CN111574535A

CN111574535A - Organic electroluminescent compound and preparation method and application thereof

Info

Publication number: CN111574535A
Application number: CN202010463443.XA
Authority: CN
Inventors: 李祥智; 蔡烨; 丁欢达; 魏定纬; 陈志宽
Original assignee: Ningbo Lumilan New Material Co ltd
Current assignee: Ningbo Research Institute of Northwestern Polytechnical University; Ningbo Lumilan Advanced Materials Co Ltd
Priority date: 2020-05-27
Filing date: 2020-05-27
Publication date: 2020-08-25
Anticipated expiration: 2040-05-27
Also published as: CN111574535B

Abstract

The invention provides an organic electroluminescent compound, a preparation method and an application thereof, wherein the organic electroluminescent compound has a structure shown in a formula I; the organic electroluminescent device comprises a substrate, a first electrode, a second electrode and at least one organic layer which is inserted between the first electrode and the second electrode, wherein the organic layer contains any one or at least two combinations of organic electroluminescent compounds; the organic electroluminescent compounds have high luminous efficiency and long service life.

Description

Organic electroluminescent compound and preparation method and application thereof

Technical Field

The invention relates to the technical field of organic electroluminescence, in particular to an organic electroluminescent compound and a preparation method and application thereof.

Background

An electroluminescent device (EL device) is a self-luminous display device, which is advantageous in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time.

An organic EL device (OLED) converts electrical energy into light by applying power to an organic light emitting material, and generally includes an anode, a cathode, and an organic layer formed between the two electrodes. The organic layers of the OLED may include a hole injection layer, a hole transport layer, a hole assist layer, a light emission assist layer, an electron blocking layer, a light emitting layer (containing host and dopant materials), an electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, and the like, if desired. Materials used in the organic layer may be classified into a hole injection material, a hole transport material, a hole assist material, a light emission assist material, an electron blocking material, a light emitting material, an electron buffer material, a hole blocking material, an electron transport material, an electron injection material, and the like according to functions. In the OLED, holes from an anode and electrons from a cathode are injected into a light emitting layer by applying a voltage, and excitons having high energy are generated by recombination of the holes and the electrons. The organic light emitting compound moves to an excited state by energy and emits light by the energy when the organic light emitting compound returns to a ground state from the excited state.

Therefore, it is necessary to develop a host material that can be used in an OLED device and can improve the lifetime and luminous efficiency of the OLED device.

Disclosure of Invention

In view of the deficiencies of the prior art, the object of the present invention is to provide an organic electroluminescent compound having high efficiency and long lifetime, and a method for preparing the same. In order to achieve the purpose, the invention adopts the following technical scheme:

an object of the present invention is to provide an organic electroluminescent compound having a structure of formula I:

wherein, X¹Selected from O, S, CR⁷R⁸、SiR⁷R⁸Or is

Any one of the above;

X²selected from O, S, CR⁷R⁸Or

Any one of the above;

Y¹、Y²and Y³Each independently selected from O, S, CR⁷R⁸Or

Any one of the above;

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷and R⁸Each independently selected from hydrogen atom, deuterium atom, tritium atom, cyano, halogen, hydroxyl, nitro, amino, substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C2-C60 alkenyl, substituted or unsubstituted C2-C60 alkynyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted C1-C60 alkoxy, substituted or unsubstituted C1-C60 thioalkoxy, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C6-C60 thioaryloxy, -NR, hydroxyl, nitro, amino¹³R¹⁴、-SiR¹⁵R¹⁶R¹⁷Any one of the above; r¹³And R¹⁴Each independently selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl; r¹⁵、R¹⁶And R¹⁷Each independently selected from substituted or unsubstituted C1-C60 alkyl, substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl;

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸wherein each group is not linked to each other or wherein 2 to 4 adjacent groups are linked to form a ring, each of said rings being independently selected from any one of a saturated or partially unsaturated carbocyclic ring of C3-C7, a saturated or partially unsaturated carbocyclic ring of C3-C7, an aromatic ring of C6-C60, or an aromatic heterocyclic ring of C3-C30;

where partial unsaturation denotes: a carbon ring or a carbon heterocyclic ring having a double bond and not having aromaticity, such as cyclopentene, cyclohexene, and the like; halogen includes fluorine, chlorine, bromine, iodine.

L¹、L²And L³Each independently selected from a single bond, substituted or unsubstituted C1-C30 alkylene, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene, and substituted or unsubstituted C3-C30 cycloalkylene;

preferably, L¹、L²And L³Each independently selected from any one of a single bond, a substituted or unsubstituted C6-C30 arylene group, and a substituted or unsubstituted C3-C30 heteroarylene group.

Ar¹、Ar²And Ar³Each independently selected from substituted or unsubstituted aryl of C6-C60, substituted or unsubstituted heteroaryl of C3-C60, substituted or unsubstituted aryloxy of C6-C60, substituted or unsubstituted arylamine of C6-C60, substituted or unsubstituted thioaryloxy of C6-C60, substituted or unsubstituted arylboron of C6-C60, substituted or unsubstituted arylphosphine of C6-C60, any one of substituted or unsubstituted C4-C60 heteroaryloxy, substituted or unsubstituted C4-C60 heteroarylamino, substituted or unsubstituted C4-C60 aromatic-C4-C60 heteroarylamino, substituted or unsubstituted C4-C60 thiaheteroaryloxy, substituted or unsubstituted C4-C60 heteroarylboryl, and substituted or unsubstituted C4-C60 heteroarylphosphino;

preferably, Ar¹、Ar²And Ar³Each independently selected from substituted or unsubstituted aryl of C6-C60, substituted or unsubstituted heteroaryl of C3-C60,Any one of substituted or unsubstituted aryloxy groups of C6-C60, substituted or unsubstituted aromatic amine groups of C6-C60, substituted or unsubstituted thioaryloxy groups of C6-C60, substituted or unsubstituted heteroaryloxy groups of C4-C60, substituted or unsubstituted heteroaromatic amine groups of C4-C60 and substituted or unsubstituted thioheteroaromatic aryloxy groups of C4-C60.

Indicating an access site, as will appear hereinafter

The meaning of the indication is the access point, which is not described in detail later;

represents an aromatic ring structure, the meaning of which is similar to that of a benzene ring, is between a double bond and a single bond, is not a double bond or a single bond, and is only a conjugated structure; if the same hereinafter appears

The meaning of the indication is the same as that of the indication, and the description is omitted;

when the above groups contain heteroatoms, the heteroatoms are selected from O, S, N, P, B or Si or the combination of at least two of the above groups;

when the above groups contain substituents, the substituted group is any one of deuterium atom, halogen, nitro, cyano or C1-C4 alkyl substituted or unsubstituted by one or more of deuterium atom, halogen, cyano or nitro, C1-C4 alkoxy substituted or unsubstituted, C1-C4 alkenyl substituted or unsubstituted, C6-C12 aryl substituted or unsubstituted, C6-C12 aryloxy substituted or unsubstituted, C6-C12 arylamine substituted or unsubstituted, C3-C12 heteroaryl substituted or unsubstituted, and C3-C12 heteroarylamine substituted or unsubstituted.

Preferably, when the above groups contain a substituent, the substituent is selected from any one of hydrogen atom, deuterium atom, halogen, nitro, C1-C4 alkyl, halogen substituted C1-C4 alkyl, deuterium substituted C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkenyl, halogen substituted C1-C4 alkenyl, deuterium substituted C1-C4 alkenyl, C6-C12 aryl, C6-C12 aryloxy, C6-C12 arylamine, halogen substituted C6-C12 aryl, deuterium substituted C6-C12 aryl, C3-C12 heteroaryl, C3-C12 heteroarylamine, halogen substituted C3-C12 membered heteroaryl or deuterium substituted C39 3-C12 heteroaryl.

C1-C4 may be C2, C3.

C1-C10 may be C2, C3, C4, C5, C6, C7, C8, C9, etc.

C1-C30 may be C2, C5, C8, C10, C12, C15, C18, C20, C22, C25, C28, etc.

C1-C60 may be C2, C5, C8, C10, C12, C15, C18, C20, C22, C25, C28, C30, C32, C35, C38, C40, C42, C45, C48, C50, C52, C55, C58, C60, and the like.

C2-C60 may be C3, C5, C8, C10, C12, C15, C18, C20, C22, C25, C28, C30, C32, C35, C38, C40, C42, C45, C48, C50, C52, C55, C58, C60, and the like.

C3-C12 may be C4, C5, C6, C7, C8, C9, C10, C11, etc.

C3-C30 may be C4, C5, C8, C10, C12, C15, C18, C20, C22, C25, C28, C30, etc.

C3-C60 may be C4, C6, C8, C10, C12, C15, C18, C20, C22, C25, C28, C30, C32, C35, C38, C40, C42, C45, C48, C50, C52, C55, C58, and the like.

C4-C60 may be C6, C8, C10, C12, C15, C18, C20, C22, C25, C28, C30, C32, C35, C38, C40, C42, C45, C48, C50, C52, C55, C58, etc.

C6-C12 may be C7, C8, C9, C10, C11, etc.

C6-C30 may be C7, C10, C4, C13, C15, C18, C20, C22, C15, C28, etc.

C6-C60 may be C8, C10, C12, C15, C18, C20, C22, C25, C28, C30, C32, C35, C38, C40, C42, C45, C48, C50, C52, C55, C58, etc.

Aryl groups in the present invention include, but are not limited to, phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthryl, anthracenyl, indenyl, triphenylene, pyrenyl, tetracenyl, perylenyl, chrysenyl, condensed tetraphenyl, fluoranthenyl, spirobifluorenyl, and the like.

Heteroaryl groups in the present invention include, but are not limited to, furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothienyl, isobenzofuranyl, dibenzofuranyl, dibenzothienyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl, and the like.

The phrase "2 to 4 adjacent groups are linked to form a ring" as used herein means that R is¹-R⁸Wherein 2-4 substituents at adjacent positions in the same six-membered ring or adjacent six-membered rings can be connected with each other to form a ring through chemical bonds, and the invention does not limit the specific connecting ring forming mode, and has the same meaning when the same description is referred to below.

Preferably, said R is¹、R²、R³、R⁴、R⁵、R⁶、R⁷And R⁸Each independently selected from the group consisting of hydrogen atom, deuterium atom, tritium atom, cyano group, halogen, hydroxyl group, nitro group, amino group, substituted or unsubstituted C1-C4 alkyl group, substituted or unsubstituted C2-C4 alkenyl group, substituted or unsubstituted C2-C4 alkynyl group, substituted or unsubstituted C6-C20 aryl group, substituted or unsubstituted C3-C20 heteroaryl group, substituted or unsubstituted C1-C4 alkoxy group, and substituted or unsubstitutedSubstituted C1-C4 thioalkoxy, substituted or unsubstituted C6-C20 aryloxy, substituted or unsubstituted C6-C20 thioaryloxy, -NR¹³R¹⁴、-SiR¹⁵R¹⁶R¹⁷Any one of the above;

R¹³、R¹⁴each independently selected from substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 membered heteroaryl; r¹⁵、R¹⁶、R¹⁷Each independently selected from substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl;

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷and R⁸Wherein each group is not linked to each other or wherein 2 to 4 adjacent groups are linked to form a ring, each of said rings being independently selected from any one of a saturated or partially unsaturated carbocyclic ring of C3-C7, a saturated or partially unsaturated carbocyclic ring of C3-C7, an aromatic ring of C6-C60, or an aromatic heterocyclic ring of C3-C30;

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷and R⁸、R¹³、R¹⁴、R¹⁵、R¹⁶、R¹⁷Wherein each of said substituted groups independently has the same limitations as above.

Preferably, Ar is¹、Ar²And Ar³Each independently selected from any one of aryl of C6-C60, substituted or unsubstituted heteroaryl of C3-C60, substituted or unsubstituted aromatic amine of C6-C60 and substituted or unsubstituted heteroaromatic amine of C4-C60;

preferably, Ar is¹、Ar²And Ar³Each independently selected from any one of the following groups:

wherein Q is¹、Q²、Q³、Q⁴And Q⁵Each independently selected from N or CR¹⁰；

X³Selected from O, S, CR¹¹R¹²Or

Any one of the above;

n1 is an integer from 0 to 2 (e.g., 0, 1 or 2);

n2 is an integer from 0 to 4 (e.g., 0, 1,2, 3, or 4);

L⁴any one selected from a single bond, substituted or unsubstituted C1-C30 alkylene, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene, and substituted or unsubstituted C3-C30 cycloalkylene;

preferably, L⁴A heteroarylene selected from a single bond, a substituted or unsubstituted C6-C30 arylene, and a substituted or unsubstituted C3-C30;

Ar⁴independently selected from any one of hydrogen atom, deuterium atom, halogen, nitro, cyano, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C2-C4 alkenyl, substituted or unsubstituted C6-C30 aryl and substituted or unsubstituted C3-C30 heteroaryl;

R⁹、R¹⁰、R¹¹and R¹²Each independently selected from any one of hydrogen atom, deuterium atom, tritium atom, cyano, halogen, hydroxyl, nitro, amino, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C2-C4 alkenyl, substituted or unsubstituted C2-C4 alkynyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl, substituted or unsubstituted C1-C4 alkoxy, substituted or unsubstituted C1-C4 thioalkoxy, substituted or unsubstituted C6-C20 aryloxy and substituted or unsubstituted C6-C20 thioaryloxy; any two adjacent R⁹And/or R¹⁰The groups are not connected with each other or 2-4 adjacent groups are connected to form a ring, and each ring is independently selected from any one of C6-C20 aromatic rings or C3-C20 aromatic heterocyclic rings;

L⁴、Ar⁴、R⁹、R¹⁰、R¹¹and R¹²Wherein each of said substituted groups independently has the same limitations as defined in claim 1.

Preferably, said Q¹、Q²And Q³At least one of them is N.

Preferably, n2 is an integer from 0-2 (e.g., 0, 1, 2).

Preferably, Ar is¹、Ar²And Ar³Each independently selected from any one of substituted or unsubstituted Ar-1 to Ar-81 groups:

preferably, said L¹、L²And L³Each independently selected from any one of L-1 to L-8:

the compound with the structure of the formula I is formed by connecting CA, CB and X:

wherein,

and

the connection is carried out by connecting the two parts,

and

the connection is carried out by connecting the two parts,

and

connecting;

R¹、R²、R³、R⁴、R⁵、R⁶、X¹、X²、Y¹、Y²and Y³Each independently having the same limitations as described above.

The organic electroluminescent compound with the structure shown in the formula I is used as a main material of a light-emitting layer of an organic electroluminescent device, CZ and CB have strong electron-rich property, so that the compound has good hole transport performance, and in order to balance hole and electron mobility, an X1 group is adopted to connect CA and CB, so that the compound can be used in the organic electroluminescent device to improve the luminous efficiency and prolong the service life of the organic electroluminescent device.

Preferably, the CA is selected from any one of the following structures shown in CA-1-CA-15:

wherein L is¹And Ar¹Each independently having the same limitations as described above.

Preferably, the CB is selected from any one of the following structures shown by CB-1 to CB-14:

preferably, X is selected from any one of the following structures shown in X-1 to X-10:

wherein L is³And Ar³Each independently having the same limitations as described above.

As a preferred embodiment of the present invention, the organic electroluminescent compounds 1 to 1810 having the structure of formula I are shown in Table 1:

TABLE 1

It is a second object of the present invention to provide the use of an organic electroluminescent compound according to the first object as an organic electroluminescent material.

Preferably, the organic electroluminescent material is used as a host material of an organic electroluminescent layer.

It is a further object of the present invention to provide 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 any one or a combination of at least two of the organic electroluminescent compounds according to one of the objects.

Preferably, the organic layer includes a light-emitting layer including a host material and a guest material, the host material including any one of the organic electroluminescent compounds described in one of the objects or a combination of at least two of the organic electroluminescent compounds.

Preferably, the organic layer further includes any one of a hole injection layer, a hole transport layer, an electron injection layer, a hole blocking layer, an electron blocking layer, a light emission auxiliary layer, or a combination of at least two thereof.

Preferably, the number of the organic electroluminescent devices is at least two, and the at least two organic electroluminescent devices are stacked with each other to form a series structure.

It is a fourth object of the present invention to provide a use of the organic electroluminescent device as described in the fourth object in a display device or a lighting device.

The organic electroluminescent device of the present invention can produce a display system such as a smart phone, a tablet computer, a notebook, a PC, a TV, or a display system for an automobile; or a lighting system, such as an outdoor or indoor lighting system.

Compared with the prior art, the invention has the following beneficial effects:

the organic electroluminescent compound with the structure shown in the formula I is used as a main material of a light emitting layer of an organic electroluminescent device, CA and CB have strong electron-rich property, so that the compound has good hole transport performance, and in order to balance hole and electron mobility, an X1 group is used for connecting CA and CB, so that the compound can be used in the organic electroluminescent device to reduce the driving voltage of the luminescent device and increase the luminous efficiency and the service life of the luminescent device (when the compound is used as a material of the light emitting layer, the driving voltage is as low as 4.4-4.5V, the current efficiency can reach 21-28cd/A, and the service life can reach 50-85 h; when the compound is used as a material of the hole transport layer, the driving voltage is as low as 4.9V, the current efficiency can reach 14cd/A, and the service life can reach 18 h).

Drawings

Fig. 1 is a schematic structural diagram of an organic electroluminescent device provided in embodiment 1, where 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, 5 is a light-emitting layer, 6 is an electron transport layer, 7 is an electron injection layer, and 8 is a cathode.

Detailed Description

The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.

The synthesis method of the compound provided by the invention belongs to a conventional method, and a person skilled in the art can synthesize the compound by the prior art, and exemplarily provides a synthesis method of several typical compounds in the following preparation examples.

Compounds of synthetic methods not mentioned in the present invention are all starting products obtained commercially. The solvent and reagent used in the present invention, such as potassium carbonate, toluene, tetrakis (triphenylphosphine) palladium, toluene, potassium tert-butoxide, triethoxyphosphine, tris (dibenzylideneacetone) dipalladium, 2-dicyclohexylphosphino-2 ', 6' -dimethoxybiphenyl, xylene and other chemical reagents, can be purchased from domestic chemical product markets, such as reagents from national drug group, TCI, shanghai Biyao, Bailingwei reagents, etc. In addition, they can be synthesized by a known method by those skilled in the art.

The analytical detection of the intermediates and compounds in the present invention uses a mass spectrometer (model Orbitrap ID-XTrib) and an organic element analyzer (model PE2400 II).

The specific production method of the above-mentioned novel compound of the present invention will be described in detail below by taking a plurality of production examples as examples, but the production method of the present invention is not limited to these production examples.

Preparation example 1

(1) Synthesis of intermediates 1 to 1548: in a 100 ml three-necked flask, raw material 1(2.67 g, 0.01mol), raw material 2(2.94 g, 0.01mol), potassium carbonate (1.66 g, 0.012mol), toluene (35 ml), water (5 ml), tetrakis (triphenylphosphine) palladium (5.8 g, 0.5mmol) were added under nitrogen protection, stirred at 100 ℃ for 10 hours, and cooled to room temperature after reaction. Adding water into a reaction system, extracting by dichloromethane, and sequentially adding magnesium sulfate into the obtained extract liquor for drying, filtering and spin-drying; the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to afford intermediates 1-1548(2.83 g, 71% yield).

(2) Synthesis of intermediates 2-1548: adding the intermediate 1-1548(3.99 g, 0.01mol), the raw material 3(1.69 g, 0.012mol), potassium tert-butoxide (0.012mol), tris (dibenzylideneacetone) dipalladium (0.5mmol), 2-dicyclohexylphosphino-2 ', 6' -dimethoxybiphenyl (0.55mmol) and xylene (30 ml) into a 100 ml three-neck bottle under the protection of nitrogen, heating to 60 ℃, reacting for 8 hours, adding water into the reaction system, extracting by dichloromethane, and sequentially adding magnesium sulfate into the obtained extract for drying, filtering and spin-drying; the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to afford intermediate 2-1548(2.38 g, 48% yield).

(3) Synthesis of intermediates 3-1548: taking a 50 ml double-neck round-bottom bottle, putting a stirrer and an upper reflux pipe, drying, introducing nitrogen, respectively adding an intermediate 2-1548(4.96 g, 0.01mol), triphenylphosphine (0.02mol) and 1, 2-dichlorobenzene (25 ml), heating at 180 ℃ for reaction for 12 hours, cooling to room temperature after the reaction is finished, concentrating a reaction system, and purifying a crude product by chromatography (ethyl acetate/n-hexane, 1/10 (volume ratio)) to obtain an intermediate 3-1548(3.25 g, yield 70%).

(4)1548 Synthesis: a100 ml two-necked round-bottom flask was taken, a stirrer and an upper reflux pipe were placed, nitrogen was introduced after drying, 3 to 1548(4.64 g, 0.01mol) as an intermediate, 4(3.16 g, 0.01mol) as a raw material, cesium carbonate (0.012mol), tris (dibenzylideneacetone) dipalladium (Pd2(dba)3, 0.5mmol) and 2-dicyclohexylphosphonium-2 ', 4 ', 6 ' -triisopropylbiphenyl (xphos, 0.55mmol) were added, toluene was then added, the mixture was refluxed for 24 hours, cooled to room temperature after reaction, the reaction system was filtered and concentrated, and the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10 (volume ratio)) to obtain 1548(6.40 g, 86% yield).

Elemental analysis: c₅₂H₃₂N₄Theoretical value of S: c, 83.84, H, 4.33, N, 7.52, S, 4.30, found: c, 83.90, H, 4.32, N, 7.50, S, 4.28, HRMS (ESI) M/z (M)⁺): theoretical value: 744.2348, found: 744.2353.

preparation example 2

(1) Synthesis of intermediates 1-1602: taking a 100 ml double-neck round-bottom flask, putting a stirrer and an upper reflux pipe, introducing nitrogen after drying, respectively adding 5(2.49 g, 0.1mol) of raw materials, 6(3.05 g, 0.01mol) of raw materials, 0.05mmol of palladium acetate, 0.055mmol of tri-tert-butylphosphine, 0.015mol of sodium tert-butoxide and 30 ml of toluene, heating to 80 ℃ for reaction for 2 hours, adding water into a reaction system, extracting by dichloromethane, and sequentially adding magnesium sulfate into obtained extract liquor for drying, filtering and spin-drying; the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to afford intermediate 1-1602(2.51 g, 53% yield).

(2) Synthesis of intermediates 2-1602: taking a 100 ml double-neck round-bottom flask, putting a stirrer and an upper reflux pipe, introducing nitrogen after drying, and respectively adding the intermediate 1-1602(4.74 g, 0.01mol) and the dichloro bis (tricyclohexylphosphine) palladium (PdCl)₂(PCy₃)₂0.5mmol), pivalic acid (t-BuCO)₂H, 0.015mol), cesium carbonate (Cs)₂CO₃0.01mol) and dimethylacetamide (30 ml), stirred at 120 ℃ for 10 hours, cooled to room temperature after completion of the reaction, concentrated the reaction, and the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10 (vol.%)) to give intermediate 2-1602(2.45 g, 56% yield).

(3)1602 Synthesis: a100 ml two-neck round bottom flask is taken and put into a stirrer and an upper reflux pipe, nitrogen is filled after drying, and the intermediate 2-1602(4.38 g, 0.01mol), the raw material 7(2.40 g, 0.01mol), cesium carbonate (0.012mol), tris (dibenzylideneacetone) dipalladium (Pd) are respectively added₂(dba)₃0.5mmol) and 2-dicyclohexylphosphonium-2 ', 4 ', 6 ' -triisopropylbiphenyl (xphos, 0.55mmol), followed by addition of toluene, refluxing of the mixture for 24 hours, cooling to room temperature after the reaction, filtration of the reaction system and concentration, and chromatography purification of the crude product (dichloromethane/n-hexane, 1/10 (vol.%)) to give compound 1602(4.69 g, 73% yield).

Elemental analysis: c₄₄H₂₆N₄Theoretical value of S: c, 82.22, H, 4.08, N, 8.72, S, 4.99, found: c, 82.16, H, 4.09, N, 8.74, S, 5.01, HRMS (ESI) M/z (M)⁺): theoretical value: 642.1878, found: 642.1884.

preparation example 3

(1) Synthesis of intermediate 1-1779: in a 100 ml three-necked flask, under the protection of nitrogen, the raw materials 8(3.93 g, 0.01mol), 9(2.56 g, 0.01mol), potassium carbonate (1.66 g, 0.012mol), toluene (35 ml), water (5 ml), tetrakis (triphenylphosphine) palladium (5.8 g, 0.5mmol) were added, stirred at 100 ℃ for 10 hours, and cooled to room temperature after reaction. Adding water into a reaction system, extracting by dichloromethane, and sequentially adding magnesium sulfate into the obtained extract liquor for drying, filtering and spin-drying; the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to afford intermediate 1-1779(1.05 g, 23% yield).

(2) Synthesis of intermediate 2-1779: taking a 100 ml double-neck round-bottom bottle, putting a stirrer and an upper connecting reflux pipe into the bottle, drying the bottle, and filling nitrogen into the bottle; intermediate 1-1779(4.57 g, 0.01mol) was added, followed by anhydrous tetrahydrofuran (30 ml) and stirred at-78 ℃ for 10 minutes, followed by dropwise addition of a 2.5M solution of butyllithium in hexane (0.02mol) followed by reaction for 30 minutes, followed by dropwise addition of N, N, N ', N' -tetramethyl-1, 2-ethylenediamine (17 ml, 2.3 equivalents) and reaction for 2 hours, and finally, dimethyldichlorosilane (0.011mol) was added dropwise; after the reaction solution is cooled down, the reaction is stopped by saturated sodium bicarbonate aqueous solution (5 ml), then ethyl acetate (3X 15 ml) is used for extraction, and the obtained extract is sequentially added with magnesium sulfate for drying, filtering and spin-drying; the crude product was purified by chromatography (ethyl acetate/hexane, 1/15) to yield intermediate 2-1779(2.24 g, 63% yield).

(3)1779 Synthesis of: a100 ml double-neck round-bottom flask is taken, a stirrer and an upper reflux pipe are placed in the flask, nitrogen is filled in the flask after drying, and the intermediate 2-1779(3.55 g and 0.01mol), the raw material 10(3.23 g and 0.01mol), cesium carbonate (0.012mol) and tris (dibenzylideneacetone) dipalladium (Pd) are respectively added₂(dba)₃0.5mmol) and 2-dicyclohexylphosphonium-2 ', 4 ', 6 ' -triisopropylbiphenyl (xphos, 0.55mmol), followed by addition of toluene, refluxing of the mixture for 24 hours, cooling to room temperature after the reaction, filtration of the reaction system and concentration, and chromatography purification of the crude product (dichloromethane/n-hexane, 1/10 (vol.%)) to give compound 1779(4.37 g, 73% yield).

Elemental analysis: c₄₀H₃₀N₂Theory of SSiTheoretical value: c, 80.23, H, 5.05, N, 4.68, S, 5.35, found: c, 80.17, H, 5.07, N, 4.70, S, 5.37, HRMS (ESI) M/z (M)⁺): theoretical value: 598.1899, found: 598.1905.

preparation example 4

(1) Synthesis of intermediates 1 to 403: in a 100 ml three-necked flask, raw material 11(2.11 g, 0.01mol), raw material 12(2.74 g, 0.01mol), potassium carbonate (1.66 g, 0.012mol), toluene (35 ml), water (5 ml), tetrakis (triphenylphosphine) palladium (5.8 g, 0.5mmol) were added under nitrogen protection, stirred at 100 ℃ for 10 hours, and cooled to room temperature after reaction. Adding water into a reaction system, extracting by dichloromethane, and sequentially adding magnesium sulfate into the obtained extract liquor for drying, filtering and spin-drying; the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to afford intermediate 1-403(1.88 g, 52% yield).

(2) Synthesis of intermediates 2 to 403: into a 100 ml two-necked round-bottomed flask, N was introduced₂Intermediate 1-403(0.01mol) and tetrahydrofuran (30 ml) were added, dissolved, the temperature was reduced to-78 ℃, n-butyllithium was slowly added, after the addition was completed, the mixture was stirred at room temperature, and after the reaction was completed, the mixture was concentrated, and the crude product was purified by chromatography (dichloromethane/n-hexane, 1/10 (volume ratio)) to obtain intermediate 2-403(2.31 g, yield 71%).

(3) Synthesis of intermediates 3-403: adding the raw material 13(2.32 g, 0.01mol) and tetrahydrofuran (30 ml) into a 100 ml three-neck bottle, adding n-butyllithium (0.011mol) at 78 ℃, dropwise adding a tetrahydrofuran solution (3.25 g, 0.01mol) of the intermediate 2-403, stirring at 78 ℃, heating to room temperature, stirring overnight, adding water for quenching, extracting with dichloromethane, and drying with anhydrous magnesium sulfate to obtain the intermediate 3-403.

(4) Synthesis of intermediates 4 to 403: in a 50 ml three-necked flask, the intermediates 3 to 403 (obtained in step (3)), acetic acid (10 ml), and hydrochloric acid (1 ml) were added and refluxed for 1 hour. After cooling, water was added for quenching, dichloromethane extraction was performed, dried over anhydrous magnesium sulfate, and toluene was recrystallized to obtain intermediate 4-403(1.89 g, yield 41%).

(5)403, synthesis: a100 ml double-neck round-bottom flask is taken and put into a stirrer and an upper reflux pipe, nitrogen is filled after drying, and the intermediate 4-403(4.61 g, 0.01mol), the raw material 14(3.60 g, 0.01mol), cesium carbonate (0.012mol), tris (dibenzylideneacetone) dipalladium (Pd) are respectively added₂(dba)₃0.5mmol) and 2-dicyclohexylphosphonium-2 ', 4 ', 6 ' -triisopropylbiphenyl (xphos, 0.55mmol), followed by addition of toluene, reflux of the mixture for 24 hours, cooling to room temperature after the reaction, filtration of the reaction system and concentration, and chromatography of the crude product (dichloromethane/n-hexane, 1/10 (vol.%)) to give compound 403(6.52 g, 88% yield).

Elemental analysis: c₅₃H₃₁N₃Theoretical value of S: c, 85.80, H, 4.21, N, 5.66, S, 4.32, found: c, 85.87, H, 4.19, N, 5.64, S, 4.30, HRMS (ESI) M/z (M)⁺): theoretical value: 741.2239, found: 741.2245.

preparation example 5

(1) Synthesis of intermediates 1 to 332: taking a 50 ml double-neck round-bottom flask, putting a stirrer and an upper reflux pipe, drying, introducing nitrogen, and respectively adding 15(2.35 g, 0.01mol) of raw material, 16(1.56 g, 0.01mol) of raw material and potassium carbonate (K)₂CO₃0.02mol), ethanol (1 ml), water (1 ml), toluene (20 ml) and tetrakis (triphenylphosphine) palladium (Pd (PPh)₃)₄0.5mmol), heated to 60 ℃ and reacted for 12 hours, cooled to room temperature after completion of the reaction, quenched by addition of 10 ml of water, extracted with dichloromethane (3 × 20 ml), the resulting extract was dried over magnesium sulfate, filtered and spun-dried in this order, and the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10 (vol.%)) to give intermediates 1 to 332(1.07 g, 40% yield).

(2) Synthesis of intermediates 2 to 332: in a 100 ml three-neck flask, under the protection of nitrogen, the intermediates 1-332(2.67 g, 0.01mol), the raw material 17(2.90 g, 0.01mol), potassium carbonate (1.66 g, 0.012mol), toluene (35 ml), water (5 ml), tetrakis (triphenylphosphine) palladium (5.8 g, 0.5mmol) were added, stirred at 100 ℃ for 10 hours, and cooled to room temperature after reaction. Adding water into a reaction system, extracting by dichloromethane, and sequentially adding magnesium sulfate into the obtained extract liquor for drying, filtering and spin-drying; the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to afford intermediate 2-332(2.09 g, 53% yield).

(3) Synthesis of intermediates 3 to 332: intermediate 3-332(0.01mol), a 47% aqueous solution of hydrobromic acid (substrate 2mmol), methyltrioctylammonium chloride (2mmol) were added to a 50 ml three-necked flask, the reaction was carried out at 60 ℃, after completion of the reaction, water was added for quenching, dichloromethane was extracted, dried over anhydrous magnesium sulfate, the solvent was removed, and the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to give intermediate 3-332(3.31 g, 87% yield).

(4) Synthesis of intermediates 4 to 332: intermediate 3-332(3.81 g, 0.1mol), potassium carbonate (0.12mol), DMF (N, N-dimethylformamide, 20 ml), 80 ℃ were added to a 50 ml three-necked flask, the mixture was heated to react for 3 hours, the solvent was removed under reduced pressure, and the crude product was purified by chromatography (ethyl acetate/N-hexane, 1/10) to give intermediate 4-332(3.21 g, 93% yield)

(5) Synthesis of intermediates 5 to 332: taking a 50 ml double-neck round-bottom bottle, putting a stirrer and an upper reflux pipe, drying, introducing nitrogen, respectively adding an intermediate 4-332(3.45 g, 0.01mol), triphenylphosphine (0.02mol) and 1, 2-dichlorobenzene (25 ml), heating at 180 ℃ for reaction for 12 hours, cooling to room temperature after the reaction is finished, concentrating a reaction system, and carrying out chromatography purification on a crude product (ethyl acetate/n-hexane, 1/10 (volume ratio)) to obtain an intermediate 5-332(2.22 g, yield 71%).

(6)332 synthesis: a100 ml double-neck round-bottom flask is taken and put into a stirrer and an upper reflux pipe, nitrogen is filled after drying, and the intermediate 2-332(3.13 g, 0.01mol), the raw material 18(2.67 g, 0.01mol), cesium carbonate (0.012mol), tris (dibenzylideneacetone) dipalladium (Pd) are respectively added₂(dba)₃0.5mmol) and 2-dicyclohexylphosphonium-2 ', 4 ', 6 ' -triisopropylbiphenyl (xphos, 0.55mmol), then toluene was added, the mixture was refluxed for 24 hours, cooled to room temperature after the reaction,the reaction was filtered and concentrated, and the crude product was purified by chromatography (dichloromethane/n-hexane, 1/10 (vol.%)) to give compound 332(4.46 g, 82% yield).

Elemental analysis: c₃₅H₂₀N₄Theoretical value of SO: c, 77.19, H, 3.70, N, 10.29, S, 5.89, found: c, 77.11, H, 3.71, N, 10.33, S, 5.91, HRMS (ESI) M/z (M)⁺): theoretical value: 544.1358, found: 544.1365.

preparation example 6

(1) Synthesis of intermediate 1-1651: taking a 100 ml double-neck round-bottom flask, putting a stirrer and an upper reflux pipe, introducing nitrogen after drying, respectively adding 19(3.31 g, 0.01mol) of raw materials, 20(2.46 g, 0.01mol) of raw materials, 0.05mmol of palladium acetate, 0.55mmol of tri-tert-butylphosphine, 0.015mol of sodium tert-butoxide and 30 ml of toluene, heating to 80 ℃ for reaction for 2 hours, adding water into a reaction system, extracting by dichloromethane, and sequentially adding magnesium sulfate into obtained extract liquor for drying, filtering and spin-drying; the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to afford intermediate 1-1651(2.44 g, 49% yield).

(2) Synthesis of intermediate 2-1651: taking a 100 ml double-neck round-bottom flask, putting a stirrer and an upper reflux pipe, introducing nitrogen after drying, and respectively adding the intermediate 1-1651(4.97 g, 0.01mol) and dichlorobis (tricyclohexylphosphine) palladium (PdCl)₂(PCy₃)₂0.5mmol), pivalic acid (t-BuCO)₂H, 0.015mol), cesium carbonate (Cs)₂CO₃0.01mol) and dimethylacetamide (35 ml), stirred at 120 ℃ for 10 hours, cooled to room temperature after completion of the reaction, concentrated the reaction system, and the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10 (vol.%)) to give intermediate 2-1651(2.07 g, 45% yield).

(3)1651 Synthesis of: taking a 100 ml double-neck round-bottom flask, putting a stirrer and an upper reflux pipe, introducing nitrogen after drying, and respectively adding the intermediate 2-1651(4.61 g, 0.01mol) and the originalMaterial 21(1.12 g, 0.01mol), cesium carbonate (0.012mol), tris (dibenzylideneacetone) dipalladium (Pd)₂(dba)₃0.5mmol) and 2-dicyclohexylphosphonium-2 ', 4 ', 6 ' -triisopropylbiphenyl (xphos, 0.55mmol), followed by addition of toluene, refluxing the mixture for 24 hours, cooling to room temperature after the reaction, filtering the reaction system, concentrating, and purifying the crude product by chromatography (dichloromethane/n-hexane, 1/10 (volume ratio)) to obtain compound 1651(3.92 g, 73% yield).

Elemental analysis: c₃₉H₂₃NS theoretical value: c, 87.12, H, 4.31, N, 2.61, S, 5.96, found: c, 87.15, H, 4.30, N, 2.61, S, 5.94, HRMS (ESI) M/z (M)⁺): theoretical value: 537.1551, found: 537.1544.

preparation example 7

(1) Synthesis of intermediates 1-1743: taking a 100 ml double-neck round-bottom flask, putting a stirrer and an upper reflux pipe, introducing nitrogen after drying, respectively adding 22(2.75 g, 0.01mol) of raw materials, 23(3.05 g, 0.01mol) of raw materials, 0.05mmol of palladium acetate, 0.55mmol of tri-tert-butylphosphine, 0.015mol of sodium tert-butoxide and 35 ml of toluene, heating to 80 ℃ for reaction for 2 hours, adding water into a reaction system, extracting by dichloromethane, and sequentially adding magnesium sulfate into obtained extract liquor for drying, filtering and spin-drying; the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to afford intermediates 1-1743(2.3 g, 46% yield).

(2) Synthesis of intermediates 2-1743: taking a 100 ml double-neck round-bottom flask, putting a stirrer and an upper reflux pipe, introducing nitrogen after drying, and respectively adding an intermediate 1-1743(5 g, 0.01mol) and dichlorobis (tricyclohexylphosphine) palladium (PdCl)₂(PCy₃)₂0.5mmol), pivalic acid (t-BuCO)₂H, 0.015mol), cesium carbonate (Cs)₂CO₃0.01mol) and dimethylacetamide (40 ml), stirring at 120 ℃ for 10 hours, cooling to room temperature after the reaction is completed, concentrating the reaction system, and purifying the crude product by chromatography (ethyl acetate/n-hexane, 1/10 (volume ratio)) Intermediate 2-1743(1.86 g, 40% yield) was obtained.

(3)1743 Synthesis of: a100 ml two-neck round bottom flask is taken and put into a stirrer and an upper reflux pipe, nitrogen is filled after drying, and the intermediate 2-1743(4.64 g, 0.01mol), the raw material 24(3.21 g, 0.01mol), cesium carbonate (0.012mol), tris (dibenzylideneacetone) dipalladium (Pd) are respectively added₂(dba)₃0.5mmol) and 2-dicyclohexylphosphonium-2 ', 4 ', 6 ' -triisopropylbiphenyl (xphos, 0.55mmol), followed by addition of toluene, reflux of the mixture for 24 hours, cooling to room temperature after the reaction, filtration of the reaction system and concentration, and chromatography of the crude product (dichloromethane/n-hexane, 1/10 (volume ratio)) to give compound 1743(5.92 g, yield 79%).

Elemental analysis: c₅₂H₂₇D₅N₄Theoretical value of S: c, 83.28, H, 4.97, N, 7.47, S, 4.27, found: c, 83.33, H, 4.96, N, 7.45, S, 4.26, HRMS (ESI) M/z (M)⁺): theoretical value: 749.2662, found: 749.2656.

preparation example 8

(1) Synthesis of intermediates 1 to 72: taking a 100 ml double-neck round-bottom flask, putting a stirrer and an upper reflux pipe, introducing nitrogen after drying, respectively adding 25(1.99 g, 0.01mol) of raw materials, 26(2.46 g, 0.01mol) of raw materials, 0.05mmol of palladium acetate, 0.55mmol of tri-tert-butylphosphine, 0.015mol of sodium tert-butoxide and 30 ml of toluene, heating to 80 ℃ for reaction for 2 hours, adding water into a reaction system, extracting by dichloromethane, and sequentially adding magnesium sulfate into obtained extract liquor for drying, filtering and spin-drying; the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10) to afford intermediates 1-72(1.61 g, 44% yield).

(2) Synthesis of intermediates 2 to 72: taking a 100 ml double-neck round-bottom flask, putting a stirrer and an upper reflux pipe, introducing nitrogen after drying, and respectively adding intermediates 1-72(3.65 g, 0.01mol) and dichlorobis (tricyclohexylphosphine) palladium (PdCl)₂(PCy₃)₂0.5mmol), pivalic acidAcid (t-BuCO)₂H, 0.015mol), cesium carbonate (Cs)₂CO₃0.01mol) and dimethylacetamide (30 ml), stirred at 120 ℃ for 10 hours, cooled to room temperature after completion of the reaction, concentrated the reaction, and the crude product was purified by chromatography (ethyl acetate/n-hexane, 1/10 (vol.%)) to give intermediates 2-72(1.35 g, 41% yield).

(3)72, synthesis: a100 ml two-neck round bottom flask is taken and put into a stirrer and an upper reflux pipe, nitrogen is filled after drying, and the intermediate 2-72(3.29 g, 0.01mol), the raw material 27(3.60 g, 0.01mol), cesium carbonate (0.012mol), tris (dibenzylideneacetone) dipalladium (Pd) are respectively added₂(dba)₃0.5mmol) and 2-dicyclohexylphosphonium-2 ', 4 ', 6 ' -triisopropylbiphenyl (xphos, 0.55mmol), followed by addition of toluene, refluxing of the mixture for 24 hours, cooling to room temperature after the reaction, filtration of the reaction system and concentration, and chromatography purification of the crude product (dichloromethane/n-hexane, 1/10 (vol.%)) to give compound 72(5.12 g, 84% yield).

Elemental analysis: c₄₀H₂₃N₃S₂Theoretical value: c, 78.79, H, 3.80, N, 6.89, S, 10.52, found: c, 78.86, H, 3.79, N, 6.87, S, 10.48, HRMS (ESI) M/z (M)⁺): theoretical value: 609.1333, found: 609.1339.

example 1

The present embodiment provides an organic electroluminescent device, which has a schematic structural diagram as shown in fig. 1, and includes an anode layer 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 disposed on a substrate 1 from bottom to top.

Wherein, the anode 2 is made of ITO material, the hole injection layer 3 is HAT (CN)₆And NPB, of which, HAT (CN)₆NPB 3:97 (mass ratio); the hole transport layer 4 is NPB; the light-emitting layer 5 is composed of a host material and a doping material, the host material is a compound 1548 synthesized in synthesis example 1, the guest material is Ir (DBQ)2(acac), and the mass ratio of the host material to the guest material is 95: 5; the electron transport layer 6 is selected from BPhen and LiQ, wherein BPhen: LiQ ═ 1:1 (mass ratio); the electron injection layer 7 is LiQ; selection of cathode 8Mg/Ag, wherein the ratio of Mg to Ag is 9:1 (mass ratio).

The preparation process of the organic electroluminescent device is as follows:

(1) substrate cleaning: carrying out ultrasonic treatment on the motor substrate coated with the transparent ITO in an aqueous cleaning agent (the components and concentration of the aqueous cleaning agent are that ethylene glycol solvent is less than or equal to 10 wt% and triethanolamine is less than or equal to 1 wt%), washing in deionized water, carrying out ultrasonic oil removal in a mixed solvent of acetone and ethanol (volume ratio is 1:1), baking in a clean environment until moisture is completely removed, and then cleaning by using ultraviolet light and ozone;

(2) evaporating, namely placing the glass substrate with the anode layer in a vacuum chamber, and vacuumizing to 1 × 10^-6To 2 × 10^-4Pa, co-evaporating a hole injection material HAT (CN) on the anode layer film in vacuum₆Adjusting the rate with NPB according to the mass ratio, wherein the total evaporation rate is 0.1nm/s, and the evaporation thickness is 10 nm;

(3) evaporating a hole transport layer on the hole injection layer at the evaporation rate of 0.1nm/s and the evaporation film thickness of 80 nm;

(4) evaporating a luminescent layer on the hole transport layer, and evaporating a luminescent host material and an object material in vacuum in a co-evaporation mode, wherein the evaporation rate of the host material and the object material is adjusted according to the mass ratio, the total evaporation rate is 0.01nm/s, and the total evaporation film thickness is 40 nm;

(5) vacuum evaporating an electron transport layer on the luminescent layer, and adjusting the evaporation rate according to the mass ratio, wherein the total evaporation rate is 0.1nm/s, and the total evaporation film thickness is 30 nm;

(6) vacuum evaporating an electron injection layer on the electron transport layer, wherein the evaporation rate is 0.05nm/s, and the total film thickness is 1 nm;

(7) Mg/Ag is used as a cathode layer of the device, the evaporation rate is adjusted according to the mass ratio, the total evaporation rate is 0.1nm/s, and the total evaporation film thickness is 80 nm.

Examples 2 to 6

Only different from example 1 in that the host material 1548 in example 1 was sequentially replaced with the compound 1602 in preparation example 2, the compound 403 in preparation example 4, the compound 332 in preparation example 5, the compound 1743 in preparation example 7, and the compound 72 in preparation example 8, examples 2 to 7 were sequentially obtained.

Comparative example 1

The only difference from example 1 is that the host material 1548 in example 1 is replaced with CBP.

Example 7

The only difference from example 1 is that the hole transporting material NPB in example 1 was replaced with the compound 1651 prepared in preparation example 6.

Example 8

The difference from example 1 is only that the hole transport material NPB in example 1 was replaced with the compound 1779 prepared in preparation example 3, the light-emitting layer was composed of a host material AND a dopant material, the host material was an AND, the guest material was an FDI, AND the mass ratio of the host material to the guest material was 1: 1.

Comparative example 2

The only difference from example 8 is that the hole transport material 1779 in example 8 was replaced with NPB.

The compounds of the embodiments were subjected to the following performance tests:

(1) thermal decomposition temperature tests were conducted on the fused ring compound material using a thermogravimetric analyzer (TA TGA55, usa) in a range from room temperature to 600 ℃, at a temperature rise rate of 10 ℃/min, and at a temperature of 5% weight loss under nitrogen atmosphere, defined as thermal decomposition temperature (Td), and the results are shown in table 1:

TABLE 1

Preparation example	Compound (I)	T_d(℃)	Preparation example	Compound (I)	T_d(℃)
						Preparation example 1	1548	430	Preparation example 5	332	311
Preparation example 2	1602	367	Preparation example 6	1651	307
						Preparation example 3	1779	348	Preparation example 7	1743	438
Preparation example 4	403	429	Preparation example 8	72	344

As shown in Table 1, the compound of the present invention has high thermal stability, and the thermal decomposition temperature can reach 307-438 ℃, so as to avoid the material decomposition during the preparation, encapsulation and the like, and improve the stability of the device.

(2) Testing HOMO and LOMO energy levels: the LUMO energy level of the organic electroluminescent compound prepared in the preparation example was measured using an electrochemical workstation using cyclic voltammetry (CV shanghai chen CHI-600E) with a platinum wire (Pt) as a counter electrode and silver/silver chloride (Ag/AgCl) as a reference electrode. Under the nitrogen atmosphere, the test is carried out in methylene chloride electrolyte containing 0.1M tetrabutylammonium hexafluorophosphate at the scanning rate of 100mV/s, the potential calibration is carried out by ferrocene, and the absolute energy level of the potential of the ferrocene in the vacuum state is set as-4.8 eV:

HOMO_{energy level}＝-e(Eox-E_{1/2,ferrocene})+(-4.8)eV

LUMO_{Energy level}＝-e(E_re-E_{1/2,ferrocene})+(-4.8)eV

E_T1(eV) triplet level.

E_oxTo oxidation potential, E_reTo reduce the potential, E_{1/2,ferrocene}Is the ferrocene potential. Triplet state energy level test conditions: fluorescence spectrophotometer (Hitachi F-4600), solution state (toluene as solvent, concentration 2 x 10)^-5mol/L) and 78 degrees centigrade.

E_T11240/shortest absorption wavelength

The test results are shown in table 2:

TABLE 2

As can be seen from table 2, the compound of the present invention has suitable HOMO and LUMO energy levels and triplet energy levels, and the HOMO and LUMO energy levels of the compound are matched with those of adjacent transport layers, so that the compound can be used as an organic electroluminescent material to effectively reduce driving voltage and improve luminous efficiency.

(3) The following tests were carried out for the organic electroluminescent devices in some of the device examples provided by the present invention and in 1 device comparative example:

the characteristics of the device such as current, voltage, brightness, light-emitting spectrum and the like are synchronously tested by adopting a PR 650 spectrum scanning luminance meter and a KeithleyK 2400 digital source meter system, and the test conditions are as follows: the current density is 20mA/cm²Room temperature;

and (3) life test: the time (in hours) was recorded when the device brightness dropped to 98% of the original brightness.

The results are shown in Table 3.

TABLE 3

Examples	Host material	Hole transport layer	Voltage (V)	Chromaticity CIE (X, Y)	Current efficiency cd/A	Life (h)
							Example 1	1548	NPB	4.5	(0.66,0.32)	23	50
Example 2	1602	NPB	4.4	(0.67,0.33)	23	53
							Example 3	403	NPB	4.4	(0.66,0.32)	20	65
Example 4	332	NPB	4.5	(0.66,0.32)	21	55
							Example 5	1743	NPB	4.4	(0.66,0.33)	24	56
Example 6	72	NPB	4.4	(0.66,0.33)	24	64
							Comparative example 1	CBP	NPB	5.2	(0.66,0.32)	12	21
Example 7	1548	1651	4.4	(0.66,0.32)	28	85
							Example 8	FDI:AND	1779	4.6	(0.15,0.24)	8	28
Comparative example 2	FDI:AND	NPB	5.3	(0.15,0.24)	2	0.7

As can be seen from table 3, the compounds of the present invention, which are used as a light emitting layer material, or a hole transport layer material, have a low driving voltage and improved current efficiency and lifespan; when the compound is used as a luminescent layer material, the driving voltage is as low as 4.4-4.5V, the current efficiency can reach 21-24cd/A, and the working life can reach 50-85 h; when the compound is used as a hole transport layer material, the driving voltage is as low as 4.4-4.6V, the current efficiency can reach 8-28cd/A, and the working life can reach 28-85 h; therefore, when the organic electroluminescent compound provided by the invention is used as a luminescent layer material or a hole transport layer material, the working voltage of the device can be effectively reduced, and the luminescent efficiency and the service life of the device are improved.

The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims

1. An organic electroluminescent compound, characterized in that it has the structure of formula I:

wherein, X¹Selected from O, S, CR⁷R⁸、SiR⁷R⁸Or is

Any one of the above;

X²selected from O, S, CR⁷R⁸Or

Any one of the above;

Y¹、Y²and Y³Each independently selected from O, S, CR⁷R⁸Or

Any one of the above;

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸wherein each group is not linked to each other or wherein 2 to 4 adjacent groups are linked to form a ring, each of said rings being independently selected from any one of a saturated or partially unsaturated carbocyclic ring of C3-C7, a saturated or partially unsaturated heterocyclic ring of C3-C7, an aromatic ring of C6-C60, or an aromatic heterocyclic ring of C3-C30;

Ar¹、Ar²and Ar³Each independently selected from substituted or substitutedAny one of unsubstituted C6-C60 aryl, substituted or unsubstituted C3-C60 heteroaryl, substituted or unsubstituted C6-C60 aryloxy, substituted or unsubstituted C6-C60 arylamine, substituted or unsubstituted C6-C60 thioaryloxy, substituted or unsubstituted C6-C60 arylboron, substituted or unsubstituted C6-C60 arylphosphine, substituted or unsubstituted C4-C60 heteroaryloxy, substituted or unsubstituted C4-C60 heteroarylamine, substituted or unsubstituted C4-C60 aromatic-C4-C60 heteroarylamine, substituted or unsubstituted C4-C60 thioheteroaryloxy, substituted or unsubstituted C4-C60 heteroarylboron, substituted or unsubstituted C4-C60 heteroarylphosphine;

indicating an access site;

represents an aromatic ring structure;

L¹、L²、L³、Ar¹、Ar²、Ar³、R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R¹³、R¹⁴、R¹⁵、R¹⁶and R¹⁷Wherein the substituted group is any one of deuterium atom, halogen, nitro, cyano or C1-C4 alkyl, C1-C4 alkoxy, C1-C4 alkenyl, C6-C12 aryl, C6-C12 aryloxy, C6-C12 arylamine, C3-C12 membered heteroaryl or C3-C12 heteroarylamine which is substituted or unsubstituted by one or more of deuterium atom, halogen, cyano or nitro.

2. The organic electroluminescent compound according to claim 1, wherein R is¹、R²、R³、R⁴、R⁵、R⁶、R⁷And R⁸Each independently selected from the group consisting of a hydrogen atom, a deuterium atom, a tritium atom, a cyano group,Halogen, hydroxyl, nitro, amino, substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C2-C4 alkenyl, substituted or unsubstituted C2-C4 alkynyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl, substituted or unsubstituted C1-C4 alkoxy, substituted or unsubstituted C1-C4 thioalkoxy, substituted or unsubstituted C6-C20 aryloxy, substituted or unsubstituted C6-C20 thioaryloxy, -NR¹³R¹⁴、-SiR¹⁵R¹⁶R¹⁷Any one of the above; r¹³And R¹⁴Each independently selected from substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl; r¹⁵、R¹⁶And R¹⁷Each independently selected from substituted or unsubstituted C1-C4 alkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C3-C20 heteroaryl; r¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸Wherein each group is not linked to each other or wherein 2 to 4 adjacent groups are linked to form a ring, each of said rings being independently selected from any one of a saturated or partially unsaturated carbocyclic ring of C3-C7, a saturated or partially unsaturated heterocyclic ring of C3-C7, an aromatic ring of C6-C60, or an aromatic heterocyclic ring of C3-C30;

R¹、R²、R³、R⁴、R⁵、R⁶、R⁷、R⁸、R¹³、R¹⁴、R¹⁵、R¹⁶and R¹⁷Wherein each of said substituted groups independently has the same limitations as defined in claim 1.

3. The organic electroluminescent compound according to claim 1 or 2, wherein Ar is¹、Ar²And Ar³Each independently selected from any one of aryl of C6-C60, substituted or unsubstituted heteroaryl of C3-C60, substituted or unsubstituted aromatic amine of C6-C60 and substituted or unsubstituted heteroaromatic amine of C4-C60;

preferably, Ar is¹、Ar²And Ar³Each is independentThe site is selected from any one of the following groups:

X³Selected from O, S, CR¹¹R¹²Or

Any one of the above;

n1 is an integer from 0 to 2;

n2 is an integer from 0 to 4;

R⁹、R¹⁰、R¹¹and R¹²Each independently selected from any one of a hydrogen atom, a deuterium atom, a tritium atom, a cyano group, a halogen, a hydroxyl group, a nitro group, an amino group, a substituted or unsubstituted C1-C4 alkyl group, a substituted or unsubstituted C2-C4 alkenyl group, a substituted or unsubstituted C2-C4 alkynyl group, a substituted or unsubstituted C6-C20 aryl group, a substituted or unsubstituted C3-C20-membered heteroaryl group, a substituted or unsubstituted C1-C4 alkoxy group, a substituted or unsubstituted C1-C4 thioalkoxy group, a substituted or unsubstituted C6-C20 aryloxy group, and a substituted or unsubstituted C6-C20 thioaryloxy group; any two adjacent R⁹And/or R¹⁰The groups are not linked to each other or wherein 2 to 4 adjacent groups are linked to form a ring, each ring being independently selected from aromatic rings of C6-C20Or any one of aromatic heterocycles of C3-C20;

L⁴、Ar⁴、R⁹、R¹⁰、R¹¹and R¹²Wherein each of said substituted groups independently has the same limitations as defined in claim 1;

preferably, said Q¹、Q²And Q³At least one of them is N;

preferably, n2 is an integer from 0 to 2.

4. The organic electroluminescent compound according to any one of claims 1 to 3, wherein Ar is Ar¹、Ar²And Ar³Each independently selected from any one of the following Ar-1 to Ar-81 groups:

5. the organic electroluminescent compound according to any one of claims 1 to 4, wherein the compound of formula I is formed by connecting CA, CB and X moieties:

wherein,

and

the connection is carried out by connecting the two parts,

and

the connection is carried out by connecting the two parts,

and

connecting;

R¹、R²、R³、R⁴、R⁵、R⁶、X¹、X²、Y¹、Y²and Y³Each independently having the same limitations as any one of claims 1-4.

6. The organic electroluminescent compound according to claim 5, wherein the CA is selected from any one of the following structures CA-1 to CA-15:

wherein L is¹And Ar¹Each independently having the same limitations as claim 1;

wherein L is³And Ar³Each independently having the same limitations as claim 1.

7. Use of an organic electroluminescent compound according to any one of claims 1 to 6 as an organic electroluminescent material;

8. 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 any one or a combination of at least two of the organic electroluminescent compounds according to any one of claims 1 to 6;

preferably, the organic layer includes a light emitting layer including a host material and a guest material, the host material including any one of the organic electroluminescent compounds according to any one of claims 1 to 6 or a combination of at least two thereof.

9. The organic electroluminescent device according to claim 8, wherein the number of the organic electroluminescent devices is at least two, and the at least two organic electroluminescent devices are stacked on each other to form a series structure.

10. Use of the organic electroluminescent device according to claim 8 or 9 in a display device or a lighting device.