CN116425730A - Organic electroluminescent compounds and use thereof - Google Patents

Organic electroluminescent compounds and use thereof Download PDF

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CN116425730A
CN116425730A CN202211732230.8A CN202211732230A CN116425730A CN 116425730 A CN116425730 A CN 116425730A CN 202211732230 A CN202211732230 A CN 202211732230A CN 116425730 A CN116425730 A CN 116425730A
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organic electroluminescent
compound
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陈志宽
刘风娇
周仁美
缪振扬
邹清华
丁欢达
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Ningbo Lumilan Advanced Materials Co Ltd
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Abstract

The invention relates to the technical field of display, in particular to an organic electroluminescent compound and application thereof. The organic electroluminescent compound provided by the invention has the following structure:
Figure DDA0004031952670000011
the organic electroluminescent device comprising the organic electroluminescent compound can have a lower driving voltage and a longer lifetime.

Description

Organic electroluminescent compounds and use thereof
Technical Field
The invention relates to the technical field of display, in particular to an organic electroluminescent compound and application thereof.
Background
Organic Light Emitting Diodes (OLEDs) convert electrical energy into light by applying electrical power to an organic electroluminescent material, which is considered to be the most promising display and lighting technology, typically comprise an anode, a cathode and an organic layer formed between the two electrodes. The organic layer of an organic light-emitting electronic version (organic EL) may include a hole injection layer, a hole transport layer, a hole assist layer, a light-emitting assist layer, an electron blocking layer, a light-emitting 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, and the like. The materials used in the organic layer may be classified into a hole injecting material, a hole transporting material, a hole assisting material, a light emitting assisting material, an electron blocking material, a light emitting material, an electron buffering material, a hole blocking material, an electron transporting material, an electron injecting material, and the like depending on their functions. In the device of the organic EL, holes from the anode and electrons from the cathode are injected into the light emitting layer by applying a voltage, and excitons having high energy are generated by recombination of the holes and electrons. Electrons of the organic electroluminescent material emit light by energy when they move to an excited state by energy and return to a ground state from the excited state.
However, the matching degree of the HOMO energy level and the LUMO energy level of the existing organic electroluminescent material with the adjacent energy levels is poor, so that the problems of low stability and unbalanced carrier mobility of the organic electroluminescent material are caused, the problems of high driving voltage and short service life of an organic electroluminescent device containing the organic electroluminescent material are caused, and the application of the organic electroluminescent device is severely limited.
Disclosure of Invention
The invention aims to solve the problems of low stability and unbalanced carrier mobility of the organic electroluminescent material caused by poor matching degree of HOMO and LUMO energy levels and adjacent energy levels of the conventional organic electroluminescent material, and the problems of low luminous efficiency and short service life of an organic electroluminescent device containing the organic electroluminescent material severely limit the application of the organic electroluminescent device, thereby providing an organic electroluminescent compound and application thereof.
Definition of substituent terms in the present invention:
as used herein, the term "halogen" may include fluorine, chlorine, bromine or iodine.
As used herein, the term "C1-C30 alkyl" refers to monovalent substituents derived from straight or branched chain saturated hydrocarbons having from 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.
As used herein, the term "C3-C30 cycloalkyl" refers to a mono-or polycyclic hydrocarbon derived from a hydrocarbon having from 1 to 30 ring backbone carbon atoms, which cycloalkanes may include cyclopropyl, cyclobutyl, adamantyl, and the like.
Aryl, arylene in the present invention includes monocyclic, polycyclic or fused ring aryl groups which may be interrupted by short non-aromatic units and may contain spiro structures, aryl groups including, but not limited to, phenyl, biphenyl, terphenyl, naphthyl, phenanthryl, anthracenyl, fluorenyl, spirobifluorenyl, and the like, arylene groups including, but not limited to, phenylene, biphenylene, terphenylene, naphthylene, phenanthrylene, anthracenyl, fluorenylene, spirobifluorenyl, and the like.
Heteroaryl, heteroarylene in the present invention includes monocyclic, polycyclic or fused ring heteroaryl groups, which rings may be interrupted by short non-aromatic units, and the heteroatoms include nitrogen, oxygen, sulfur. Heteroaryl groups include, but are not limited to, furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazayl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothienyl, isobenzofuranyl, dibenzofuranyl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl, derivatives thereof, and the like; heteroarylene includes, but is not limited to, furanylene, thiophenylene, pyrrolylene, imidazolylene, pyrazolylene, thiazolylene, thiadiazolylene, isothiazolylene, isoxazolylene, oxazolylene, oxadiazolylene, triazinylene, tetrazinylene, triazolylene, tetrazolylene, furazaylene, pyridinyl, pyrazinylene, pyrimidinylene, pyridazinylene, benzofuranylene, benzothiophenylene, isobenzofuranylene, dibenzofuranylene, benzimidazolylene, benzothiazolylene, benzisothiazolylene, benzisoxazolylene, benzoxazolylene, isoquinolene, cinnolylene, cinnoline, quinazolinylene, quinoxaline, carbazolylene, phenazinylene, phenanthrenezine, phenanthrenedinylene, dioxolylene, dihydroacridine, and the like.
As used herein, the term "substituted" refers to a compound in which a hydrogen atom is replaced with another substituent. The position is not limited to a specific position as long as hydrogen at the position can be substituted with a substituent. When two or more substituents are present, the two or more substituents may be the same or different.
As used herein, unless otherwise indicated, hydrogen atoms include protium, deuterium, and tritium.
In the present invention, the definition of a group defines a range of carbon atoms, the number of carbon atoms being any integer within the defined range, for example, a C6-C30 aryl group, and the number of carbon atoms representing the aryl group may be any integer within the range of 6-60, for example, 6, 8, 10, 13, 15, 17, 20, 22, 25, 30, or the like.
The scheme adopted by the invention is as follows:
the invention provides an organic electroluminescent compound, which has the following structure:
Figure BDA0004031952650000031
wherein Ar is 1 -Ar 3 Each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C5-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl; wherein Ar is 1 -Ar 3 At least one of which is selected from the structures shown in formula 2,
Figure BDA0004031952650000032
Wherein T is 1 ，T 2 ，T 3 ，T 4 ，T 5 Each independently selected from CR or N, R is selected from hydrogen orDeuterium, and T 1 ，T 2 ，T 3 ，T 4 ，T 5 At least one of which is selected from N;
L 1 -L 4 each independently selected from the group consisting of a bond, a substituted or unsubstituted C1-C6 alkylene, a substituted or unsubstituted C6-C30 arylene, and a substituted or unsubstituted C3-C60 heteroarylene;
x is selected from O or S;
the substituent of the substituted C1-C30 alkyl, substituted C3-C30 cycloalkyl, substituted C5-C60 aryl, substituted C3-C60 heteroaryl, substituted C1-C6 alkylene, substituted C6-C30 arylene and substituted C3-C60 heteroarylene is selected from one or two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C5-C12 aryl and C3-C12 heteroaryl.
Wherein, the liquid crystal display device comprises a liquid crystal display device,
Figure BDA0004031952650000041
representing a connection key.
Preferably, the organic electroluminescent compound has a structure as shown below:
Figure BDA0004031952650000042
wherein Ar is 2 -Ar 3 Each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C5-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl;
T 1 ，T 2 ，T 3 ，T 4 ，T 5 each independently selected from CR or N, R is selected from hydrogen or deuterium, and T 1 ，T 2 ，T 3 ，T 4 ，T 5 At least one of which is selected from N;
L 2 -L 3 Each independently selected from the group consisting of a bond, a substituted or unsubstituted C1-C6 alkylene, a substituted or unsubstituted C6-C30 arylene, and a substituted or unsubstituted C3-C60 heteroarylene;
x is selected from O or S;
the substituent of the substituted C1-C30 alkyl, substituted C3-C30 cycloalkyl, substituted C5-C60 aryl, substituted C3-C60 heteroaryl, substituted C1-C6 alkylene, substituted C6-C30 arylene and substituted C3-C60 heteroarylene is selected from one or two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C5-C12 aryl and C3-C12 heteroaryl.
Preferably, the L 1 -L 4 Each independently selected from the group consisting of a linkage, a substituted or unsubstituted C6-C30 arylene group.
Preferably, the connection bond is a single bond.
Preferably, said Ar 1 -Ar 3 Each independently selected from the group consisting of substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C5-C60 aryl, and substituted or unsubstituted C3-C60 heteroaryl.
Preferably, L 2 -L 3 Each independently selected from single bond, C6-C30 arylene;
Ar 2 -Ar 3 each independently selected from the group consisting of C6-C30 aryl, C3-C18 heteroaryl;
x is selected from O or S.
Preferably T 1 Selected from N, T 2 ，T 3 ，T 4 ，T 5 Each independently selected from CR;
or T is 2 Selected from N, T 1 ，T 3 ，T 4 ，T 5 Each independently selected from CR;
or T is 1 ，T 5 Selected from N, T 2 ，T 3 ，T 4 Each independently selected from CR;
or T is 2 ，T 5 Selected from N, T 1 ，T 3 ，T 4 Each independently selected from CR;
or T is 1 ，T 4 Selected from N, T 2 ，T 3 ，T 5 Each independently selected from CR;
r is selected from hydrogen or deuterium.
Preferably, L 2 -L 3 Each independently selected from a single bond, phenylene, naphthylene;
Ar 2 -Ar 3 each independently selected from phenyl, naphthyl, pyridyl, pyrimidinyl.
The organic electroluminescent compound has a structure as shown below:
Figure BDA0004031952650000051
it will be appreciated that the bond La may be bonded to T 1 ，T 2 ，T 3 ，T 4 ，T 5 Any of the five elements representing C being joined, e.g. T 1 Selected from N, T 2 ，T 3 ，T 4 ，T 5 Independently of one another, selected from C, la and T 2 ，T 3 ，T 4 ，T 5 Any one of which is connected; for example when T 3 When selected from C, la may be combined with T 3 Directly connected.
It will be appreciated that the linkage Lb may be attached to any one of the C1-C4 carbon atoms in ring A.
Preferably, the organic electroluminescent compound is selected from the group consisting of:
Figure BDA0004031952650000052
Figure BDA0004031952650000061
Figure BDA0004031952650000071
Figure BDA0004031952650000081
Figure BDA0004031952650000091
Figure BDA0004031952650000101
Figure BDA0004031952650000111
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Figure BDA0004031952650000121
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Figure BDA0004031952650000131
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Figure BDA0004031952650000141
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Figure BDA0004031952650000151
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Figure BDA0004031952650000161
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Figure BDA0004031952650000171
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Figure BDA0004031952650000181
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Figure BDA0004031952650000191
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Figure BDA0004031952650000201
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Figure BDA0004031952650000211
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Figure BDA0004031952650000221
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Figure BDA0004031952650000231
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Figure BDA0004031952650000241
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Figure BDA0004031952650000251
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Figure BDA0004031952650000261
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Figure BDA0004031952650000271
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Figure BDA0004031952650000281
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Figure BDA0004031952650000291
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Figure BDA0004031952650000301
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Figure BDA0004031952650000311
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Figure BDA0004031952650000321
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Figure BDA0004031952650000331
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Figure BDA0004031952650000341
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Figure BDA0004031952650000351
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Figure BDA0004031952650000361
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Figure BDA0004031952650000371
/>
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Figure BDA0004031952650000391
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Figure BDA0004031952650000401
the compound shown in formula 1 claimed in the present invention can be used as a host material of a light-emitting layer alone or together with other materials, and the invention is not limited in particular to the types of other materials, and can be a material of a light-emitting layer host as is conventional in the art, and further, the present invention also provides an organic electroluminescent composition comprising the above-mentioned organic electroluminescent compound and a compound having the following structure:
Figure BDA0004031952650000402
Wherein Ar is W1 、Ar W2 、Ar W3 Each independently selected from hydrogen, deuterium, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, ar W1 、Ar W2 、Ar W3 Are not connected with each other or are connected with adjacent two to form a ring; l (L) W1 、L W2 、L W3 Each independently selected from the group consisting of a bond, a substituted or unsubstituted C6-C30 arylene, a substituted or unsubstituted C3-C30 heteroarylene;
the substituent of the substituted C6-C60 aryl, the substituted C3-C60 heteroaryl, the substituted C6-C30 arylene and the substituted C3-C30 heteroarylene is selected from one or two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C5-C12 aryl and C3-C12 heteroaryl.
Preferably, in formula 3, ar W1 、Ar W2 、Ar W3 Each independently selected from hydrogen, deuterium, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted naphthyl, substituted or unsubstituted triphenylene, substituted or unsubstituted triazinyl, substituted or unsubstituted C3-C30 heteroaryl, and substituted or unsubstituted group Q, wherein the group Q is selected from one of the following structures:
Figure BDA0004031952650000403
Figure BDA0004031952650000411
or Ar W1 、Ar W2 、Ar W3 Any two of which are linked to form a ring a, wherein ring a is: />
Figure BDA0004031952650000412
Wherein the substituent in the substituted phenyl, substituted biphenyl, substituted dibenzofuranyl, substituted naphthyl, substituted triphenylene, substituted triazinyl, substituted C3-C30 heteroaryl, and substituted group Q is selected from at least one of deuterium, phenyl, C1-C5 alkyl, and biphenyl;
Ar is selected from deuterium, halogen, cyano, C6-C60 aryl;
R 10 -R 17 each independently selected from the group consisting of a bond, hydrogen, deuterium, halogen, cyano, C1-C30 alkyl, C3-C30 alkyl wherein one or more methylene groups are each substituted in a non-adjacent manner by-O-and/or-S atoms, C7-C30 aralkyl, C6-C30 aryl, C3-C30 heteroaryl, C4-C30 heteroaralkyl, C3-C30 cycloalkyl, C3-C30 heterocycloalkyl, C3-C30 cycloalkenyl, C1-C30 alkoxy, C6-C30 aryloxy;
alternatively, R 10 -R 17 The two adjacent rings are connected with a ring B, wherein the ring B is selected from a C6-C30 aromatic ring and a C3-C30 heteroaromatic ring.
Preferably, L W1 、L W2 、L W3 Each independently selected from the group consisting of a linkage, phenylene, biphenylene, and naphthylene.
Preferably, the compound of formula 3 is selected from one of the following compounds:
Figure BDA0004031952650000413
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Figure BDA0004031952650000421
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Figure BDA0004031952650000431
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Figure BDA0004031952650000441
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Figure BDA0004031952650000451
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Figure BDA0004031952650000461
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Figure BDA0004031952650000471
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Figure BDA0004031952650000481
/>
Figure BDA0004031952650000491
the compound with the structure of the formula 3 is a known material and can be prepared by the conventional technical means.
Preferably, the mass ratio of the organic electroluminescent compound to the compound having the structure of formula 3 is: 1:9-9:1;
preferably, the mass ratio of the organic electroluminescent compound to the compound having the structure of formula 3 is: 2:8-8:2;
more preferably, the mass ratio of the organic electroluminescent compound to the compound having the structure of formula 3 is: 3:7-7:3;
Further preferably, the mass ratio of any one of the above organic electroluminescent compounds to the compound having the structure of formula 3 is: 4:6-6:4.
The invention also provides an organic electroluminescent device, which comprises a first electrode, a second electrode and an organic layer positioned between the first electrode and the second electrode, wherein the organic layer comprises the organic electroluminescent compound.
Preferably, the organic layer comprises an electron transport layer comprising the organic electroluminescent compound described above.
Preferably, the organic layer includes a light emitting layer, and a material of the light emitting layer includes a host material and a guest material; the host material comprises the organic electroluminescent composition described above;
preferably, the guest material comprises a phosphorescent dopant or a thermally activated delayed fluorescence compound;
preferably, the phosphorescent dopant comprises a complex of a transition metal;
the organic electroluminescent device is an organic light emitting diode.
In an embodiment of the organic electroluminescent device, the first electrode of the organic electroluminescent device is an anode, the second electrode of the organic electroluminescent device 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 which are sequentially stacked, and the organic electroluminescent device further comprises a substrate, wherein the substrate is positioned on the surface of one side of the anode, which is opposite to the cathode.
Optionally, an electron blocking layer is further included between the hole transport layer and the light emitting layer.
In the present invention, the synthetic route of any one of the above organic electroluminescent compounds comprises the steps of:
step one:
Figure BDA0004031952650000501
step two:
Figure BDA0004031952650000502
step three:
Figure BDA0004031952650000503
the invention has the beneficial effects that:
1. the present invention provides organic electroluminescent compounds based on the structure of formula 1, and further defining Ar 1 -Ar 3 At least one of the structures shown in the formula 2 is selected from the structures, and the HOMO energy level and the LUMO energy level of the organic electroluminescent compound are matched with each other through the two structures so that the organic electroluminescent compound has higher matching degree with the adjacent energy level, the organic electroluminescent compound has higher stability and more balanced carrier mobility, and the organic electroluminescent device containing the organic electroluminescent material has lower driving voltage and longer service life.
2. The invention provides an organic electroluminescent composition, which is characterized in that a compound of formula 1 and a compound of formula 3 are combined with each other, so that the stability and carrier mobility balance of the organic electroluminescent composition are further improved, the driving voltage of an organic electroluminescent device comprising the organic electroluminescent composition is further reduced, and the service life of the organic electroluminescent device is further prolonged.
Further, the organic electroluminescent device comprising the organic electroluminescent composition has higher current efficiency.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a block diagram of an organic electroluminescent device in an embodiment of the device of the present invention
1-a substrate; 2-anode; 3-a hole injection layer; a 4-hole transport layer; a 5-light emitting layer; 6-an electron transport layer; 7-an electron injection layer; 8-cathode.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
Example 1
The embodiment provides an organic electroluminescent compound N-2, and the preparation method of the compound N-2 specifically comprises the following steps:
Figure BDA0004031952650000511
step 1) Synthesis of intermediate N-B2 (reaction scheme above)
Taking a 100mL three-necked round bottom bottle, placing the bottle into a stirrer and a top reflux pipe, adding raw material 2-B (1 mmol), raw material 2-A (1 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), adding tetraphenylphosphine palladium (0.05 mmol), heating to 90, reacting for 12h, cooling to room temperature, extracting with water and ethyl acetate, drying an organic phase with anhydrous magnesium sulfate, removing a solvent by using a rotary evaporator, separating a crude product by column chromatography (DCM: n-hexane=1:50) to obtain an intermediate 2-B-1 (yield 80%);
a100 mL three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, 2-B-1 (1 mmol), (methoxymethyl) triphenylphosphine chloride (1.8 mmol) obtained above, THF (10 mL) was added, the temperature was lowered to-10%, and a solution of t-BuOK (27 g) in tetrahydrofuran (150 mL) was slowly added dropwise using a constant pressure dropping funnel, the temperature was maintained below-5. After the completion of the dropwise addition, the reaction was carried out at this temperature for 20 minutes. Then slowly heating to room temperature, and after the reaction liquid reaches the room temperature, continuing the reaction for 1h, and stopping the reaction. The reaction was extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: n-hexane=1:50) to give intermediate 2-B-2 (80% yield);
A100 mL three-necked round bottom flask was taken and placed in a stirrer and an upper return tube, and 2-B-2 (1 mmol) and hexafluoroisopropanol (14 mL) obtained above were added. Under the protection of nitrogen, the temperature is reduced to-10 ℃, after the temperature is reached, the triflic acid (3 mmol) is slowly added dropwise by using a constant pressure dropping funnel, and the temperature is always kept below-5 ℃. After the completion of the dropwise addition, the reaction was carried out at this temperature for 20 minutes. Then slowly heating to room temperature, and after the reaction liquid reaches the room temperature, continuing the reaction for 1h, and stopping the reaction. The reaction was extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: n-hexane=1:50) to give intermediate 2-B-3 (80% yield);
taking a 100mL three-necked round bottom bottle, placing the bottle into a stirrer and an upper return pipe, adding the obtained 2-B-3 (1 mmol), adding 10mL of dioxane, adding 1,1' -bis-diphenylphosphine ferrocene palladium dichloride (0.05 mmol) and potassium acetate (2 mmol), heating to 110 ℃, reacting for 12 hours, cooling to room temperature after the reaction is finished, extracting with water and ethyl acetate, drying an organic phase with anhydrous magnesium sulfate, removing a solvent by using a rotary evaporator, and separating a crude product by using column chromatography (DCM: N-hexane=1:50) to obtain an intermediate N-B2 (yield 80%);
Figure BDA0004031952650000521
Step 2) Synthesis of intermediate N-A2 (reaction scheme above)
A100 mL three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, raw N-B2 (1 mmol), 2-bromo-5- (4, 5-tetramethyl-1, 3, 2-dioxapentaborane-2-yl) pyridine (1.05 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), tetrakis triphenylphosphine palladium (0.05 mmol), potassium carbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, after completion of the reaction, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: N-hexane=1:50) to give intermediate N-A2 (80% yield).
Figure BDA0004031952650000531
Step 3) Synthesis of Compound N-2
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate N-A2 (1.05 mmol), 2-chloro-4, 6-diphenyl-1, 3, 5-triazine (1 mmol) toluene (9 mL), water (3 mL), palladium 132 (0.02 mmol), sodium bicarbonate (2 mmol) were added, the reaction was heated to 90℃for 12 hours, after the completion of the reaction, cooled to room temperature, water and ethyl acetate were used to extract the organic phase, dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: N-hexane=1:50) to give structure N-2 (yield 80%).
Elemental analysis: c (C) 40 H 24 N 4 Theoretical value of O: c,83.31; h,4.20; n,9.72; o,2.77; actual measurement value: c,83.37; h,4.19; n,9.68; HRMS (ESI) M/z (m+): theoretical value: 576.20; actual measurement value: 577.21.
example 2
The embodiment provides an organic electroluminescent compound N-3, and the preparation method of the compound N-3 specifically comprises the following steps:
Figure BDA0004031952650000532
(1) Synthesis of intermediate 3-D (shown in the above formula)
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, 2-pyridineboronic acid (1 mmol), 6-bromo-2-naphthol (1 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), tetraphenylphosphine palladium (0.05 mmol), potassium carbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, after completion of the reaction, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: n-hexane=1:50) to give intermediate 3-D-2 (yield 80%).
A100 mL three-necked round bottom bottle is taken and placed into a stirrer and an upper return pipe, an intermediate 3-D-2 (1 mmol), DCM (10 mmol) and triethylamine (1.5 mmol) are added, the temperature is reduced to about 0 ℃ in a nitrogen atmosphere, then trifluoromethanesulfonic anhydride (1.2 mmol) is slowly added dropwise, the reaction environment at 0 ℃ is maintained, the reaction time is maintained at 0 ℃ for 0.5h after the dropwise addition is finished, and then the reaction time is increased to room temperature for 12h. After the reaction, a saturated ammonium chloride solution is slowly added dropwise to quench the reaction, a large amount of solid is precipitated when the solution is neutral, the solution is filtered by suction, washed with ethanol (2 mmol) and dried to obtain an intermediate 3-D-3 (yield 80%).
100mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate 3-D-3 (1 mmol) was added, raw material bispinacol borate (1 mmol), dioxane 10mL, 1' -bisdiphenylphosphino ferrocene palladium dichloride (0.05 mmol) and potassium acetate (2 mmol) were added, the reaction was heated to 110℃for 12 hours, after the reaction was completed, the temperature was lowered to room temperature, water and ethyl acetate were used for extraction, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed by using a rotary evaporator, and the crude product was separated by column chromatography (DCM: n-hexane=1:50) to obtain intermediate 3-D (yield 80%).
Figure BDA0004031952650000541
(2) Synthesis of intermediate N-C3 (shown in the above formula)
A100 mL three-necked round bottom flask was taken and placed in a stirrer and upper reflux tube, 2, 4-dichloro-6-phenyl-1, 3, 5-triazine (1.05 mmol) was added, 3-D (0.95 mmol) of intermediate toluene (9 mL), water (3 mL), 1' -bis-diphenylphosphino ferrocene palladium dichloride (0.05 mmol) and sodium carbonate (2 mmol) were added, heated to 90℃for 12 hours, cooled to room temperature after the reaction was completed, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give intermediate N-C3 (yield 80%).
Figure BDA0004031952650000542
Figure BDA0004031952650000551
(3) Synthesis of Compound N-3
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate N-C3 (1 mmol), intermediate N-A2 (1 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), palladium 132 (0.02 mmol), sodium bicarbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, after completion of the reaction, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give structure N-3 (yield 80%).
Elemental analysis: c (C) 49 H 29 N 5 Theoretical value of O: c,83.62; h,4.15; n,9.95; o,2.27; actual measurement value: c,83.67; h,4.13; n,9.91; HRMS (ESI) M/z (m+): theoretical value: 703.24; actual measurement value: 704.61.
example 3
The embodiment provides an organic electroluminescent compound N-5, and the preparation method of the compound N-5 specifically comprises the following steps:
Figure BDA0004031952650000552
(1) Synthesis of intermediate N-C5 (shown in the above formula)
A100 mL three-necked round bottom flask was taken and placed in a stirrer and upper reflux tube, intermediate 2, 4-dichloro-6-naphthalen-1-yl- [1,3,5] triazine (1.05 mmol), intermediate 3-D (0.95 mmol) toluene (9 mL), water (3 mL), 1' -bis-diphenylphosphino ferrocene palladium dichloride (0.05 mmol), sodium carbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: N-hexane=1:50) to give intermediate N-C5 (80% yield).
Figure BDA0004031952650000561
(2) Synthesis of Compound N-5
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate N-C5 (1 mmol), intermediate N-A2 (1 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), palladium 132 (0.02 mmol), sodium bicarbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, after completion of the reaction, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give structure N-5 (yield 80%).
Elemental analysis: c (C) 53 H 31 N 5 Theoretical value of O: c,84.44; h,4.15; n,9.29; o,2.12; actual measurement value: c,84.46; h,4.16; n,9.26; HRMS (ESI) M/z (m+): theoretical value: 753.25; actual measurement value: 754.34.
example 4
The embodiment provides an organic electroluminescent compound N-14, and the preparation method of the compound N-14 specifically comprises the following steps:
Figure BDA0004031952650000562
(1) Synthesis of intermediate N-C14
A100 mL three-necked round bottom flask was taken and placed in a stirrer and upper reflux tube, intermediate 2, 4-dichloro-6-phenyl-1, 3, 5-triazine (1.05 mmol), 4- (3-pyridyl) phenylboronic acid (0.95 mmol) toluene (9 mL), water (3 mL), 1' -bis-diphenylphosphino ferrocene palladium dichloride (0.05 mmol), sodium carbonate (2 mmol) were added, heated to 90℃for 12 hours, cooled to room temperature after the reaction was completed, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: N-hexane=1:50) to give structure N-C14 (80% yield).
Figure BDA0004031952650000571
(2) Synthesis of Compound N-14
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate N-A2 (1.05 mmol), intermediate N-C14 (1 mmol), toluene (9 mL), water (3 mL), palladium 132 (0.02 mmol), sodium bicarbonate (2 mmol) were added, the temperature was heated to 90℃for 12 hours, after the reaction was completed, the temperature was lowered to room temperature, water and ethyl acetate were used for extraction, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: N-hexane=1:50) to give structure N-14 (yield 80%).
Elemental analysis: c (C) 45 H 27 N 5 Theoretical value of O: c,82.68; h,4.16; n,10.71; o,2.45; actual measurement value: c,82.64; h,4.17; n,10.74; HRMS (ESI) M/z (m+): theoretical value: 653.22; actual measurement value: 654.25.
example 5
The embodiment provides an organic electroluminescent compound N-18, and the preparation method of the compound N-18 specifically comprises the following steps:
Figure BDA0004031952650000572
synthesis of intermediate N-C18 (shown in the above formula)
A100 mL three-necked round bottom flask was taken and placed in a stirrer and upper reflux tube, intermediate 2, 4-dichloro-6-naphthalen-1-yl- [1,3,5] triazine (1.05 mmol), 4- (3-pyridyl) phenylboronic acid (0.95 mmol) toluene (9 mL), water (3 mL), 1' -bis-diphenylphosphino ferrocene palladium dichloride (0.05 mmol) and sodium carbonate (2 mmol) were added, heated to 90℃for 12 hours, cooled to room temperature after the reaction was completed, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: N-hexane=1:50) to give intermediate N-C18 (80% yield).
Figure BDA0004031952650000581
Synthesis of Compound N-18 (represented by the above formula)
100mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate N-C18 (1.05 mmol), intermediate N-A2 (1 mmol), toluene (9 mL), water (3 mL), palladium 132 (0.02 mmol), sodium bicarbonate (2 mmol) were added, the temperature was heated to 90℃for 12 hours, after the reaction was completed, the temperature was lowered to room temperature, water and ethyl acetate were used for extraction, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: N-hexane=1:50) to give structure N-18 (yield 80%).
Elemental analysis: c (C) 49 H 29 N 5 Theoretical value of O: c,83.62; h,4.15; n,9.95; o,2.27; actual measurement value: c,83.67; h,4.14; n,9.91; HRMS (ESI) M/z (m+): theoretical value: 703.24; actual measurement value: 704.19.
example 6
The embodiment provides an organic electroluminescent compound N-84, and the preparation method of the compound N-84 specifically comprises the following steps:
Figure BDA0004031952650000582
1) Synthesis of intermediate N-B84 (reaction scheme above)
100mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, 84-B (1 mmol) as a raw material, 2-A (1 mmol) as a raw material, toluene (9 mL), ethanol (3 mL), water (3 mL), and tetrakis triphenylphosphine palladium (0.05 mmol) were added, potassium carbonate (2 mmol) was heated to 90℃and reacted for 12 hours, after completion of the reaction, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: n-hexane=1:50) to give intermediate 84-B-2 (yield 80%).
A100 mL three-neck round bottom bottle is taken and placed into a stirrer and an upper return pipe, 84-B-2 (1 mmol) of (methoxymethyl) triphenylphosphine chloride (1.8 mmol) as a raw material is added, THF (10 mL) is cooled to-5 ℃ to-10 ℃, a tetrahydrofuran (150 mL) solution of t-BuOK (27 g) is slowly added dropwise by a constant pressure dropping funnel, and the temperature is always kept below-5 ℃. After the completion of the dropwise addition, the reaction was carried out at this temperature for 20 minutes. Then slowly heating to room temperature, and after the reaction liquid reaches the room temperature, continuing the reaction for 1h, and stopping the reaction. The reaction was extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: n-hexane=1:50) to give intermediate 84-B-3 (yield 80%).
A100 mL three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, and 84-B-3 (1 mmol) and hexafluoroisopropanol (14 mL) were added. Under the protection of nitrogen, the temperature is reduced to minus 5 ℃ to minus 10 ℃, after the temperature is reached, the triflic acid (3 mmol) is slowly added dropwise by a constant pressure dropping funnel, and the temperature is always kept below minus 5 ℃. After the completion of the dropwise addition, the reaction was carried out at this temperature for 20 minutes. Then slowly heating to room temperature, and after the reaction liquid reaches the room temperature, continuing the reaction for 1h, and stopping the reaction. The reaction was extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: n-hexane=1:50) to give intermediate 84-B-4 (yield 80%).
100mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, 84-B-4 (1 mmol) was added, raw material bispinacol borate (1 mmol), dioxane (10 mL) was added, 1' -bisdiphenylphosphino ferrocene palladium dichloride (0.05 mmol), potassium acetate (2 mmol) was added, the temperature was heated to 110℃for 12 hours, after the reaction was completed, the temperature was lowered to room temperature, water and ethyl acetate were used for extraction, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: N-hexane=1:50) to obtain intermediate N-B84 (yield 80%).
Figure BDA0004031952650000591
2) Synthesis of intermediate N-A84 (shown by the formula above)
A100 mL three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, raw N-B84 (1 mmol), 2-bromo-5- (4, 5-tetramethyl-1, 3, 2-dioxapentaborane-2-yl) pyridine (1.05 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), tetrakis triphenylphosphine palladium (0.05 mmol), potassium carbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, after completion of the reaction, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: N-hexane=1:50) to give intermediate N-A84 (80% yield).
3) Synthesis of Compound N-84
Figure BDA0004031952650000601
(1) Synthesis of intermediate N-C84 (shown in the above formula)
A100 mL three-necked round bottom flask was taken and placed in a stirrer and upper reflux tube, intermediate 2, 4-dichloro-6- (3-biphenyl) -1,3, 5-triazine (1.05 mmol), 2- (4-pyridyl) phenylboronic acid (0.95 mmol) toluene (9 mL), water (3 mL), 1' -bis-diphenylphosphino ferrocene palladium dichloride (0.05 mmol), sodium carbonate (2 mmol) were added, heated to 90℃for 12 hours, after the reaction was completed, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: N-hexane=1:50) to give intermediate N-C84 (80% yield).
Figure BDA0004031952650000602
(2) Synthesis of Compound N-84
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate N-C84 (1 mmol), intermediate N-A84 (1 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), palladium 132 (0.02 mmol), sodium bicarbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, after completion of the reaction, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give structure N-84 (yield 80%).
Elemental analysis: c (C) 51 H 31 N 5 S theory: c,82.12; h,4.19; n,9.39; s,4.30; actual measurement value: c,82.15; h,4.19; n,9.36; s,4.30; HRMS (ESI) M/z (m+): theoretical value: 745.23; actual measurement value: 746.19.
example 7
The embodiment provides an organic electroluminescent compound N-19, and the preparation method of the compound N-19 specifically comprises the following steps:
Figure BDA0004031952650000611
synthesis of intermediate N-A19 (shown by the following formula)
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate N-B84 (1 mmol), 2-bromopyridine-5-boronic acid (1.05 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), and tetrakis triphenylphosphine palladium (0.05 mmol), potassium carbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, after the reaction was completed, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: N-hexane=1:50) to give intermediate N-A19 (yield 80%).
Synthesis of Compound N-19
Figure BDA0004031952650000612
Synthesis of intermediate N-C19 (shown in the above formula)
A100 mL three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate 2- (4-biphenyl) -4, 6-dichloro-1, 3, 5-triazine (1.05 mmol), 4- (3-pyridyl) phenylboronic acid (0.95 mmol) toluene (9 mL), water (3 mL), 1' -bis-diphenylphosphino ferrocene palladium dichloride (0.05 mmol) and sodium carbonate (2 mmol) were added, heated to 90℃for 12 hours, after the reaction was completed, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: N-hexane=1:50) to give intermediate N-C19 (80% yield).
Figure BDA0004031952650000621
Synthesis of Compound N-19 (represented by the above formula)
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, raw material N-C19 (1 mmol), intermediate N-A19 (1 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), palladium 132 (0.02 mmol), sodium bicarbonate (2 mmol) were added, heated to 90℃for 12 hours, cooled to room temperature after the reaction was completed, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give structure N-19 (yield 80%).
Elemental analysis: c (C) 51 H 31 N 5 S theory: c,82.12; h,4.19; n,9.39; s,4.30; actual measurement value: c,82.15; h,4.19; n,9.37; s,4.29HRMS (ESI) M/z (M+): theoretical value: 745.23; actual measurement value: 746.37.
example 8
The embodiment provides an organic electroluminescent compound N-96, and the preparation method of the compound N-96 specifically comprises the following steps:
Figure BDA0004031952650000622
synthesis of intermediate N-C96 (shown in the above formula)
A100 mL three-necked round bottom flask was taken and placed in a stirrer and upper reflux tube, intermediate 2, 4-dichloro-6-phenyl-1, 3, 5-triazine (1.05 mmol) was added, B- [4- (4-pyrimidinyl) phenyl ] boronic acid (0.95 mmol) toluene (9 mL), water (3 mL), 1' -bis-diphenylphosphino ferrocene palladium dichloride (0.05 mmol) was added, sodium carbonate (2 mmol) was heated to 90℃and reacted for 12 hours, after completion of the reaction, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give intermediate N-C96 (80% yield).
Figure BDA0004031952650000631
Synthesis of Compound N-96 (represented by the above formula)
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate N-C96 (1 mmol), intermediate N-A84 (1 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), palladium 132 (0.02 mmol), sodium bicarbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, after completion of the reaction, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give structure N-96 (yield 80%).
Elemental analysis: c (C) 44 H 26 N 6 S theory: c,78.78; h,3.91; n,12.53; s,4.78; actual measurement value: c,78.83; h,3.91; n,12.47; s,4.79; HRMS (ESI) M/z (m+): theoretical value: 670.19; actual measurement value: 671.22.
example 9
The embodiment provides an organic electroluminescent compound N-100, and the preparation method of the compound N-100 specifically comprises the following steps:
Figure BDA0004031952650000632
synthesis of intermediate 100-D (shown in the above figure)
A100 mL three-necked round bottom flask was taken and placed in a stirrer and upper reflux tube, 5-bromopyrimidine (1 mmol), 1, 3-phenyldiboronic acid (1 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), tetrakis triphenylphosphine palladium (0.05 mmol), potassium carbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, after completion of the reaction, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: n-hexane=1:50) to give intermediate 100-D (yield 80%).
Synthesis of intermediate N-C100 (shown in the above figure)
A100 mL three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, 100-D (1 mmol), 2- (4-biphenyl) -4, 6-dichloro-1, 3, 5-triazine (1 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), palladium tetraphenylphosphine (0.05 mmol), potassium carbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, cooled to room temperature after the reaction, extracted with water and ethyl acetate, the organic phase was dried with anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: N-hexane=1:50) to give N-C100 (yield 80%).
Figure BDA0004031952650000641
Synthesis of Compound N-100
A100 mL three-necked round bottom flask was taken and placed in a stirrer and upper reflux tube, raw N-C100 (1 mmol), intermediate N-A2 (1 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), palladium 132 (0.02 mmol), sodium bicarbonate (2 mmol) were added, heated to 90℃for 12 hours, cooled to room temperature after the reaction was completed, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give structure N-100 (yield 80%).
Elemental analysis: c (C) 50 H 30 N 6 Theoretical value of O: c,82.17; h,4.14; n,11.50; o,2.19; actual measurement value: c,82.22; h,4.13; n,11.47;HRMS (ESI) M/z (m+): theoretical value: 730.25; actual measurement value: 731.22.
example 10
The embodiment provides an organic electroluminescent compound N-233, and the preparation method of the compound N-233 specifically comprises the following steps:
step 1) is the same as step 1 of example 1;
Figure BDA0004031952650000642
step 2) Synthesis of intermediate N-A233 (represented by the above formula)
A100 mL three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, raw material N-B2 (1 mmol), 2-bromo-5- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) pyrimidine (1.05 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), and tetrakis triphenylphosphine palladium (0.05 mmol) were added, potassium carbonate (2 mmol) was heated to 90℃and reacted for 12 hours, after completion of the reaction, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give intermediate N-A233 (80% yield).
Step 3) Synthesis of Compound N-233
Figure BDA0004031952650000651
Synthesis of intermediate N-C233
A100 mL three-necked round bottom flask was placed in a stirrer and an upper reflux tube, intermediate 2, 4-dichloro-6-naphthalen-1-yl- [1,3,5] triazine (1.05 mmol) was added, B- [2- (3-pyridyl) phenyl ] boronic acid (0.95 mmol) toluene (9 mL), water (3 mL), 1' -bis-diphenylphosphino ferrocene palladium dichloride (0.05 mmol), sodium carbonate (2 mmol) were added, heated to 90℃C, reacted for 12 hours, cooled to room temperature after the reaction was completed, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: N-hexane=1:50) to give intermediate N-C233 (80% yield).
Figure BDA0004031952650000652
Synthesis of Compound N-233 (represented by the above formula)
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate N-C233 (1.05 mmol), intermediate N-A233 (1 mmol), toluene (9 mL), water (3 mL), palladium 132 (0.02 mmol), sodium bicarbonate (2 mmol) were added, the temperature was heated to 90℃for 12 hours, after the reaction was completed, the temperature was lowered to room temperature, water and ethyl acetate were used for extraction, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give structure N-233 (yield 80%).
Elemental analysis: c (C) 48 H 28 N 6 Theoretical value of O: c,81.80; h,4.00; n,11.93; o,2.27; actual measurement value: c,81.82; h,4.01; n,11.90; HRMS (ESI) M/z (m+): theoretical value: 704.23; actual measurement value: 705.25.
example 11
The embodiment provides an organic electroluminescent compound N-172, and the preparation method of the compound N-172 specifically comprises the following steps:
Figure BDA0004031952650000661
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate N-5C (1 mmol), intermediate N-A233 (1 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), palladium 132 (0.02 mmol), sodium bicarbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, after completion of the reaction, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give structure N-172 (yield 80%).
Elemental analysis: c (C) 52 H 30 N 6 O theory ofValue: c,82.74; h,4.01; n,11.13; o,2.12; actual measurement value: c,82.76; h,4.03; n,11.09; HRMS (ESI) M/z (m+): theoretical value: 754.25; actual measurement value: 755.30.
example 12
The embodiment provides an organic electroluminescent compound N-180, and the preparation method of the compound N-180 specifically comprises the following steps:
Figure BDA0004031952650000662
synthesis of intermediate N-180A (shown in the above formula)
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, raw material N-B84 (1 mmol), 5-bromopyrazine-2-boronic acid (1.05 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), and tetrakis triphenylphosphine palladium (0.05 mmol), potassium carbonate (2 mmol) were added, heated to 90℃C, reacted for 12 hours, cooled to room temperature after the completion of the reaction, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: N-hexane=1:50) to give intermediate N-180A (yield 80%).
Synthesis of Compound N-180
Figure BDA0004031952650000671
Synthesis of Compound N-180 (represented by the above formula)
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate N-180A (1.05 mmol), intermediate N-C18 (1 mmol), toluene (9 mL), water (3 mL), palladium 132 (0.02 mmol), sodium bicarbonate (2 mmol) were added, the temperature was heated to 90℃for 12 hours, after the reaction was completed, the temperature was lowered to room temperature, water and ethyl acetate were used for extraction, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give structure N-180 (yield 80%).
Elemental analysis: c (C) 48 H 28 N 6 S theory: c,79.98; h,3.92; n,11.66; s,4.45; actual measurement value: c,80.00; h,3.93; n,11.64; s,4.44HRMS (ESI) M/z (M+): theoretical value: 720.21; actual measurement value: 721.37.
example 13
The embodiment provides an organic electroluminescent compound N-239, and the preparation method of the compound N-239 specifically comprises the following steps:
Figure BDA0004031952650000672
synthesis of intermediate N-A239 (shown as the formula above)
A100 mL three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, raw material N-B84 (1 mmol), 2-bromo-5- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) pyrimidine (1.05 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), and tetrakis triphenylphosphine palladium (0.05 mmol) were added, potassium carbonate (2 mmol) was heated to 90℃and reacted for 12 hours, after completion of the reaction, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give intermediate N-A239 (80% yield).
Synthesis of Compound N-239
Figure BDA0004031952650000681
Synthesis of Compound N-239 (represented by the above formula)
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate N-C233 (1.05 mmol), intermediate N-A239 (1 mmol), toluene (9 mL), water (3 mL), palladium 132 (0.02 mmol), sodium bicarbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give structure N-239 (yield 80%).
Elemental analysis: c (C) 48 H 28 N 6 S theory: c,79.98; h,3.92; n,11.65; s,4.45; actual measurement value: c,80.00; h,3.93; n,11.62; s,4.45; HRMS (ESI) M/z (m+): theoretical value: 720.21; actual measurement value: 721.23.
example 14
The embodiment provides an organic electroluminescent compound N-303, and the preparation method of the compound N-303 specifically comprises the following steps:
Figure BDA0004031952650000682
synthesis of intermediate 303-D (shown by the formula above)
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, 2-bromopyrimidine (1 mmol), 1, 3-phenylboronic acid (1 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), tetrakis triphenylphosphine palladium (0.05 mmol), potassium carbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, after completion of the reaction, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: n-hexane=1:50) to give intermediate 303-D (yield 80%).
Synthesis of intermediate N-C303 (shown by the formula)
A100 mL three-necked round bottom flask was taken and placed in a stirrer and upper reflux tube, raw material intermediate 303-D (1 mmol), 2- (4-biphenyl) -4, 6-dichloro-1, 3, 5-triazine (1 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), tetrakis triphenylphosphine palladium (0.05 mmol), potassium carbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, cooled to room temperature after the end of the reaction, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give intermediate N-C303 (80% yield).
Figure BDA0004031952650000691
Synthesis of Compound N-303 (represented by the above formula)
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate N-C303 (1 mmol), intermediate N-A233 (1 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), palladium 132 (0.02 mmol), sodium bicarbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, after completion of the reaction, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give structure N-303 (yield 80%).
Elemental analysis: c (C) 49 H 29 N 7 Theoretical value of O: c,80.42; h,3.99; n,13.40; o,2.19; actual measurement value: c,80.45;
h,3.98; n,13.37; HRMS (ESI) M/z (m+): theoretical value: 731.24; actual measurement value: 732.21.
example 15
The embodiment provides an organic electroluminescent compound N-310, and the preparation method of the compound N-310 specifically comprises the following steps:
Figure BDA0004031952650000701
synthesis of intermediate 310-D (shown by the formula above)
Taking a 100 ml three-neck round bottom bottle, placing the bottle into a stirrer and an upper return pipe, adding 2-bromopyrimidine (1 mmol), 1, 2-phenylboronic acid (1 mmol), toluene (9 ml), ethanol (3 ml), water (3 ml), adding tetraphenylphosphine palladium (0.05 mmol), potassium carbonate (2 mmol), heating to 90 ℃, reacting for 12 hours, cooling to room temperature, extracting with water and ethyl acetate, drying an organic phase by using anhydrous magnesium sulfate, removing a solvent by using a rotary evaporator, and separating a crude product by column chromatography (DCM: n-hexane=1:50) to obtain an intermediate 310-D (yield 80%);
Synthesis of intermediate N-C310 (shown by the formula above)
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate 310-D (1 mmol), 2- (4-phenyl) -4, 6-dichloro-1, 3, 5-triazine (1 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), palladium tetraphenylphosphine (0.05 mmol), potassium carbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, cooled to room temperature after the completion of the reaction, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give intermediate N-C310 (yield 80%).
Figure BDA0004031952650000702
Synthesis of Compound N-310
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate N-C310 (1 mmol), intermediate N-A239 (1 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), palladium 132 (0.02 mmol), sodium bicarbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, after completion of the reaction, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give structure N-310 (yield 80%).
Elemental analysis: c (C) 43 H 25 N 7 S theory: c,80.42; h,3.99; n,13.40; o,2.19; actual measurement value: c,76.88; h,3.75; n,14.60; s,4.77; HRMS (ESI) M/z (m+): theoretical value: 671.19; actual measurement value: 672.21.
example 16
The embodiment provides an organic electroluminescent compound N-353, and the preparation method of the compound N-353 specifically comprises the following steps:
Figure BDA0004031952650000711
step 1) Synthesis of intermediate N-B353 (reaction scheme above)
100mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, raw material 2-B (1 mmol), raw material 353-A (1 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), and tetrakis triphenylphosphine palladium (0.05 mmol) were added, potassium carbonate (2 mmol) was heated to 90℃and reacted for 12 hours, after completion of the reaction, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: n-hexane=1:50) to give intermediate B-353-2 (yield 80%).
A100 mL three-neck round bottom bottle is taken and placed into a stirrer and an upper return pipe, raw material B-353-2 (1 mmol), (methoxymethyl) triphenylphosphine chloride (1.8 mmol) and THF (10 mL) are added, the temperature is reduced to-5 ℃ to-10 ℃, and a tetrahydrofuran (150 mL) solution of t-BuOK (27 g) is slowly added dropwise by a constant pressure dropping funnel, wherein the temperature is always kept below-5 ℃. After the completion of the dropwise addition, the reaction was carried out at this temperature for 20 minutes. Then slowly heating to room temperature, and after the reaction liquid reaches the room temperature, continuing the reaction for 1h, and stopping the reaction. The reaction was extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: n-hexane=1:50) to give intermediate B-353-3 (yield 80%).
A100 mL three-necked round bottom flask was taken and placed in a stirrer and a top reflux tube, and B-353-3 (1 mmol) and hexafluoroisopropanol (14 mL) were added. Under the protection of nitrogen, the temperature is reduced to minus 5 ℃ to minus 10 ℃, after the temperature is reached, the triflic acid (3 mmol) is slowly added dropwise by a constant pressure dropping funnel, and the temperature is always kept below minus 5 ℃. After the completion of the dropwise addition, the reaction was carried out at this temperature for 20 minutes. Then slowly heating to room temperature, and after the reaction liquid reaches the room temperature, continuing the reaction for 1h, and stopping the reaction. The reaction was extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: n-hexane=1:50) to give intermediate B-353-4 (yield 80%).
A100 mL three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, raw material B-353-4 (1 mmol) was added, raw material bispinacol borate (1 mmol), dioxane 10mL, 1' -bisdiphenylphosphino ferrocene palladium dichloride (0.05 mmol), potassium acetate (2 mmol) were added, the reaction was heated to 110℃for 12 hours, after the reaction was completed, the temperature was lowered to room temperature, water and ethyl acetate were used for extraction, the organic phase was dried over anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: N-hexane=1:50) to obtain intermediate N-B353 (yield 80%).
Figure BDA0004031952650000721
Step 2) Synthesis of intermediate N-A353 (reaction scheme above)
A100 mL three-necked round bottom flask was placed in a stirrer and an upper reflux tube, intermediate N-B353 (1 mmol), 2-bromo-5- (4, 5-tetramethyl-1, 3, 2-dioxapentaborane-2-yl) pyridine (1.05 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), tetrakis triphenylphosphine palladium (0.05 mmol), potassium carbonate (2 mmol), heating to 90℃and reacting for 12 hours were added, after completion of the reaction, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give intermediate N-A353 (80% yield).
Step 3) Synthesis of Compound N-353
Figure BDA0004031952650000731
Synthesis of intermediate N-C353 (reaction scheme above)
100 ml of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate 2- (4-biphenyl) -4, 6-dichloro-1, 3, 5-triazine, 4- (4-pyridyl) phenylboronic acid (0.95 mmol) toluene (9 ml) was added, water (3 ml), 1' -bis-diphenylphosphino ferrocene palladium dichloride (0.05 mmol) and sodium carbonate (2 mmol) were added, heated to 90℃for 12 hours, after the reaction was completed, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: N-hexane=1:50) to obtain intermediate N-C353 (yield 80%).
Figure BDA0004031952650000732
Synthesis of Compound N-353 (reaction scheme above)
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate N-C353 (1 mmol), intermediate N-A353 (1 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), palladium 132 (0.02 mmol), sodium bicarbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, after completion of the reaction, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give structure N-353 (yield 80%).
Elemental analysis: c (C) 51 H 31 N 5 Theoretical value of O: c,83.93; h,4.28; n,9.60; o, found 2.19: c,83.95; h,4.28; n,9.58; HRMS (ESI) M/z (m+): theoretical value: 729.25; actual measurement value: 729.26.
example 17
The embodiment provides an organic electroluminescent compound N-341, and the preparation method of the compound N-341 specifically comprises the following steps:
Figure BDA0004031952650000741
synthesis of intermediate N-A341 (reaction scheme above)
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate N-B353 (1 mmol), 2-bromopyridine-5-boronic acid (1.05 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), and tetrakis triphenylphosphine palladium (0.05 mmol), potassium carbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, after the reaction was completed, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: N-hexane=1:50) to give intermediate N-A431 (yield 80%).
Synthesis of Compound N-341
Figure BDA0004031952650000742
Synthesis of Compound N-341 (reaction scheme above)
100mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate N-A341 (1.05 mmol), intermediate N-C14 (1 mmol), toluene (9 mL), water (3 mL), palladium 132 (0.02 mmol), sodium bicarbonate (2 mmol) were added, the temperature was heated to 90℃for 12 hours, after the reaction was completed, the temperature was lowered to room temperature, water and ethyl acetate were used for extraction, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give structure N-341 (yield 80%).
Elemental analysis: c (C) 45 H 27 N 5 Theoretical value of O: c,82.68; h,4.16; n,10.71; o,2.45; actual measurement value: c,82.71; h,4.15; n,10.69; o,2.45; HRMS (ESI) M/z (m+): theoretical value: 653.22; actual measurement value: 654.21.
example 18
The embodiment provides an organic electroluminescent compound N-399, and the preparation method of the compound N-399 specifically comprises the following steps:
Figure BDA0004031952650000751
step 1) Synthesis of intermediate N-B399 (reaction scheme above)
100mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, raw material 399-A (1 mmol), raw material 2-B (1 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), and tetrakis triphenylphosphine palladium (0.05 mmol) were added, potassium carbonate (2 mmol) was heated to 90℃and reacted for 12 hours, after completion of the reaction, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: n-hexane=1:50) to give intermediate 399-B-2 (yield 80%).
A100 mL three-neck round bottom bottle is taken and placed into a stirrer and an upper return pipe, raw materials 399-B-2 (1 mmol), (methoxymethyl) triphenylphosphine chloride (1.8 mmol) and THF (10 mL) are added, the temperature is reduced to-5 ℃ to-10 ℃, and a tetrahydrofuran (150 mL) solution of t-BuOK (27 g) is slowly added dropwise by a constant pressure dropping funnel, wherein the temperature is always kept below-5 ℃. After the completion of the dropwise addition, the reaction was carried out at this temperature for 20 minutes. Then slowly heating to room temperature, and after the reaction liquid reaches the room temperature, continuing the reaction for 1h, and stopping the reaction. The reaction was extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: n-hexane=1:50) to give intermediate 399-B-3 (yield 80%).
A100 mL three-necked round bottom flask was taken and placed in a stirrer and a reflux tube attached thereto, and 399-B-3 (1 mmol) and hexafluoroisopropanol (14 mL) were added. Under the protection of nitrogen, the temperature is reduced to minus 5 ℃ to minus 10 ℃, after the temperature is reached, the triflic acid (3 mmol) is slowly added dropwise by a constant pressure dropping funnel, and the temperature is always kept below minus 5 ℃. After the completion of the dropwise addition, the reaction was carried out at this temperature for 20 minutes. Then slowly heating to room temperature, and after the reaction liquid reaches the room temperature, continuing the reaction for 1h, and stopping the reaction. The reaction was extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: n-hexane=1:50) to give intermediate 399-B-4 (yield 80%).
A100 mL three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, raw material 399-B-4 (1 mmol) was added, raw material bispinacol borate (1 mmol), dioxane 10mL, 1' -bisdiphenylphosphino ferrocene palladium dichloride (0.05 mmol), potassium acetate (2 mmol) were added, the reaction was heated to 110℃for 12 hours, after the reaction was completed, the temperature was lowered to room temperature, water and ethyl acetate were used for extraction, the organic phase was dried over anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: N-hexane=1:50) to obtain intermediate N-B399 (yield 80%).
Figure BDA0004031952650000761
Step 2) Synthesis of intermediate N-A399 (reaction scheme above)
A100 mL three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, raw material N-B399 (1 mmol), 2-bromo-5- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) pyrimidine (1.05 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), and tetrakis triphenylphosphine palladium (0.05 mmol) were added, potassium carbonate (2 mmol) was heated to 90℃and reacted for 12 hours, after completion of the reaction, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give intermediate N-A399 (80% yield).
Step 3) Synthesis of Compound N-399
Figure BDA0004031952650000762
Synthesis of intermediate 399-D (reaction scheme above)
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, 5-bromopyrimidine (1 mmol), 1, 2-phenylboronic acid (1 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), tetrakis triphenylphosphine palladium (0.05 mmol), potassium carbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, after completion of the reaction, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: n-hexane=1:50) to give intermediate 399-D (yield 80%).
Synthesis of intermediate N-C399 (reaction scheme above)
A100 mL three-necked round bottom flask was taken and placed in a stirrer and upper reflux tube, raw material intermediate 399-D (1 mmol), 2- (4-biphenyl) -4, 6-dichloro-1, 3, 5-triazine (1 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), tetrakis triphenylphosphine palladium (0.05 mmol), potassium carbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, cooled to room temperature after the end of the reaction, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give intermediate N-C399 (80% yield).
Figure BDA0004031952650000771
Synthesis of Compound N-399 (reaction scheme above)
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate N-C399 (1 mmol), intermediate N-A399 (1 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), palladium 132 (0.02 mmol), sodium bicarbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, after completion of the reaction, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give structure N-399 (yield 80%).
Elemental analysis: c (C) 49 H 29 N 7 S theory: c,78.69; h,3.91; n,13.11; s,4.29 found: c,78.72; h,3.93; n,13.08; s,4.27; HRMS (ESI) M/z (m+): theoretical value: 747.22; actual measurement value: 748.24.
example 19
The embodiment provides an organic electroluminescent compound N-344, and the preparation method of the compound N-344 specifically comprises the following steps:
Figure BDA0004031952650000772
synthesis of intermediate N-A344 (reaction scheme above)
A100 mL three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, raw material N-B399 (1 mmol), 2-bromopyridine-5-boronic acid (1.05 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), and tetrakis triphenylphosphine palladium (0.05 mmol), potassium carbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, after the reaction was completed, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: N-hexane=1:50) to give intermediate N-A344 (yield 80%).
Synthesis of Compound N-344
Figure BDA0004031952650000781
Synthesis of Compound N-344 (reaction scheme above)
100mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate N-A344 (1.05 mmol), intermediate N-C14 (1 mmol), toluene (9 mL), water (3 mL), palladium 132 (0.02 mmol), sodium bicarbonate (2 mmol) were added, the temperature was heated to 90℃for 12 hours, after the reaction was completed, the temperature was lowered to room temperature, water and ethyl acetate were used for extraction, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give structure N-344 (yield 80%).
Elemental analysis: c (C) 45 H 27 N 5 S theory: c,80.69; h,4.06; n,10.46; s,4.79; actual measurement value: c,80.71; h,4.08; n,10.43; s,4.78; HRMS (ESI) M/z (m+): theoretical value: 669.20; actual measurement value: 670.33.
example 20
The embodiment provides an organic electroluminescent compound N-350, and the preparation method of the compound N-350 specifically comprises the following steps:
Figure BDA0004031952650000782
step 1) Synthesis of intermediate N-B350 (reaction scheme above)
100mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, raw material 350-A (1 mmol), raw material 2-B (1 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), and tetrakis triphenylphosphine palladium (0.05 mmol) were added, potassium carbonate (2 mmol) was heated to 90℃and reacted for 12h, after completion of the reaction, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: n-hexane=1:50) to give intermediate 350-B-2 (yield 80%).
A100 mL three-neck round bottom bottle is taken and placed into a stirrer and an upper return pipe, raw materials 350-B-2 (1 mmol), (methoxymethyl) triphenylphosphine chloride (1.8 mmol) and THF (10 mL) are added, the temperature is reduced to-5 ℃ to-10 ℃, and a tetrahydrofuran (150 mL) solution of t-BuOK (27 g) is slowly added dropwise by a constant pressure dropping funnel, wherein the temperature is always kept below-5 ℃. After the completion of the dropwise addition, the reaction was carried out at this temperature for 20 minutes. Then slowly heating to room temperature, and after the reaction liquid reaches the room temperature, continuing the reaction for 1h, and stopping the reaction. The reaction was extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: n-hexane=1:50) to give intermediate 350-B-3 (yield 80%).
A100 mL three-necked round bottom flask was taken and placed in a stirrer and a top reflux tube, and 350-B-3 (1 mmol) and hexafluoroisopropanol (14 mL) were added. Under the protection of nitrogen, the temperature is reduced to minus 5 ℃ to minus 10 ℃, after the temperature is reached, the triflic acid (3 mmol) is slowly added dropwise by a constant pressure dropping funnel, and the temperature is always kept below minus 5 ℃. After the completion of the dropwise addition, the reaction was carried out at this temperature for 20 minutes. Then slowly heating to room temperature, and after the reaction liquid reaches the room temperature, continuing the reaction for 1h, and stopping the reaction. The reaction was extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: n-hexane=1:50) to give intermediate 350-B-4 (yield 80%).
A100 mL three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, raw material 350-B-4 (1 mmol) was added, raw material bispinacol borate (1 mmol), dioxane 10mL, 1' -bisdiphenylphosphino ferrocene palladium dichloride (0.05 mmol), potassium acetate (2 mmol) were added, the reaction was heated to 110℃for 12 hours, after the reaction was completed, the temperature was lowered to room temperature, water and ethyl acetate were used for extraction, the organic phase was dried over anhydrous magnesium sulfate, and the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: N-hexane=1:50) to obtain intermediate N-B350 (yield 80%).
Figure BDA0004031952650000791
Step 2) Synthesis of intermediate N-A350 (reaction scheme above)
A100 mL three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, raw material N-B350 (1 mmol), 2-bromo-5- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) pyridine 1.05 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), tetrakis triphenylphosphine palladium (0.05 mmol), potassium carbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, after completion of the reaction, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was purified by column chromatography (DCM: n-hexane=1: 50 Isolation of intermediate N-a350 (80% yield).
Step 3) Synthesis of Compound N-350
Figure BDA0004031952650000801
Synthesis of intermediate N-C350 (reaction scheme above)
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, 5-bromopyrimidine (1 mmol), 1, 2-phenylboronic acid (1 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), tetrakis triphenylphosphine palladium (0.05 mmol), potassium carbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, after completion of the reaction, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give intermediate N-C350 (yield 80%).
Figure BDA0004031952650000802
Synthesis of Compound N-350 (reaction scheme above)
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate N-C350 (1 mmol), intermediate N-A353 (1 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), palladium 132 (0.02 mmol), sodium bicarbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, after completion of the reaction, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give structure N-350 (yield 80%).
Elemental analysis: c (C) 49 H 29 N 5 Theoretical value of O: c,83.62; h,4.15; n,9.95; o,2.27 found: c,83.64; h,4.16; n,9.92; HRMS (ESI) M/z (m+): theoretical value: 703.24; actual measurement value: 704.25.
example 21
The embodiment provides an organic electroluminescent compound N-391, the preparation method of the compound N-391 specifically comprises the following steps:
Figure BDA0004031952650000811
synthesis of intermediate N-A391 (reaction scheme above)
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate N-B353 (1 mmol) was added, 2-bromo-5- (4, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) pyrimidine (1.05 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), tetrakis triphenylphosphine palladium (0.05 mmol), potassium carbonate (2 mmol) was added, heated to 90℃for 12 hours, after completion of the reaction, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give intermediate N-A391 (80% yield).
Synthesis of Compound N-391
Figure BDA0004031952650000812
Synthesis of intermediate N-C391 (reaction scheme above)
A100 mL three-necked round bottom flask was placed in a stirrer and an upper reflux tube, intermediate 2, 4-dichloro-6-naphthalen-1-yl- [1,3,5] triazine (1.05 mmol) was added, B- [4- (2-pyrimidinyl) phenyl ] boronic acid (0.95 mmol) toluene (9 mL), water (3 mL), 1' -bis-diphenylphosphino ferrocene palladium dichloride (0.05 mmol), sodium carbonate (2 mmol) were added, heated to 90℃C, reacted for 12 hours, cooled to room temperature after completion of the reaction, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give intermediate N-C391 (80% yield).
Figure BDA0004031952650000821
/>
Synthesis of Compound N-391 (reaction scheme above)
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate N-C391 (1.05 mmol), intermediate N-A391 (1 mmol), toluene (9 mL), water (3 mL), palladium 132 (0.02 mmol), sodium bicarbonate (2 mmol) were added, the temperature was heated to 90℃for 12 hours, after the reaction was completed, the temperature was lowered to room temperature, water and ethyl acetate were used for extraction, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give structure N-391 (yield 80%).
Elemental analysis: c (C) 47 H 27 N 7 Theoretical value of O: c,79.98; h,3.86; n,13.89; o,2.27; actual measurement value: c,80.00; h,3.87; n,13.86; HRMS (ESI) M/z (m+): theoretical value: 705.23; actual measurement value: 706.27.
example 22
The embodiment provides a preparation method of an organic electroluminescent compound N-393, wherein the preparation method of the compound N-393 specifically comprises the following steps:
Figure BDA0004031952650000822
synthesis of intermediate N-C393 (reaction scheme above)
A100 mL three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, 2, 4-dichloro-6-biphenyl-1, 3, 5-triazine (1.05 mmol), 3- (pyrimidin-4-yl) phenylboronic acid (0.95 mmol) toluene (9 mL), water (3 mL), 1' -bis-diphenylphosphino ferrocene palladium dichloride (0.05 mmol), sodium carbonate (2 mmol) were added, heated to 90℃for 12 hours, cooled to room temperature after the reaction was completed, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give structure N-C393 (yield 80%).
Figure BDA0004031952650000831
Synthesis of Compound N-393 (reaction scheme above)
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate N-A391 (1.05 mmol), intermediate N-C393 (1 mmol), toluene (9 mL), water (3 mL), palladium 132 (0.02 mmol), sodium bicarbonate (2 mmol) were added, heated to 90℃for 12 hours, cooled to room temperature after the reaction was completed, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give structure N-393 (yield 80%).
Elemental analysis: c (C) 49 H 29 N 7 Theoretical value of O: c,80.42; h,3.99; n,13.40; o,2.19; actual measurement value: c,80.45; h,3.98; n,13.38; HRMS (ESI) M/z (m+): theoretical value: 731.24; actual measurement value: 732.37.
example 23
The embodiment provides an organic electroluminescent compound N-415, and the preparation method of the compound N-415 specifically comprises the following steps:
Figure BDA0004031952650000832
synthesis of intermediate N-A415 (reaction scheme above)
A100 mL three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, raw material N-B2 (1 mmol), 5-bromopyridine-3-boronic acid (1.05 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), and tetrakis triphenylphosphine palladium (0.05 mmol), potassium carbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, after the reaction was completed, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: N-hexane=1:50) to give intermediate N-A415 (yield 80%).
Figure BDA0004031952650000841
Synthesis of Compound N-415 (reaction scheme above)
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate N-C14 (1.05 mmol), intermediate N-C415 (1 mmol), toluene (9 mL), water (3 mL), palladium 132 (0.02 mmol), sodium bicarbonate (2 mmol) were added, the temperature was heated to 90℃for 12 hours, after the reaction was completed, the temperature was lowered to room temperature, water and ethyl acetate were used for extraction, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give structure N-415 (yield 80%).
Elemental analysis: c (C) 45 H 27 N 5 Theoretical value of O: c,82.68; h,4.16; n,10.71; o,2.45; actual measurement value: c,82.72; h,4.15; n,10.68; HRMS (ESI) M/z (m+): theoretical value: 747.22; actual measurement value: 748.24.
example 24
The embodiment provides an organic electroluminescent compound N-422, and the preparation method of the compound N-422 specifically comprises the following steps:
Figure BDA0004031952650000842
synthesis of intermediate N-A422 (reaction scheme above)
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate N-B353 (1 mmol), 2-bromopyrazine 6-boronic acid (1.05 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), and tetrakis triphenylphosphine palladium (0.05 mmol), potassium carbonate (2 mmol) were added, heated to 90℃and reacted for 12 hours, after the reaction was completed, cooled to room temperature, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: N-hexane=1:50) to give intermediate N-A422 (yield 80%).
Synthesis of Compound N-422 (reaction scheme above)
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate N-C14 (1.05 mmol), intermediate N-A422 (1 mmol), toluene (9 mL), water (3 mL), palladium 132 (0.02 mmol), sodium bicarbonate (2 mmol) were added, the temperature was heated to 90℃for 12 hours, after the reaction was completed, the temperature was lowered to room temperature, water and ethyl acetate were used for extraction, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was separated by column chromatography (DCM: N-hexane=1:50) to give structure N-422 (yield 80%).
Elemental analysis: c (C) 44 H 26 N 6 Theoretical value of O: c,80.72; h,4.00; n,12.84; o,2.44; actual measurement value: c,80.75; h,4.01; n,12.81; HRMS (ESI) M/z (m+): theoretical value: 654.22; actual measurement value: 655.21.
example 25
The embodiment provides an organic electroluminescent compound N-426, and the preparation method of the compound N-426 specifically comprises the following steps:
Figure BDA0004031952650000852
synthesis of intermediate N-A426 (reaction scheme above)
A100 mL three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, raw material N-B399 (1 mmol), 2-bromopyrazine 6-boronic acid (1.05 mmol), toluene (9 mL), ethanol (3 mL), water (3 mL), and tetrakis triphenylphosphine palladium (0.05 mmol), potassium carbonate (2 mmol) were added, heated to 90℃C, reacted for 12 hours, cooled to room temperature after the reaction was completed, extracted with water and ethyl acetate, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give intermediate N-A426 (yield 80%).
Figure BDA0004031952650000861
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Synthesis of Compound N-426 (reaction scheme above)
100 mL of a three-necked round bottom flask was taken and placed in a stirrer and an upper reflux tube, intermediate N-C14 (1.05 mmol), intermediate N-A426 (1 mmol), toluene (9 mL), water (3 mL), palladium 132 (0.02 mmol), sodium bicarbonate (2 mmol) were added, the temperature was heated to 90℃for 12 hours, after the reaction was completed, the temperature was lowered to room temperature, water and ethyl acetate were used for extraction, the organic phase was dried over anhydrous magnesium sulfate, the solvent was removed using a rotary evaporator, and the crude product was isolated by column chromatography (DCM: N-hexane=1:50) to give structure N-426 (yield 80%).
Elemental analysis: c (C) 44 H 26 N 6 S theory: c,78.78; h,3.91; n,12.53; s,4.78; actual measurement value: c,78.81; h,3.92; n,12.50; s,4.77; HRMS (ESI) M/z (m+): theoretical value: 670.19; actual measurement value: 671.30.
device embodiment
The embodiment provides an organic electroluminescent device, as shown in fig. 1, including an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, an electron transport layer 6, an electron injection layer 7 and a cathode 8, which are sequentially stacked on a substrate 1, wherein the device structure is as follows: 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).
The materials for manufacturing the organic electroluminescent device are as follows:
Figure BDA0004031952650000862
Figure BDA0004031952650000871
the preparation of the organic electroluminescent device comprises the following steps:
1) Cleaning a substrate:
the glass substrate coated with transparent ITO is subjected to ultrasonic treatment in an aqueous cleaning agent (the components and the concentration of the aqueous cleaning agent are that the glycol solvent is less than or equal to 10wt percent and the triethanolamine is less than or equal to 1wt percent), then washed in deionized water, subjected to ultrasonic degreasing in a mixed solvent of acetone and ethanol (the volume ratio of the acetone to the ethanol is 1:1), baked in a clean environment until the moisture is completely removed, and then cleaned by ultraviolet light and ozone.
2) Organic layer preparation:
: transferring ITO transparent substrate into vapor deposition equipment, and vacuumizing to 1×10 -6 Up to 2X 10 -4 Pa, sequentially evaporating a 10nm Hole Injection Layer (HIL)/80 nm Hole Transport Layer (HTL)/38 nm light emitting layer (EML)/30 nm Electron Transport Layer (ETL)/1 nm Electron Injection Layer (EIL)/80 nm thick cathode (Al) on the anode film.
Wherein:
the Hole Injection Layer (HIL) is made of a mixture of NDP-9 and HT, wherein the mass ratio of the NDP-9 to the HT is 3:97;
the Hole Transport Layer (HTL) is made of HT;
the material of the light emitting layer (EML) comprises a host material and a guest material, wherein the host material is the organic electroluminescent composition shown in the formula 1 prepared by the invention, or the organic electroluminescent composition shown in the formula 1 and the organic electroluminescent composition shown in the formula 3 prepared by the invention, and the guest material is (piq) 2Ir (acac); the specific materials and the proportions are shown in table 1;
The materials of the Electron Transport Layer (ETL) are shown in table 1;
the material of the Electron Injection Layer (EIL) is LiQ; the organic electroluminescent device part layer, and materials and thicknesses thereof are shown in table 1.
TABLE 1
Figure BDA0004031952650000872
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Figure BDA0004031952650000881
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Figure BDA0004031952650000891
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Figure BDA0004031952650000901
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Figure BDA0004031952650000911
Test case
The organic electroluminescent devices obtained in device examples 1 to 25 and comparative examples 1 to 4 in device examples were tested.
Instrument: the characteristics of current, voltage, brightness, luminescence spectrum and the like of the device are synchronously tested by adopting a PR 650 spectrum scanning luminance meter and a Keithley K2400 digital source meter system;
test conditions: photoelectric characteristic test conditions: the current density was 10mA/cm2.
Life test: the current density was 50mA/cm2 and the time (in hours) was recorded when the device brightness was reduced to 95% of the original brightness.
The device performance test results are shown in table 2:
TABLE 2
Figure BDA0004031952650000912
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Figure BDA0004031952650000921
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.

Claims (15)

1. An organic electroluminescent compound characterized by having the structure shown below:
Figure FDA0004031952640000011
wherein Ar is 1 -Ar 3 Each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C5-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl; wherein Ar is 1 -Ar 3 At least one of which is selected from the structures shown in formula 2,
Figure FDA0004031952640000012
wherein T is 1 ，T 2 ，T 3 ，T 4 ，T 5 Each independently selected from CR or N, R is selected from hydrogen or deuterium, and T 1 ，T 2 ，T 3 ，T 4 ，T 5 At least one of which is selected from N;
L 1 -L 4 each independently selected from the group consisting of a bond, a substituted or unsubstituted C1-C6 alkylene, a substituted or unsubstituted C6-C30 arylene, and a substituted or unsubstituted C3-C60 heteroarylene;
x is selected from O or S;
the substituent of the substituted C1-C30 alkyl, substituted C3-C30 cycloalkyl, substituted C5-C60 aryl, substituted C3-C60 heteroaryl, substituted C1-C6 alkylene, substituted C6-C30 arylene and substituted C3-C60 heteroarylene is selected from one or two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C5-C12 aryl and C3-C12 heteroaryl.
2. The organic electroluminescent compound as claimed in claim 1, wherein,
The organic electroluminescent compound has a structure as shown below:
Figure FDA0004031952640000021
wherein Ar is 2 -Ar 3 Each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C5-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl;
T 1 ，T 2 ，T 3 ，T 4 ，T 5 each independently selected from CR or N, R is selected from hydrogen or deuterium, and T 1 ，T 2 ，T 3 ，T 4 ，T 5 At least one of which is selected from N;
L 2 -L 3 each independently selected from the group consisting of a bond, a substituted or unsubstituted C1-C6 alkylene, a substituted or unsubstituted C6-C30 arylene, and a substituted or unsubstituted C3-C60 heteroarylene;
x is selected from O or S;
the substituent of the substituted C1-C30 alkyl, substituted C3-C30 cycloalkyl, substituted C5-C60 aryl, substituted C3-C60 heteroaryl, substituted C1-C6 alkylene, substituted C6-C30 arylene and substituted C3-C60 heteroarylene is selected from one or two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C5-C12 aryl and C3-C12 heteroaryl.
3. The organic electroluminescent compound according to claim 1 or 2, which isCharacterized in that L 1 -L 4 Each independently selected from the group consisting of a linkage, a substituted or unsubstituted C6-C30 arylene group.
4. An organic electroluminescent compound as claimed in any one of claims 1 to 3, wherein Ar 1 -Ar 3 Each independently selected from the group consisting of substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C5-C60 aryl, and substituted or unsubstituted C3-C60 heteroaryl.
5. The organic electroluminescent compound as claimed in claim 1 or 2, wherein L 2 -L 3 Each independently selected from single bond, C6-C30 arylene;
Ar 2 -Ar 3 each independently selected from the group consisting of C6-C30 aryl, C3-C18 heteroaryl;
x is selected from O or S.
6. The organic electroluminescent compound as claimed in claim 1 or 2, wherein,
T 1 selected from N, T 2 ，T 3 ，T 4 ，T 5 Each independently selected from CR;
or T is 2 Selected from N, T 1 ，T 3 ，T 4 ，T 5 Each independently selected from CR;
or T is 1 ，T 5 Selected from N, T 2 ，T 3 ，T 4 Each independently selected from CR;
or T is 2 ，T 5 Selected from N, T 1 ，T 3 ，T 4 Each independently selected from CR;
or T is 1 ，T 4 Selected from N, T 2 ，T 3 ，T 5 Each independently selected from CR;
r is selected from hydrogen or deuterium.
7. The organic electroluminescent compound as claimed in claim 1 or 2, wherein,
L 2 -L 3 each independently selected from a single bond, phenylene, naphthylene;
Ar 2 -Ar 3 each independently selected from phenyl, naphthyl, pyridyl, pyrimidinyl.
8. The organic electroluminescent compound according to any one of claims 1 to 7, wherein the organic electroluminescent compound is selected from the group consisting of:
Figure FDA0004031952640000031
Figure FDA0004031952640000041
Figure FDA0004031952640000051
Figure FDA0004031952640000061
Figure FDA0004031952640000071
Figure FDA0004031952640000081
Figure FDA0004031952640000091
Figure FDA0004031952640000101
/>
Figure FDA0004031952640000111
/>
Figure FDA0004031952640000121
/>
Figure FDA0004031952640000131
/>
Figure FDA0004031952640000141
/>
Figure FDA0004031952640000151
/>
Figure FDA0004031952640000161
/>
Figure FDA0004031952640000171
/>
Figure FDA0004031952640000181
/>
Figure FDA0004031952640000191
/>
Figure FDA0004031952640000201
/>
Figure FDA0004031952640000211
/>
Figure FDA0004031952640000221
/>
Figure FDA0004031952640000231
/>
Figure FDA0004031952640000241
/>
Figure FDA0004031952640000251
/>
Figure FDA0004031952640000261
/>
Figure FDA0004031952640000271
/>
Figure FDA0004031952640000281
/>
Figure FDA0004031952640000291
/>
Figure FDA0004031952640000301
/>
Figure FDA0004031952640000311
/>
Figure FDA0004031952640000321
/>
Figure FDA0004031952640000331
/>
Figure FDA0004031952640000341
/>
Figure FDA0004031952640000351
/>
Figure FDA0004031952640000361
/>
Figure FDA0004031952640000371
9. An organic electroluminescent composition comprising the organic electroluminescent compound as claimed in any one of claims 1 to 8, and a compound having a structure as shown below:
Figure FDA0004031952640000372
wherein Ar is W1 、Ar W2 、Ar W3 Each independently selected from hydrogen, deuterium, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, ar W1 、Ar W2 、Ar W3 Are not connected with each other or are connected with adjacent two to form a ring;
L W1 、L W2 、L W3 each independently selected from the group consisting of a bond, a substituted or unsubstituted C6-C30 arylene, a substituted or unsubstituted C3-C30 heteroarylene;
the substituent of the substituted C6-C60 aryl, the substituted C3-C60 heteroaryl, the substituted C6-C30 arylene and the substituted C3-C30 heteroarylene is selected from one or two of deuterium, halogen, cyano, C1-C6 alkyl, C3-C30 cycloalkyl, C5-C12 aryl and C3-C12 heteroaryl.
10. The organic electroluminescent composition according to claim 9, wherein in formula 3, ar W1 、Ar W2 、Ar W3 Each independently selected from hydrogen, deuterium, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted naphthyl, substituted or unsubstituted triphenylene, substituted or unsubstituted triazinyl, substituted or unsubstituted C3-C30 heteroaryl, and substituted or unsubstituted group Q, wherein the group Q is selected from one of the following structures:
Figure FDA0004031952640000381
Figure FDA0004031952640000382
Or Ar W1 、Ar W2 、Ar W3 Any two of which are linked to form a ring a, wherein ring a is:
Figure FDA0004031952640000383
wherein the substituent in the substituted phenyl, substituted biphenyl, substituted dibenzofuranyl, substituted naphthyl, substituted triphenylene, substituted triazinyl, substituted C3-C30 heteroaryl, and substituted group Q is selected from at least one of deuterium, phenyl, C1-C5 alkyl, and biphenyl;
ar is selected from deuterium, halogen, cyano, C6-C60 aryl;
R 10 -R 17 each independently selected from the group consisting of a bond, hydrogen, deuterium, halogen, cyano, C1-C30 alkyl, C3-C30 alkyl wherein one or more methylene groups are each substituted in a non-adjacent manner by-O-and/or-S atoms, C7-C30 aralkyl, C6-C30 aryl, C3-C30 heteroaryl, C4-C30 heteroaralkyl, C3-C30 cycloalkyl, C3-C30 heterocycloalkyl, C3-C30 cycloalkenyl, C1-C30 alkoxy, C6-C30 aryloxy;
alternatively, R 10 -R 17 The two adjacent rings are connected with a ring B, wherein the ring B is selected from a C6-C30 aromatic ring and a C3-C30 heteroaromatic ring;
preferably, L W1 、L W2 、L W3 Each independently selected from the group consisting of a linkage, phenylene, biphenylene, and naphthylene.
11. The organic electroluminescent composition according to claim 9 or 10, wherein the compound of formula 3 is selected from one of the following compounds:
Figure FDA0004031952640000384
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Figure FDA0004031952640000391
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Figure FDA0004031952640000401
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Figure FDA0004031952640000411
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Figure FDA0004031952640000421
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Figure FDA0004031952640000431
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Figure FDA0004031952640000441
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Figure FDA0004031952640000451
/>
Figure FDA0004031952640000461
12. The organic electroluminescent composition according to any one of claims 9 to 11, wherein the mass ratio of the organic electroluminescent compound according to any one of claims 1 to 8 to the compound having the structure of formula 3 is: 1:9-9:1;
preferably, the mass ratio of the organic electroluminescent compound according to any one of claims 1 to 8 to the compound having the structure of formula 3 is: 2:8-8:2;
more preferably, the mass ratio of the organic electroluminescent compound according to any one of claims 1 to 8 to the compound having the structure of formula 3 is: 3:7-7:3;
further preferably, the mass ratio of the organic electroluminescent compound according to any one of claims 1 to 8 to the compound having the structure of formula 3 is: 4:6-6:4.
13. An organic electroluminescent device comprising a first electrode, a second electrode, and an organic layer between the first electrode and the second electrode, the organic layer comprising the organic electroluminescent compound of any one of claims 1-8.
14. The organic electroluminescent device of claim 13, wherein the organic layer comprises an electron transport layer comprising the organic electroluminescent compound of any one of claims 1-8.
15. The organic electroluminescent device according to claim 13 or 14, wherein the organic layer comprises a light-emitting layer, and a material of the light-emitting layer comprises a host material and a guest material; the host material comprising the organic electroluminescent composition of any one of claims 9-12;
preferably, the guest material comprises a phosphorescent dopant or a thermally activated delayed fluorescence compound;
preferably, the phosphorescent dopant comprises a complex of a transition metal;
the organic electroluminescent device is an organic light emitting diode.
CN202211732230.8A 2022-12-30 2022-12-30 Organic electroluminescent compounds and use thereof Pending CN116425730A (en)

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