 (14.69mmol), 4.05g of K2CO3 (29.38mmol), 339mg of Pd(PPh3)4 (0.294mmol) were added to a 250mL three-necked flask equipped with a thermometer and magnetic stirring, and 45mL of toluene, 20mL of ethanol and 20mL of water were added. Under nitrogen protection, the temperature was raised to 85°C for 4h. After the reaction was completed, the product N-178 (6g, yield: 66%) was obtained by purification by column chromatography and drying.

[0141] Elemental analysis: C 50 H 37 N theoretical value: C, 92.13; H, 5.72; N, 2.15; found value: C, 92.10; H, 5.73; N, 2.17; HRMS (ESI) m / z [M+H] +: theoretical value: 651.29; found value: 652.58.

[0142] Example 6

[0143] This embodiment provides a triptycene derivative N-227, and the preparation method of the triptycene derivative N-227 specifically comprises the following steps:

[0144]

[0145] Synthesis of N227-b: Take a 250mL four-necked round-bottom flask and put it in a stirring bar and a reflux tube. After drying, fill it with nitrogen. At room temperature, take 10g N227-a (55.48mmol, CAS: 613-31-0) and add it to the flask. Dissolve it with 20mL deuterated dimethyl sulfoxide ((99.9% atom D, CAS: 2206-27-1), add 4.48g potassium hydride (0.1122mol), and the reaction mixture turns dark red. After stirring and reacting for 2h, 16mL of heavy water (99.9% atom D, CAS: 7789-20-0) is added to the system, and a white precipitate appears immediately. Stir the reaction for another 1h, filter to obtain 8g of the product, rinse with water, and then recrystallize and purify it with ethanol to obtain the target product N227-b (7g, yield: 73%).

[0146] Synthesis of N227-A: 7 g of N227-b (38.04 mmol) obtained above was added to a 250 mL four-necked round-bottom flask, 37 g of 3,4,5,6-tetrachloro-1,2-benzoquinone (0.152 mol, CAS: 2435-53-2) was added, 70 mL of 1,4-dioxane was added to the system, and heated to 30°C for 48 h. After the reaction was completed, the target product, compound N227-A (6 g, yield: 88%) was obtained by purification by column chromatography.

[0147] Synthesis of N227-1: Take a 1-liter four-mouth round-bottom flask and put it in a stirrer and a reflux tube. After drying, fill it with nitrogen. Take 6g N227-A (33.3mmol) and add it to the flask. Dissolve it with 100mL of anhydrous DCM and heat it to reflux. Dissolve 14.4g N1-B (66.6mmol, CAS: 20776-48-1) in 84mL of anhydrous THF to prepare N1-B / THF solution, and dissolve 9.75g of isoamyl nitrite (83.3mmol, CAS: 110-46-3) in 76mL of anhydrous DCE to prepare isoamyl nitrite / DCE solution. Add N1-B / THF and isoamyl nitrite / DCE solution dropwise at the same time, and keep the content of isoamyl nitrite in the system always greater than the content of N1-B in the system. The dropping time is controlled at about 4h. After the dropwise addition is completed, stir the reaction under reflux for 12h. Purification by column chromatography gave the target product, compound N227-1 (7 g, yield: 63%).

[0148] Synthesis of N-227: 7 g of the compound N227-1 (20.9 mmol), 3.7 g of the compound N1-C (21.9 mmol, CAS: 122-39-4), 382 mg of Pd2(dba)3 (0.418 mmol), 428 mg of S-Phos (1.04 mmol), and 4.01 g of t-BuONa (41.79 mmol) were added to a 250 mL four-necked flask, 70 mL of toluene was added thereto, and the mixture was stirred at 110° C. for 5 hours. After the reaction was completed, the solid was purified by column chromatography to obtain compound N-227 (6.6 g, yield: 75%).

[0149] Elemental analysis: C 32 H 21 D2N theoretical value: C, 90.74; H, 5.95; N, 3.31; found value: C, 90.71; H, 5.96; N, 3.33; HRMS (ESI) m / z [M+H]+: theoretical value: 423.20; found value: 424.54.

[0150] Example 7

[0151] This embodiment provides a triptycene derivative N-277, and the preparation method of the triptycene derivative N-277 specifically includes the following steps:

[0152]

[0153] Synthesis of N277-c: Take a 250mL four-necked round-bottom flask and put a stirring rod and a reflux tube on it, fill it with nitrogen after drying, take 10g N277-a (37.5mmol, CAS: 194-59-2) and add it to the flask, 6.76g compound N277-b (39.33mmol, CAS: 106-40-1), 685mg Pd2(dba)3 (0.75mmol), 614mg S-Phos (1.50mmol), 7.34g t-BuONa (74.9mmol) and add it to a 250mL four-necked flask, measure 100mL toluene and add it, and stir the mixture at 110°C for 4 hours. After the reaction is completed, the solid obtained is purified by column chromatography to obtain compound N277-c (12g, yield: 76%).

[0154] Synthesis of N277-C: 12 g of the compound N277-c (28.44 mmol) obtained above, 2.78 g of aniline (29.86 mmol, CAS: 62-53-3), 520 mg of Pd2(dba)3 (0.569 mmol), 466 mg of S-Phos (11.37 mmol), 5.57 gt-BuONa (56.87 mmol) were added to a 250 mL four-necked flask, 120 mL of toluene was added thereto, and the mixture was stirred at 110° C. for 3 hours. After the reaction was completed, the solid obtained was purified by column chromatography to obtain compound N277-C (9 g, yield: 75%).

[0155] Synthesis of N-277: Take a 250mL four-necked round-bottom flask and put in a stirrer and a reflux tube, fill with nitrogen after drying, take 9g N277-C (20.74mmol) and add it to the flask, 7.84g compound N1-1 (21.77mmol), 379mg Pd2(dba)3 (0.415mmol), 340g S-Phos (0.829mmol), 4.06g t-BuONa (41.5mmol) and add it to a 250mL four-necked flask, add 90mL xylene, and stir the mixture at 140°C for 4 hours. After the reaction is completed, cool and filter to obtain the target product, and then slurry with ethanol to obtain compound N-277 (11g, yield: 74%).

[0156] Elemental analysis: C 54 H 38 N2 theoretical value: C, 90.72; H, 5.36; N, 3.92; found value: C, 90.68; H, 5.38; N, 3.94; HRMS (ESI) m / z [M+H]+: theoretical value: 714.30; found value: 715.44.

[0157] Example 8

[0158] This embodiment provides a triptycene derivative N-278, and the preparation method of the triptycene derivative N-278 specifically includes the following steps:

[0159]

[0160] Synthesis of N278-b: Take a 250mL four-necked round-bottom flask and put it in a stirring bar and a reflux tube. After drying, fill it with nitrogen. At room temperature, take 10g N278-a (55.48mmol, CAS: 613-31-0) and add it to the flask. Dissolve it with 20mL deuterated dimethyl sulfoxide ((99.9% atom D, CAS: 2206-27-1), add 4.48g potassium hydride (0.1122mol), and the reaction mixture turns dark red. After stirring and reacting for 2h, 16mL of heavy water (99.9% atom D, CAS: 7789-20-0) is added to the system, and a white precipitate appears immediately. Stir the reaction for another 1h, filter to obtain 8g of the product, rinse with water, and then recrystallize and purify it with ethanol to obtain the target product N278-b (7g, yield: 73%).

[0161] Synthesis of N278-A: 7 g of N278-b (38.04 mmol) obtained above was added to a 250 mL four-necked round-bottom flask, 37 g of 3,4,5,6-tetrachloro-1,2-benzoquinone (0.152 mol, CAS: 2435-53-2) was added, 70 mL of 1,4-dioxane was added to the system, and the mixture was heated to 30°C and reacted for 48 hours. After the reaction was completed, the target product, compound N278-A (6 g, yield: 88%) was obtained by purification by column chromatography.

[0162] Synthesis of N278-1: Take 1 liter of four-mouth round-bottom flask and put in a stirrer and a reflux tube, fill with nitrogen after drying, take 6g N278-A (33.3mmol) and add it to the flask, dissolve it with 100mL of anhydrous DCM, and heat it to reflux. 14.4g N71-B (66.6mmol, CAS: 20776-48-1) is dissolved in 84mL of anhydrous THF to prepare N71-B / THF solution, 9.75g isoamyl nitrite (83.3mmol, CAS: 110-46-3) is dissolved in 76mL of anhydrous DCE to prepare isoamyl nitrite / DCE solution. N71-B / THF and isoamyl nitrite / DCE solution are added dropwise at the same time, and the content of isoamyl nitrite in the system is always greater than the content of N71-B in the system. The addition time is controlled to be about 4h. After the addition was completed, the mixture was stirred and reacted for 12 hours under reflux. The target product, compound N278-1 (7.5 g, yield: 68%), was obtained by purification by column chromatography.

[0163] Synthesis of N-278: 7.5 g of compound N278-1 (22.38 mmol), 3.97 g of compound N1-C (23.5 mmol, CAS: 122-39-4), 410 mg of Pd2(dba)3 (0.447 mmol), 459 mg of S-Phos (1.12 mmol), and 4.3 g of t-BuONa (44.78 mmol) were added to a 250 mL four-necked flask, 75 mL of xylene was added thereto, and the mixture was stirred at 110° C. for 5 hours. After the reaction was completed, the solid was purified by column chromatography to obtain compound N-278 (8 g, yield: 84%).

[0164] Elemental analysis: C 32 H 21 D2N theoretical value: C, 90.74; H, 5.95; N, 3.31; found value: C, 90.72; H, 5.95; N, 3.33; HRMS (ESI) m / z [M+H]+: theoretical value: 423.20; found value: 424.16.

[0165] Example 9

[0166] This embodiment provides a triptycene derivative N-308, and the preparation method of the triptycene derivative N-308 specifically comprises the following steps:

[0167]

[0168] Synthesis of N308-2: To a 250mL three-necked flask equipped with a thermometer and a magnetic stirrer, 7g of compound N71-1 (19.4mmol), 5.9g of bispinacol borate (23.3mmol, CAS: 73183-34-3), 3.8g of potassium acetate (38.8mmol) and 282mg of Pd(dppf)Cl2 (0.39mmol) were added, and 70mL of 1,4-dioxane was added. Under nitrogen protection, the temperature was raised to 110°C and the reaction was reacted for 4h. 100mL of toluene was added to the reaction solution, and 100mL of water was used for extraction and separation. The organic phase was mixed and passed through a column to obtain the intermediate N308-2 (6g, yield: 76%).

[0169] Synthesis of N-308: Add 6g of compound N308-2 (14.7mmol), 5.0g of compound N308-D (15.4mmol, CAS: 36809-26-4), 4.06g of K2CO3 (29.4mmol), and 340mg of Pd(PPh3)4 (0.294mmol) obtained above into a 250mL four-necked flask, add 50mL of toluene, 20mL of ethanol and 20mL of water, and heat to 85℃ for 6h under nitrogen protection. After the reaction is completed, 50mL of water and 50mL of toluene are added in turn, and the organic phase is mixed and passed through a column to obtain the final product N-308 (5.6g, yield: 73%).

[0170] Elemental analysis: C 40 H 31 N theoretical value: C, 91.39; H, 5.94; N, 2.66; found value: C, 91.36; H, 5.93; N, 2.71; HRMS (ESI) m / z [M+H] +: theoretical value: 525.25; found value: 525.11.

[0171] Example 10

[0172] This embodiment provides a triptycene derivative N-315, and the preparation method of the triptycene derivative N-315 specifically comprises the following steps:

[0173]

[0174] Synthesis of N315-D: 8 g of compound N315-a (24.6 mmol, CAS: 101606-18-2), 6.9 g of compound N315-b (29.6 mmol, CAS: 2052-07-5), 214 mg of Pd2(dba)3 (0.233 mmol), 192 mg of S-Phos (0.48 mmol), and 2.3 g of t-BuONa (23.4 mmol) were added to a 250 mL four-necked flask, 80 mL of toluene was added thereto, and the mixture was stirred at 110° C. for 3 hours. After the reaction was completed, the obtained solid was purified by column chromatography to obtain compound N315-D (9.5 g, yield: 82%).

[0175] Synthesis of N-315: 9g of the above-obtained compound N315-D (18.9mmol), 8.5g of the compound N308-2 (20.8mmol), 4.06g of K2CO3 (29.4mmol), and 340mg of Pd(PPh3)4 (0.294mmol) were added to a 250mL four-necked flask, and 50mL of toluene, 20mL of ethanol, and 20mL of water were added. Under nitrogen protection, the temperature was raised to 85°C for 4h. After the reaction was completed, the solid was purified by column chromatography to obtain compound N-315 (9g, yield: 70%).

[0176] Elemental analysis: C 52 H 39 N theoretical value: C, 92.13; H, 5.80; N, 2.07; found value: C, 92.10; H, 5.79; N, 2.11; HRMS (ESI) m / z [M+H] +: theoretical value: 677.31; found value: 678.23.

[0177] Embodiment 11

[0178] This embodiment provides a triptycene derivative N-322, and the preparation method of the triptycene derivative N-322 specifically includes the following steps:

[0179]

[0180] Synthesis of N322-D: Take a 250mL four-necked round-bottom flask and put a stirring bar and a reflux tube on it, fill it with nitrogen after drying, take 10g N322-a (35.0mmol, CAS: 13720-06-4) and add it to the flask, 9g compound N322-b (36.7mmol, CAS: 32228-99-2), 640mg Pd2(dba)3 (0.699mmol), 573mg S-Phos (1.40mmol), 6.85g t-BuONa (69.9mmol) and add it to a 250mL four-necked flask, measure 100mL toluene and add it thereto, and stir the mixture at 110°C for 4 hours. After the reaction is completed, the solid obtained is purified by column chromatography to obtain compound N322-D (12g, yield: 76%).

[0181] Synthesis of N-322: 12g of compound N322-D (26.6mmol), 10.88g of compound N308-2 (26.67mmol), 7.36g of K2CO3 (53.3mmol), 616mg of Pd(PPh3)4 (0.533mmol) were added to a 250mL three-necked flask equipped with a thermometer and magnetic stirring, and 85mL of toluene, 35mL of ethanol and 35mL of water were added. Under nitrogen protection, the temperature was raised to 85°C for 4h. After the reaction was completed, the product N-322 (12g, yield: 70%) was obtained by purification by column chromatography and drying.

[0182] Elemental analysis: C 50 H 37 N theoretical value: C, 92.13; H, 5.72; N, 2.15; found value: C, 92.10; H, 5.73; N, 2.17; HRMS (ESI) m / z [M+H] +: theoretical value: 651.29; found value: 652.38.

[0183] The preparation methods of Examples 12-21 are similar to those of Example 1. Specifically, the raw materials used in Examples 12-21 and the products obtained are shown in Table 1 below.

[0184] Table 1

[0185]

[0186]

[0187]

[0188] The characterization data of the products prepared in Examples 12-21 are shown in Table 2:

[0189] Table 2

[0190]

[0191]

[0192] Device Example 1

[0193] This embodiment provides an organic electroluminescent device, such as Figure 1As shown, it includes an anode 2, a hole injection layer 3, a hole transport layer 4, an electron blocking layer 5, a light-emitting layer 6, an electron transport layer 7, an electron injection layer 8 and a cathode 9 which are sequentially stacked on a substrate 1, and its device structure is: substrate + anode (indium tin oxide (ITO) coated glass substrate) / hole injection layer (HIL) / hole transport layer (HTL) / electron blocking layer (EBL) / light-emitting layer (EML) / electron transport layer (ETL) / electron injection layer (EIL) / cathode (Al).

[0194] The materials used to manufacture the organic electroluminescent device are as follows:

[0195]

[0196]

[0197] The preparation of the organic electroluminescent device comprises the following steps:

[0198] 1) Substrate cleaning:

[0199] The glass substrate coated with transparent ITO is ultrasonically treated in an aqueous cleaning agent (the composition and concentration of the aqueous cleaning agent: ethylene glycol solvent ≤ 10wt%, triethanolamine ≤ 1wt%), then rinsed in deionized water, ultrasonically degreased in a mixed solvent of acetone and ethanol (the volume ratio of acetone to ethanol is 1:1), baked in a clean environment until the moisture is completely removed, and then cleaned with ultraviolet light and ozone.

[0200] 2) Preparation of organic layer:

[0201] Transfer the ITO transparent substrate to the evaporation equipment and evacuate to 1×10 -6 Up to 2×10 -4 Pa, 10nm hole injection layer (HIL) / 60nm hole transport layer (HTL) / 80nm electron blocking layer (EBL) / 25nm light emitting layer (EML) / 30nm electron transport layer (ETL) / 1nm electron injection layer (EIL) / 80nm thick cathode (Al) are evaporated on the anode in sequence.

[0202] in:

[0203] The material of the hole injection layer (HIL) is a mixture of NDP-9 and HT, wherein the mass ratio of NDP-9 to HT is 3:97; the evaporation is carried out by co-evaporation, and the total evaporation rate is 0.1 nm / s;

[0204] The material of the hole transport layer (HTL) is HT;

[0205] The electron blocking layer (EBL) material is the triptycene derivative N-1 in the present invention;

[0206] The material of the light-emitting layer (EML) includes a host material and a guest material, wherein the host material is CBP and the guest material is (piq)2Ir(acac); the mass ratio of the host material to the guest material is 95:5, and the evaporation is carried out by co-evaporation, and the total evaporation rate is 0.1 nm / s;

[0207] The material of the electron transport layer (ETL) is a mixture of ET-1 and LiQ, the mass ratio of ET-1 to LiQ is 1:1, and the evaporation is carried out by co-evaporation, and the total evaporation rate is 0.1nm / s;

[0208] The material of the electron injection layer (EIL) is LiQ;

[0209] The thickness and material of each layer are shown in Table 3.

[0210] Device Examples 2-14

[0211] The preparation method of device examples 2-14 is similar to that of device example 1, except that N-37, N-71, N-141, N-178, N-198, N-218, N-227, N-253, N-277, N-278, N-308, N-315 and N-322 are used instead of N-1 as the material of the electron blocking layer (EBL). The thickness and material of each layer are shown in Table 3.

[0212] Device Comparison Examples 1, 2, and 4

[0213] The preparation methods of device comparative examples 1, 2, and 4 are similar to those of device embodiment 1, except that REF-1, REF-2, and REF-3 are used instead of N-1 as the materials of the electron blocking layer (EBL). The thickness and materials of each layer are shown in Table 3.

[0214] Device Comparison Example 3

[0215] The present comparative example provides an organic electroluminescent device, comprising an anode, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode which are sequentially stacked on a substrate, and the device structure is: substrate + anode (indium tin oxide (ITO) coated glass substrate) / hole injection layer (HIL) / hole transport layer (HTL) / light-emitting layer (EML) / electron transport layer (ETL) / electron injection layer (EIL) / cathode (Al).

[0216] The names and structures of the materials used to manufacture the organic electroluminescent device are the same as those in Device Example 1;

[0217] The preparation of the organic electroluminescent device comprises the following steps:

[0218] 1) Substrate cleaning: the same as the corresponding steps in device embodiment 1;

[0219] 2) Preparation of organic layer:

[0220] Transfer the ITO transparent substrate to the evaporation equipment and evacuate to 1×10 -6 Up to 2×10 -4 Pa, 10nm hole injection layer (HIL) / 80nm hole transport layer (HTL) / 25nm light emitting layer (EML) / 30nm electron transport layer (ETL) / 1nm electron injection layer (EIL) / 80nm thick cathode (Al) are deposited on the anode film in sequence.

[0221] in:

[0222] The material of the hole injection layer (HIL) is a mixture of NDP-9 and HT, wherein the mass ratio of NDP-9 to HT is 3:97; the evaporation is carried out by co-evaporation, and the total evaporation rate is 0.1 nm / s;

[0223] The material of the hole transport layer (HTL) is HT;

[0224] The material of the light-emitting layer (EML) includes a host material and a guest material, wherein the host material is CBP and the guest material is (piq)2Ir(acac); the mass ratio of the host material to the guest material is 95:5, and the evaporation is carried out by co-evaporation, and the total evaporation rate is 0.1 nm / s;

[0225] The material of the electron transport layer (ETL) is a mixture of ET-1 and LiQ, the mass ratio of ET-1 to LiQ is 1:1, and the evaporation is carried out by co-evaporation, and the total evaporation rate is 0.1nm / s;

[0226] The material of the electron injection layer (EIL) is LiQ;

[0227] The thickness and material of each layer are shown in Table 3.

[0228] Some layers, materials and thicknesses of device examples 1-14 and device comparative examples 1-4 are shown in Table 3.

[0229] Table 3

[0230]

[0231]

[0232]

[0233] The examples in Table 3 refer to device examples, and the comparative examples refer to device comparative examples, wherein “ / ” means that the layer is not included.

[0234] Device Example 15

[0235] The present embodiment provides an organic electroluminescent device, including an anode, a hole injection layer, a hole transport layer, an auxiliary hole transport layer, a light-emitting layer, an electron transport layer, an electron injection layer and a cathode which are sequentially stacked on a substrate, and the device structure is: substrate + anode (indium tin oxide (ITO) coated glass substrate) / hole injection layer (HIL) / hole transport layer (HTL1) / auxiliary hole transport layer (HTL2) / light-emitting layer (EML) / electron transport layer (ETL) / electron injection layer (EIL) / cathode (Al).

[0236] The names and structures of the materials used to manufacture the organic electroluminescent device are the same as those in Device Example 1;

[0237] The preparation of the organic electroluminescent device comprises the following steps:

[0238] 1) Substrate cleaning: the same as the corresponding steps in device embodiment 1;

[0239] 2) Preparation of organic layer:

[0240] Transfer the ITO transparent substrate to the evaporation equipment and evacuate to 1×10 -6 Up to 2×10 -4 Pa, 10nm hole injection layer (HIL) / 60nm hole transport layer (HTL1) / 20nm auxiliary hole transport layer (HTL2) / 25nm light-emitting layer (EML) / 30nm electron transport layer (ETL) / 1nm electron injection layer (EIL) / 80nm thick cathode (Al) are deposited on the anode film in sequence.

[0241] in:

[0242] The material of the hole injection layer (HIL) is a mixture of NDP-9 and HT, wherein the mass ratio of NDP-9 to HT is 3:97; the evaporation is carried out by co-evaporation, and the total evaporation rate is 0.1 nm / s;

[0243] The material of the hole transport layer (HTL1) is HT;

[0244] The material of the auxiliary hole transport layer (HTL2) is N-45;

[0245] The material of the light-emitting layer (EML) includes a host material and a guest material, wherein the host material is CBP and the guest material is (piq)2Ir(acac); the mass ratio of the host material to the guest material is 95:5, and the evaporation is carried out by co-evaporation, and the total evaporation rate is 0.1 nm / s;

[0246] The material of the electron transport layer (ETL) is a mixture of ET-1 and LiQ, the mass ratio of ET-1 to LiQ is 1:1, and the evaporation is carried out by co-evaporation, and the total evaporation rate is 0.1nm / s;

[0247] The material of the electron injection layer (EIL) is LiQ.

[0248] Device Examples 16-28

[0249] The preparation methods of device embodiments 16-28 are similar to those of device embodiment 15, except that N-79, N-117, N-135, N-139, N-163, N-176, N-219, N-273, N-289, N-304, N-307, N-318 or N-326 are used instead of compound N-45 as the material of the auxiliary hole transport layer (HTL2). The thickness and materials of each layer are shown in Table 4.

[0250] Device Comparison Examples 5-6

[0251] The preparation method of device comparative examples 5-6 is similar to that of device example 15, except that REF-1 and REF-2 are used instead of compound N-45 as the materials of the auxiliary hole transport layer (HTL2). The thickness and materials of each layer are shown in Table 4.

[0252] Some layers, materials and thicknesses of device embodiments 15-28 and device comparative examples 5-6 are shown in Table 4.

[0253] Table 4

[0254]

[0255]

[0256]

[0257] The examples in Table 4 refer to device examples, and the comparative examples refer to device comparative examples.

[0258] Test Example 1

[0259] The organic electroluminescent devices obtained from device examples 1 to 28 and comparative examples 1 to 6 in the device examples were tested.

[0260] Instruments: The device's current, voltage, brightness, luminous spectrum and other characteristics are tested synchronously using a PR 650 spectrum scanning luminance meter and a Keithley K 2400 digital source meter system;

[0261] Test conditions: Photoelectric characteristics test conditions: Current density is 10mA / cm2.

[0262] Life test: The current density is 50 mA / cm2, and the time (in hours) when the device brightness drops to 95% of the original brightness is recorded.

[0263] The device performance test results are shown in Table 5-6:

[0264] Table 5

[0265] project Driving voltage(V) Current efficiency (Cd / A) Lifespan T95(hrs) Example 1 3.81 20.47 124.3 Example 2 3.94 19.94 110.8 Example 3 3.85 20.09 117.9 Example 4 3.80 20.49 125.0 Example 5 3.88 20.08 131.7 Example 6 3.77 21.74 124.8 Example 7 3.90 19.98 122.6 Example 8 3.71 21.78 129.7 Example 9 3.95 19.78 114.7 Example 10 3.86 20.03 115.8 Embodiment 11 3.82 21.00 124.9 Example 12 3.80 20.77 120.5 Example 13 3.78 21.50 129.6 Embodiment 14 3.91 20.69 126.4 Comparative Example 1 6.11 15.24 82.5 Comparative Example 2 4.91 17.90 77.8 Comparative Example 3 4.80 5.00 5.0 Comparative Example 4 4.86 16.57 88.6

[0266] The examples in Table 5 refer to device examples, and the comparative examples refer to device comparative examples.

[0267] Table 6

[0268]

[0269]

[0270] The examples in Table 6 refer to device examples, and the comparative examples refer to device comparative examples.

[0271] Device Example 29

[0272] The preparation method of device example 29 is similar to that of device example 13, except that aged N-315 is used instead of compound N-315.

[0273] The aging process of N-315 includes the following steps:

[0274] 1) Charging: Weigh 2.0 g of compound N-315 and put it into the ampoule tube so that all of it is located at the bottom of the ampoule bottle;

[0275] 2) Sealing the tube: Start the sintering equipment, put the ampoule tube containing the material into the corresponding position of the sintering equipment and tighten it; start vacuuming, and wait until the vacuum reaches 5*10 -3 After pa, close the main valve. Turn on the rotary switch, and the ampoule tube rotates at a speed of 30rpm; connect the butane gas tank and nozzle, turn the knob and ignite, adjust the firepower, and start sintering with the outer flame; wait for the center of the ampoule tube to be softened by the flame, wear gloves and pull the ampoule tube slightly down and burn it off, finally open the vacuum valve to break the vacuum to normal pressure and remove the other half of the ampoule tube.

[0276] 3) Heat resistance test: Place the sealed ampoule tube into the center of the heating furnace chamber of the thermal stabilization equipment and heat it at 360°C for 255 hours (perform the aging heating program for aging).

[0277] 4) Material collection: After stopping heating, start the cooling program. After cooling to room temperature, take out the ampoule tube, pour out the material and grind it into powder with a mortar to obtain aged N-315.

[0278] Device Comparison Example 7

[0279] The preparation method of device comparative example 7 is similar to that of device comparative example 4, except that aged REF-3 is used instead of REF-3; the aging process of REF-3 is similar to the aging process of N-315 in device example 29.

[0280] Test Example 2

[0281] The organic electroluminescent devices obtained from device example 29 and device comparative example 7 in the device examples were tested.

[0282] Instruments: The device's current, voltage, brightness, luminous spectrum and other characteristics are tested synchronously using a PR 650 spectrum scanning luminance meter and a Keithley K 2400 digital source meter system;

[0283] Test conditions: Photoelectric characteristics test conditions: Current density is 10mA / cm2.

[0284] Life test: The current density is 50 mA / cm2, and the time (in hours) when the device brightness drops to 95% of the original brightness is recorded.

[0285] The device performance test results are shown in Table 7:

[0286] Table 7

[0287] Compound Driving voltage(V) Current efficiency (Cd / A) Lifespan T95(hrs) Device Example 29 3.80 21.03 130.4 Device Comparison Example 7 4.88 15.78 7.54

[0288] Table 8 shows the test results of device Example 13 and device Comparative Example 4 corresponding to N-315 and REF-3 before aging:

[0289] Table 8

[0290] Compound Driving voltage(V) Current efficiency (Cd / A) Lifespan T95(hrs) Device Example 13 3.78 21.50 129.6 Device Comparison Example 4 4.86 16.57 88.6

[0291] By comparing the data in Table 7 and Table 8, it can be seen that the compound provided by the present invention has good stability, and its device performance does not decrease significantly after aging. It is an organic electroluminescent compound with high stability.

[0292] Obviously, the above embodiments are merely examples for the purpose of clear explanation, and are not intended to limit the implementation methods. For those skilled in the art, other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the implementation methods here. The obvious changes or modifications derived therefrom are still within the scope of protection of the invention.

Claims

1. A triptycene derivative, characterized in that: Has the following structure: Among them, R 1 -R 12 One of them has the structure shown below, and the others are independently selected from hydrogen and deuterium; n is 0 or 1; L1 is selected from a single bond, a substituted or unsubstituted C6-C30 arylene group; Ar 1 -Ar 2 Each is independently selected from a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C3-C30 heteroaryl group; The substituents in the substituted C6-C30 aryl group and the substituted C3-C30 heteroaryl group are selected from one or a combination of two of deuterium, C1-C6 alkyl group, C5-C12 aryl group and C3-C12 heteroaryl group; The substituent of the substituted C6-C30 arylene group is selected from deuterium and C5-C12 aryl groups; or, R 1 -R 12 One of them has the structure shown below, and the others are independently selected from hydrogen and deuterium; L2 is selected from a single bond, unsubstituted C6-C30 arylene group; R T1 -R T8 are each independently selected from hydrogen, deuterium, or R T1 -R T8 The two adjacent rings are connected to form ring B, and the ring B is an unsubstituted C6-C30 aromatic ring; R 13 , R 14 Each is independently selected from unsubstituted C1-C20 alkyl groups.

2. The triptycene derivative according to claim 1, characterized in that L1 is selected from a single bond, an unsubstituted phenylene group, an unsubstituted biphenylene group, an unsubstituted terphenylene group, and an unsubstituted naphthylene group.

3. The triptycene derivative according to claim 1 or 2, characterized in that: R 1 -R 12 One of them has the structure shown in Formula 2, and the other is hydrogen; L1 is selected from phenylene, biphenylene, and naphthylene.

4. The triptycene derivative according to claim 1, characterized in that Ar 1 -Ar 2 Each is independently selected from an unsubstituted C6-C30 aryl group and an unsubstituted C3-C30 heteroaryl group.

5. The triptycene derivative according to claim 1, characterized in that Ar 1 -Ar 2 Each is independently selected from the unsubstituted A group: Wherein the A group is selected from one of the following groups: Phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracenyl, triphenylene, pyrenyl, phenylnaphthyl, naphthylphenyl, pyridyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, dinaphthofuranyl, dinaphthothiophenyl, dibenzofuranylphenyl, dibenzothiophenylphenyl, phenyldibenzocarbazolyl, phenylbenzocarbazolyl, phenylcarbazolyl, dibenzocarbazolyl, dimethylfluorenyl, benzodimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, and dimethylfluorenylphenyl.

6. The triptycene derivative according to claim 1, characterized in that The formula c is selected from any one of the following c-1, c-2, c-3, c-4, c-5, c-6 and c-7, Among them, R T1 -R T8 Each is independently selected from hydrogen and deuterium.

7. The triptycene derivative according to claim 1, characterized in that R 13 , R 14 Each is independently selected from C1-C6 alkyl.

8. The triptycene derivative according to claim 1, characterized in that R 13 , R 14 Each is independently selected from methyl and ethyl.

9. The triptycene derivative according to claim 1, characterized in that The triptycene derivatives are selected from the following:

10. An organic electroluminescent device, characterized in that: The organic electroluminescent device comprises a cathode, an anode and an organic layer located between the cathode and the anode, wherein the organic layer comprises the triptycene derivative according to any one of claims 1 to 9.

11. The organic electroluminescent device according to claim 10, characterized in that: The organic layer comprises a hole transport layer, and the hole transport layer comprises the triptycene derivative according to any one of claims 1 to 9.

12. The organic electroluminescent device according to claim 10, characterized in that: The organic layer comprises an electron blocking layer and / or an exciton blocking layer, and the electron blocking layer and / or the exciton blocking layer comprises the triptycene derivative according to any one of claims 1 to 9.

13. The organic electroluminescent device according to claim 10, characterized in that: The organic layer comprises a light-emitting layer, and the light-emitting layer comprises the triptycene derivative according to any one of claims 1 to 9.

14. Use of the triptycene derivative according to any one of claims 1 to 9 in the preparation of optical devices.

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