CN115701766A - Organic material composition and application thereof - Google Patents

Abstract

The invention provides an organic material composition and application thereof, wherein the organic material composition comprises a fused heterocyclic compound containing a quinoxaline structure and a hole transport type compound, the fused heterocyclic compound containing the quinoxaline structure has a structure shown as a formula (1), and the hole transport type compound has a structure shown as a formula (2). The composition of the invention enables the organic electroluminescent device to have lower driving voltage (below 3.85V), higher current efficiency (above 25 Cd/A) and longer service life (above 267 h).

Description

Organic material composition and application thereof

Technical Field

The invention belongs to the technical field of organic electroluminescence, and relates to an organic material composition and application thereof.

Background

Among display devices, an electroluminescent device (EL device) is an automatic light emitting device, which is advantageous in that it provides a wide viewing angle, a large contrast ratio, and a fast response time. The first organic EL device was developed by Eastman Kodak (Eastman Kodak) in 1987 by using a small aromatic diamine molecule and an aluminum complex as materials for forming a light-emitting layer (appl. Physics. Lett.) 51,913, 1987.

The most important factor determining the luminous efficiency of the organic electroluminescent device is a light emitting material. Heretofore, fluorescent materials have been widely used as light-emitting materials. However, in view of the electroluminescence mechanism, since the phosphorescent light emitting material theoretically enhances the light emitting efficiency four (4) times as compared with the fluorescent light emitting material, the phosphorescent light emitting material has been widely studied. Iridium (III) complexes have been widely known as phosphorescent light emitting materials, with 4,4'-N, N' -dicarbazole-biphenyl (CBP) being the most widely known phosphorescent host material.

Although these materials provide good luminescent characteristics, they have the following disadvantages: the power efficiency of the organic electroluminescent device is derived from [ (pi/voltage) × current efficiency ], and the power efficiency is inversely proportional to the voltage. Although the organic electroluminescent device including the phosphorescent host material provides higher current efficiency (cd/a) than the organic electroluminescent device including the fluorescent material, a significantly high driving voltage is necessary. Therefore, there is no advantage in terms of power efficiency (lm/W). In addition, the organic electroluminescent device has a short lifetime, and improvement in luminous efficiency is still required. Therefore, materials constituting organic layers in the device, particularly, a host of a light emitting material should be appropriately selected in order to achieve excellent characteristics of the organic EL device.

Disclosure of Invention

In view of the deficiencies of the prior art, it is an object of the present invention to provide an organic material composition and uses thereof. The organic material composition of the present invention can provide an organic electroluminescent device having a long driving life.

In order to achieve the purpose, the invention adopts the following technical scheme:

in one aspect, the present invention provides an organic material composition comprising a fused heterocyclic compound having a quinoxaline structure and a hole transport type compound, wherein the fused heterocyclic compound having a quinoxaline structure has a structure represented by formula (1), and the hole transport type compound has a structure represented by formula (2):

R ¹ -R ⁶ each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, C1-C30 alkyl wherein one or more methylene groups are substituted by-O-or-S-in such a way that O atoms or S atoms are not adjacent substituted or unsubstituted C2-C30 alkenyl, C2-C30 alkenyl in which one or more methylene groups are substituted by-O-or-S-in such a manner that O atoms or S atoms are not adjacent, substituted or unsubstituted C2-C30 alkynyl substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroaralkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C1-C30 alkoxy, or substituted or unsubstituted C6-C30 aryloxy,

R ¹ -R ⁶ each independently exists or two adjacent rings are connected to form a ring A which is a substituted or unsubstituted benzene ring,

l is selected from a linkage, a substituted or unsubstituted C6-C30 arylene, a substituted or unsubstituted C5-C30 heteroarylene,

Ar ¹ selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C5-C60 heteroaryl, substituted or unsubstituted C6-C60 arylamine, substituted or unsubstituted C5-C60 heteroarylamine, substituted or unsubstituted C5-C60 arylheteroarylamine,

n is selected from an integer of 0 to 3 (e.g. may be 0, 1, 2 or 3),

m is selected from an integer of 0-5 (e.g., may be 0, 1, 2, 3,4 or 5),

n1 is selected from the integer of 0-1,

m1 is an integer selected from 0 to 1;

in formula (2), p is selected from integers ranging from 0 to 4 (e.g., 0, 1, 2, 3 or 4),

q is selected from an integer of 0 to 4 (e.g., 0, 1, 2, 3 or 4),

R ⁷ 、R ⁸ each independently selected from the group consisting of substituted or unsubstituted C1-C30 alkyl, C1-C30 alkyl wherein one or more methylene groups are substituted by-O-or-S-in such a way that O atoms or S atoms are not adjacent substituted or unsubstituted C2-C30 alkenyl, C2-C30 alkenyl in which one or more methylene groups are substituted by-O-or-S-in such a manner that O atoms or S atoms are not adjacent, substituted or unsubstituted C2-C30 alkynyl substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroaralkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C1-C30 alkoxy, or substituted or unsubstituted C6-C30 aryloxy,

R ⁷ 、R ⁸ each independently exists, or two or four adjacent to each other are connected through a chemical bond, or through phenylene, or through naphthylene to form a ring B;

L ² 、L ³ each independently selected from a linkage, a substituted or unsubstituted C6-C30 arylene, a substituted or unsubstituted C2-C30 heteroarylene,

Ar ⁴ -Ar ⁷ each independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, w1 is selected from an integer from 0 to 1,

w2 is an integer selected from 0 to 1.

In the organic material composition, the electron hole combination rate is improved and the current efficiency is improved by adopting the quinoxaline structure-containing fused heterocyclic compound as the electron transport material and the hole transport type compound as the electron transport material.

Preferably, the ring B is a substituted or unsubstituted group as follows: a benzene ring, a naphthalene ring, a benzothiophene ring, a benzofuran ring, an indene ring, an indole ring or a seven-membered ring.

Preferably, in the formula (2), L ² 、L ³ Each independently selected from the group consisting of a linking bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, and a substituted or unsubstituted phenylene groupNaphthylene group of (a);

preferably, ar ⁴ -Ar ⁷ Each is independently selected from the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, naphthyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, dibenzofuranyl, dibenzothiophenyl, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, carbazolyl, phenyl-substituted carbazolyl, pyridyl-substituted carbazolyl, dibenzocarbazolyl, benzonaphthofuranyl, dinaphthofuranyl, benzonaphthothiophenyl, or dinaphthothiophenyl;

preferably, w1+ w2=1;

preferably, R ⁷ 、R ⁸ Each independently selected from deuterium, halogen, cyano, substituted or unsubstituted groups as follows: methyl, ethyl, tert-butyl, adamantyl, phenyl, biphenyl, terphenyl, naphthyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, dibenzofuranyl, dibenzothiophenyl, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, carbazolyl, phenyl-substituted carbazolyl, pyridyl-substituted carbazolyl, dibenzocarbazolyl, benzonaphthofuranyl, dinaphthofuranyl, benzonaphthothiophenyl, dinaphthothiophenyl;

preferably, in formula (2), when the group contains a substituent, each of the substituents is independently selected from deuterium, halogen, cyano, unsubstituted or R ' substituted C1-C6 alkyl, unsubstituted or R ' substituted C6-C12 aryl, unsubstituted or R ' substituted C2-C20 heteroaryl; r' is selected from deuterium, halogen, cyano, deuterium substituted methyl or halogen substituted methyl.

Preferably, the compound of the structure represented by the formula (2) comprises any one of the following compounds:

preferably, n1+ m1=1.

Preferably, -L-Ar ¹ Is selected from

Wherein Ar ² 、Ar ³ Each independently selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C5-C60 heteroaryl.

Preferably, ar ² 、Ar ³ Each is independently selected from the following substituted or unsubstituted groups: phenyl, biphenyl, terphenyl, naphthyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, phenyl-substituted carbazolyl, pyridyl-substituted carbazolyl, naphthyl-substituted carbazolyl, biphenyl-substituted carbazolyl, dibenzofuran-substituted phenyl, dibenzothiophene-substituted phenyl, dimethylfluorenyl, diphenyl-substituted fluorenyl, spirobifluorenyl, benzonaphthofuranyl, benzonaphthothiophenyl, benzocarbazolyl, or dibenzocarbazolyl;

preferably, -L-Ar ¹ Is selected from

Wherein the dotted line represents L and Ar ³ Forming a ring through chemical bond connection;

more preferably, -L-Ar ¹ Selected from the group consisting of substituted or unsubstituted:

preferably, -L-Ar ¹ Is selected from

Wherein the dotted line represents Ar ² 、Ar ³ Is connected with a ring through a chemical bond,

more preferably, -L-Ar ¹ Selected from the group consisting of substituted or unsubstituted

Preferably, ar ¹ Is selected from

Wherein X ¹ Selected from N or CR ^X1 ，X ² Selected from N or CR ^X2 ，X ³ Selected from N or CR ^X3 ，X ⁴ Selected from N or CR ^X4 ，X ⁵ Selected from N or CR ^X5 ，

R ^X1 、R ^X2 、R ^X3 、R ^X4 、R ^X5 Each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, C1-C30 alkyl in which one or more methylene groups are substituted by-O-or-S-in such a way that the O atom or S atom is not adjacent, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroaralkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C3-C30 cycloalkenylA substituted or unsubstituted C1-C30 alkoxy group or a substituted or unsubstituted C6-C30 aryloxy group,

R ^X1 、R ^X2 、R ^X3 、R ^X4 、R ^X5 independently exist or are connected with each other to form a ring, the ring is a substituted or unsubstituted benzene ring, pyridine ring, naphthalene ring, anthracene ring, phenanthrene ring, naphthooxazole ring, naphthothiazole ring, benzofuran ring or benzothiophene ring,

preferably, ar ¹ Is selected from

Preferably, ar ¹ Is selected from

Wherein X ¹ 、X ² 、X ⁵ Any two of which are selected from the group consisting of N,

Y ¹ selected from N, CR ^Y1 ，Y ² Selected from N, CR ^Y2 ，Y ³ Selected from N, CR ^Y3 ，Y ⁴ Selected from N, CR ^Y4 ，

R ^Y1 、R ^Y2 、R ^Y3 、R ^Y4 Each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, C1-C30 alkyl in which one or more methylene groups are substituted by-O-or-S-in such a way that the O atom or S atom is not adjacent, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroaralkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C1-C30 alkoxy, or substituted or unsubstituted C6-C30 aryloxy,

R ^Y1 、R ^Y2 、R ^Y3 、R ^Y4 each independently exists, or two adjacent rings are connected to form a ring which is a substituted or unsubstituted benzene ring.

More preferably, X ² 、X ⁵ Is selected from N.

More preferably, X ¹ 、X ⁵ Is selected from N.

More preferably, Y ¹ Selected from the group consisting of CR ^Y1 ，Y ² Selected from the group consisting of CR ^Y2 ，Y ³ Selected from the group consisting of CR ^Y3 ，Y ⁴ Selected from the group consisting of CR ^Y4 ，

More preferably, R ^X1 、R ^X2 、R ^X3 、R ^X4 、R ^X5 、R ^Y1 、R ^Y2 、R ^Y3 、R ^Y4 Each independently selected from hydrogen, substituted or unsubstituted: phenyl, biphenyl, terphenyl, naphthyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, phenyl-substituted carbazolyl, pyridyl-substituted carbazolyl, naphthyl-substituted carbazolyl, biphenyl-substituted carbazolyl, dibenzofuran-substituted phenyl, dibenzothiophene-substituted phenyl, dimethylfluorenyl, diphenyl-substituted fluorenyl, and spirobifluorenyl.

Preferably, each L is independently selected from phenylene, biphenylene, naphthylene,

preferably, R ¹ -R ⁶ Each independently selected from hydrogen, deuterium, cyano, fluorine, methyl, ethyl, tert-butyl, deuterium-substituted methyl, fluorine-substituted methyl, phenyl, biphenyl, pyridyl, dibenzofuranyl, dibenzothienyl, dimethylfluorenyl, carbazolyl, phenyl-substituted carbazolyl, pyridyl-substituted carbazolyl, naphthyl-substituted carbazolyl, biphenyl-substituted carbazolyl,

preferably, ar1 is selected from phenyl, biphenyl, terphenyl, naphthyl, benzophenanthryl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, dibenzofuranyl, dibenzothienyl, dibenzofuran-substituted phenyl, dibenzothiophene-substituted phenyl, dimethylfluorenyl, diphenyl-substituted fluorenyl, spirobifluorenyl, 2-phenylphenanthrene [3,4-d ] oxazolyl, 2-phenylphenanthrene [3,4-d ] thiazolyl;

in the present invention, when the group contains a substituent, the substituents are each independently selected from deuterium, halogen, cyano, unsubstituted or R ' substituted C1-C6 alkyl, unsubstituted or R ' substituted C6-C12 aryl, unsubstituted or R ' substituted C2-C20 heteroaryl; r' is selected from deuterium, halogen, cyano, deuterium substituted methyl, halogen substituted methyl.

More preferably, the C1-C6 alkyl group is selected from methyl, ethyl, tert-butyl;

the aryl of C6-C12 is selected from phenyl, biphenyl and naphthyl;

the heteroaryl of C3-C20 is selected from triazinyl, pyridyl, phenyl-substituted pyridyl, pyridyl-substituted phenyl, dibenzofuranyl and dibenzothiophenyl.

Preferably, the compound having the structure represented by formula (1) is any one of the following compounds:

wherein D represents deuterium.

Preferably, the organic material composition has a thermal decomposition temperature difference of not more than 20 ℃, preferably not more than 10 ℃, and further preferably not more than 5 ℃.

As used in the present invention, the term "halogen" may include fluorine, chlorine, bromine or iodine, preferably fluorine.

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

As used herein, unless otherwise specified, the term "cycloalkyl" refers to a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 30 carbon atoms. Examples of such cycloalkyl groups include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, adamantane and the like.

Heteroaryl, heteroarylene groups of the present invention include monocyclic, polycyclic or fused ring aryl groups, which rings may be interrupted by short non-aromatic units, including, but 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, quinolinyl, isoquinolinyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenazinyl, phenothiazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl, derivatives thereof, and the like.

Preferably, the aryl group is selected from phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, 9 '-dimethylfluorenyl, 9' -diphenylfluorenyl or spirobifluorenyl.

Preferably, the heteroaryl group is selected from dibenzofuranyl, dibenzothienyl, carbazolyl, triazinyl, pyridyl, pyrimidinyl, imidazolyl, oxazolyl, thiazolyl, benzimidazolyl, benzoxazolyl, benzothiazolyl, naphthoimidazolyl, naphthooxazolyl, naphthothiazolyl, phenanthroimidazolyl, phenanthrooxazolyl, quinoxalinyl, quinazolinyl, indolocarbazolyl, indolofluorenyl, benzothiophenopyrazinyl, benzothiophenopyrimidyl, benzofuropyrazinyl, benzofuropyrimidinyl, indolopyrazinyl, indolopyrimidinyl, indenopyrazinyl, indenopyrimidinyl, spiro (fluorene-9, 1 '-indene) pyrazinyl, spiro (fluorene-9, 1' -indene) pyrimidinyl, benzofurocarbazolyl, or benzothiophenocarbazolyl.

As used herein, the term "aryloxy" refers to a monovalent substituent represented by RO-, wherein R represents an aryl group having 6 to 30 carbon atoms. Examples of such aryloxy groups include, but are not limited to, phenoxy, naphthoxy, diphenoxy, and the like.

As used herein, the term "substituted" means that the hydrogen atom in the compound is replaced with another substituent. The position is not limited to a specific position as long as hydrogen at the position can be substituted by 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 specified, hydrogen atoms include protium, deuterium, and tritium.

The term "two adjacent groups are linked to form a ring" in the present invention means that 2 substituents at adjacent positions in the same ring or adjacent rings can be linked to each other to form a ring through chemical bonds, and the present invention does not limit the specific linking and ring-forming manner (for example, linking through a single bond, linking through a benzene ring, linking through a naphthalene ring, etc.)

Thickening and passing

Thickening and passing

Thickening and passing

Thickening and passing

Thickening; wherein

Indicating a thick and positional relationship) have the same meaning as described below with respect to the same description.

In the present invention, the definition of a group defines a range of carbon numbers, the number of carbon atoms of which is any integer within the defined range, such as a C6-C60 aryl group, and the number of carbon atoms representing an aryl group can be any integer within the range encompassed by 6-60, such as 6, 8, 10, 15, 20, 30, 35, 40, 45, 50, 55, 60, or the like.

In the present invention, the preparation route of the compound having the structure represented by formula (1) is as follows:

wherein OTf represents

In the present invention, the preparation route of the compound having the structure represented by formula (2) is as follows:

in another aspect, the present invention provides the use of an organic material composition as described above for the manufacture of an optical device.

Preferably, the optical device comprises any one of an organic electroluminescent device, an organic field effect transistor, an organic thin film transistor, an organic light emitting transistor, an organic integrated circuit, an organic solar cell, an organic field quenching device, a light emitting electrochemical cell, an organic laser diode or an organic photoreceptor.

In another aspect, the present invention provides an organic electroluminescent device comprising an anode and a cathode, and an organic layer disposed between the anode and the cathode, the organic layer comprising the organic material composition as described above.

Preferably, the organic layer includes a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, which are stacked in this order from the anode side to the cathode side.

Preferably, the material of the light-emitting layer comprises a host material and a guest material, the host material comprising the organic material composition as described above;

preferably, the guest material includes a phosphorescent dopant comprising a complex comprising Ir or Pt.

Preferably, the material of the electron transport layer contains at least any one of the above-described quinoxaline structure-containing fused heterocyclic compounds or a combination of at least two thereof.

In another aspect, the present invention provides an organic electroluminescent device comprising the organic electroluminescent device as described above.

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

the organic material composition of the invention enables the organic electroluminescent device to have lower driving voltage (below 3.85V), higher current efficiency (above 25 Cd/A) and longer service life (above 267 h).

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.

Synthetic examples

(1) Synthesis of 1-C: taking a 50 ml double-neck round-bottom flask, putting a stirrer and an upper reflux pipe, introducing nitrogen after drying, and respectively adding a compound 1-A (1 mmol), a compound 1-B (1 mmol) and potassium carbonate (K) ₂ CO ₃ 1.5mmol, ethanol (3 ml), water (3 ml), toluene (15 ml) and tetrakis (triphenylphosphine) palladium (Pd (PPh) ₃ ) ₄ 0.05 mmol), heated to 60 ℃ and reacted for 12 hours, cooled to room temperature after completion of the reaction, quenched by addition of 20 ml of water, extracted with dichloromethane (3 × 20 ml), the resulting extract was dried over magnesium sulfate in this order, filtered and spin-dried, and the crude product was purified by column chromatography (ethyl acetate/n-hexane: volume ratio 1/10) to obtain 1-C (0.17 g, yield 54%).

(2) Synthesis of 1-D: a50 ml two-neck round-bottom flask is taken and placed with a stirrer and an upper reflux pipe, nitrogen is filled after drying, 1-C (1 mmol), bis (pinacolato) diboron (1.2 mmol), potassium acetate (2 mmol), 1, 4-dioxane (20 ml) are respectively added, nitrogen protection is carried out, 1-bis (diphenylphosphino) ferrocene ] palladium (II) dichloride (0.05 mmol) is added, reflux is carried out for 12 hours, and after the reaction is finished, a crude product is purified by column chromatography (ethyl acetate/n-hexane: volume ratio is 1/10) to obtain 1-D (0.27 g, yield is 97%).

(3) Synthesis of 1-F: the same synthesis as 1-C, except that 1-D was used instead of 1-B,1-E was used instead of 1-A, gave 1-F (0.24 g, 61% yield).

(4) Synthesis of 1-G: taking a 50 ml double-neck round-bottom flask, putting a stirrer and an upper reflux pipe, introducing nitrogen after drying, and respectively adding 1-F (1 mmol) and dichlorobis (tricyclohexylphosphine) palladium (PdCl) ₂ (PCy ₃ ) ₂ 0.05 mmol), pivalic acid (t-BuCO) ₂ H,2 mmol), cesium carbonate (Cs) ₂ CO ₃ 2 mmol) and dimethylacetamide (20 ml) at 120 ℃ for 10 hours, after the reaction is completed, cooling to room temperature, concentrating the reaction system, and purifying the crude product by column chromatography (ethyl acetate/n-hexane: volume ratio 1/10) to obtain 1-G(0.17 g, 47% yield).

(5) 1-H Synthesis: 1-G (1 mmol), dichloromethane (20 ml) and a solution of boron tribromide (2 mmol) in dichloromethane were added dropwise at 0 ℃ to a 50 ml three-necked flask, and after completion of the reaction, the solvent was removed and the crude product was purified by column chromatography (ethyl acetate/n-hexane, 1/10) to give 1-H (0.29G, 84% yield).

(6) 1-J Synthesis: taking a 50 ml double-neck round-bottom flask, putting a stirrer and an upper reflux pipe, adding 1-H (1 mmol), dichloromethane (20 ml) and pyridine (6 mmol), cooling a reaction system to 0 ℃, adding Tf ₂ O (1.5 mmol), stirring at room temperature for 30 min, cooling to 0 deg.C, adding 30 ml dichloromethane, 40 ml water, drying the organic phase over anhydrous magnesium sulfate, distilling under reduced pressure to remove the solvent, separating the crude product by column chromatography (ethyl acetate/n-hexane, 1/10) to obtain 1-J (0.42 g, 88% yield)

(7) 1, synthesis: a50-milliliter two-neck round-bottom flask is taken and placed into a stirrer and an upper connecting reflux pipe, nitrogen is introduced after drying, 1-J (1 mmol), 1-K (1 mmol), cesium carbonate (0.012 mol), tris (dibenzylideneacetone) dipalladium (Pd 2 (dba) 3, 0.05mmol) and 2-dicyclohexylphosphorus-2 ',4',6' -triisopropylbiphenyl (xphos, 0.055 mmol) are respectively added, then toluene is added, the mixture is refluxed for 24 hours, after reaction, the temperature is cooled to room temperature, a reaction system is filtered and concentrated, and a crude product is purified by column chromatography (dichloromethane/n-hexane, 1/10 (volume ratio)) to obtain a compound 1 (0.46 g, the yield is 70%).

Elemental analysis: c ₄₈ H ₃₁ N ₃ Theoretical value: c,88.72; h,4.81; n,6.47; measured value: c,88.67; h,4.83; n,6.50; HRMS (ESI) M/z (M +): theoretical value: 649.2518; measured value: 649.2525.

(1) Synthesis of 8-C: the same synthesis as 1-C except that 1-B was replaced with 8-B gave 8-C (0.16 g, 51% yield). (2) Synthesis of 8-D, identical to 1-D except that 1-C was replaced with 8-C, to give 8-D (0.25 g, 90% yield)

(3) Synthesis of 8-F: same as the synthesis of 1-C, except that 1-B and 1-A were replaced with 8-D to give 8-F (0.21 g, 53% yield)

(4) Synthesis of 8-G: the same synthesis as 1-G, except that 1-F was replaced with 8-F, gave 8-G (0.18G, 50% yield)

(5) Synthesis of 8-H: the same synthesis as 1-H except that 1-G was replaced with 8-G gave 8-H (0.31G, 89% yield)

(6) Synthesis of 8-J: the same synthesis as 1-J, except that 1-H was replaced by 8-H, gave 8-J (0.41 g, 86% yield)

(7) Synthesis of compound 8: synthesis of Compound 1, except that 1-J was replaced with 8-J and 1-K was replaced with 8-K, compound 8 (0.53 g, 81% yield) was obtained.

Elemental analysis: c ₄₆ H ₂₅ N ₃ Theoretical value of S: c,84.77; h,3.87; n,6.45; s,4.92; measured value: c,84.76; h,3.86; n,6.47; s,4.91; HRMS (ESI) M/z (M +): theoretical values are as follows: 651.1769; measured value: 651.1775.

the same preparation method as above was used except that the raw materials as in table 1 below were used to prepare the corresponding products, and the elemental analysis and HRMS test results of the products are shown in table 2.

TABLE 1

TABLE 2

Device embodiment

An organic electroluminescent device is provided, which has the following layer structure: a base (indium tin oxide (ITO) coated glass substrate)/a Hole Injection Layer (HIL)/a Hole Transport Layer (HTL)/an emission layer (EML)/an Electron Transport Layer (ETL)/an Electron Injection Layer (EIL), and finally a cathode.

The materials used are specified in table 2, and the materials required to make the OLED are as follows.

The preparation of the organic electroluminescent device comprises the following steps:

(1) Substrate cleaning: carrying out ultrasonic treatment on the ITO-coated glass substrate in an aqueous cleaning agent (the components and the concentration of the aqueous cleaning agent are less than or equal to 10wt% of glycol solvent and less than or equal to 1wt% of triethanolamine), washing in deionized water, and carrying out ultrasonic treatment in the following steps of: ultrasonic degreasing is carried out in an ethanol mixed solvent (volume ratio is 1.

(2) Evaporating an organic light-emitting functional layer:

placing the glass substrate with the anode layer in a vacuum chamber, and vacuumizing to 110 ^-6 To 2X 10 ^-4 Pa, evaporating HAT (CN) 6 as a hole injection layer on the anode layer film in vacuum, wherein the evaporation thickness is 5nm;

a hole transport layer is evaporated on the hole injection layer, and the thickness of the evaporated film is 80nm;

the luminescent layer is vapor-plated on the hole transport layer, and the specific preparation method comprises the following steps: carrying out vacuum evaporation on a luminescent host material and a guest material in a co-evaporation manner, wherein the total thickness of the evaporation is 30nm;

a layer of electron transport layer is vacuum evaporated on the luminescent layer, and the preparation method comprises the following steps: carrying out vacuum evaporation on Bphen and LiQ in a co-evaporation mode, wherein the total film thickness of evaporation is 30nm;

vacuum evaporating an electron injection layer on the electron transport layer, wherein the total film thickness of the evaporation is 1nm;

al is evaporated on the electron injection layer, and the total thickness of the evaporated film is 80nm.

The parameters of the layers in the device, their materials and thicknesses, etc., are shown in table 3.

TABLE 3

Testing the performance of the device:

the instrument comprises the following steps: the characteristics of the device such as current, voltage, brightness, luminescence spectrum and the like are synchronously tested by adopting a PR 650 spectrum scanning luminance meter and a Keithley K2400 digital source meter system;

and (3) testing conditions: the current density is 20mA/cm ² Room temperature.

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

The device performance test results are shown in table 4:

TABLE 4

As can be seen from Table 4, the composition of the present invention allows the organic electroluminescent device to have a lower driving voltage (below 3.85V), a higher current efficiency (above 25 Cd/A) and a longer lifetime (above 267 h).

The applicant states that the present invention is illustrated by the above examples of the organic material composition and the application thereof, but the present invention is not limited to the above examples, i.e. it does not mean that the present invention must be implemented by relying on the above examples. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of the raw materials of the product of the present invention, and the addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.

Claims (10)

1. An organic material composition is characterized by comprising a quinoxaline structure-containing fused heterocyclic compound and a hole-transporting compound, wherein the quinoxaline structure-containing fused heterocyclic compound has a structure shown in a formula (1), and the hole-transporting compound has a structure shown in a formula (2):

R ¹ -R ⁶ each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, C1-C30 alkyl wherein one or more methylene groups are substituted by-O-or-S-in such a way that O atoms or S atoms are not adjacent a substituted or unsubstituted C2-C30 alkenyl group, a C2-C30 alkenyl group in which one or more methylene groups are substituted by-O-or-S-in such a manner that O atom or S atom is not adjacent substituted or unsubstituted C2-C30 alkynyl, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroaralkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C1-C30 alkoxy or substituted or unsubstituted C6-C30 aryloxy,

R ¹ -R ⁶ each independently exists or two adjacent rings are connected to form a ring A which is a substituted or unsubstituted benzene ring,

l is selected from a linkage, a substituted or unsubstituted C6-C30 arylene, a substituted or unsubstituted C5-C30 heteroarylene,

Ar ¹ selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C5-C60 heteroaryl, substituted or unsubstituted C6-C60 arylamine, substituted or unsubstituted C5-C60 heteroarylamine, substituted or unsubstituted C5-C60 arylheteroarylamine,

n is an integer selected from 0 to 3,

m is an integer selected from 0 to 5,

n1 is selected from the integer of 0-1,

m1 is an integer selected from 0 to 1;

in the formula (2), p is an integer of 0 to 4,

q is selected from the group consisting of integers from 0 to 4,

R ⁷ 、R ⁸ each independently selected from the group consisting of substituted or unsubstituted C1-C30 alkyl, C1-C30 alkyl wherein one or more methylene groups are substituted by-O-or-S-in such a manner that O atoms or S atoms are not adjacent substituted or unsubstituted C2-C30 alkenyl, C2-C30 alkenyl in which one or more methylene groups are substituted by-O-or-S-in such a manner that O atoms or S atoms are not adjacent, substituted or unsubstituted C2-C30 alkynyl substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroaralkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C1-C30 alkoxy, or substituted or unsubstituted C6-C30 aryloxy,

R ⁷ 、R ⁸ each independently present, orTwo adjacent to four are connected to form a ring B through a chemical bond, or through phenylene or through naphthylene,

L ² 、L ³ each independently selected from the group consisting of a bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C2-C30 heteroarylene,

Ar ⁴ -Ar ⁷ each independently selected from substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl,

w1 is selected from the group consisting of integers from 0 to 1,

w2 is an integer selected from 0 to 1.

2. The organic material composition according to claim 1, wherein the ring B is a substituted or unsubstituted group selected from the group consisting of: a benzene ring, a naphthalene ring, a benzothiophene ring, a benzofuran ring, an indene ring, an indole ring or a seven-membered ring;

preferably, in the formula (2), L ² 、L ³ Each independently selected from the group consisting of a linking bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, and a substituted or unsubstituted naphthylene group;

preferably, ar ⁴ -Ar ⁷ Each independently selected from the group consisting of substituted or unsubstituted: phenyl, biphenyl, terphenyl, naphthyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, dibenzofuranyl, dibenzothiophenyl, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, carbazolyl, phenyl-substituted carbazolyl, pyridyl-substituted carbazolyl, dibenzocarbazolyl, benzonaphthofuranyl, dinaphthofuranyl, benzonaphthothiophenyl, or dinaphthothiophenyl;

preferably, w1+ w2=1;

preferably, R ⁷ 、R ⁸ Each independently selected from deuterium, halogen, cyano, substituted or unsubstituted groups as follows: methyl, ethyl, tert-butyl, adamantyl, phenyl, biphenyl, terphenyl, naphthyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, dibenzofuranyl, dibenzothiophenyl, dimethylfluorenyl, diphenylfluorenyl, spirobifluorenyl, carbazolyl, phenyl-substituted carbazolyl, pyridyl-substituted carbazolyl, biscarbazolylBenzocarbazolyl, benzonaphthofuranyl, dinaphthofuran, benzonaphthothienyl, dinaphthothiophenyl; plural R ⁷ Same or different, a plurality of R ⁸ The same or different;

preferably, in formula (2), when the group contains a substituent, each of the substituents is independently selected from deuterium, halogen, cyano, unsubstituted or R ' substituted C1-C6 alkyl, unsubstituted or R ' substituted C6-C12 aryl, unsubstituted or R ' substituted C2-C20 heteroaryl; r' is selected from deuterium, halogen, cyano, deuterium substituted methyl or halogen substituted methyl.

3. The organic material composition according to claim 1 or 2, wherein the compound having the structure represented by formula (2) comprises any one of the following compounds:

4. the organic material composition according to any one of claims 1 to 3, wherein n1+ m1=1.

Preferably, -L-Ar ¹ Is selected from

Wherein Ar is ² 、Ar ³ Each independently selected from substituted or unsubstituted C6-C60 aryl, substituted or unsubstituted C5-C60 heteroaryl;

preferably, ar ² 、Ar ³ Each independently selected from the group consisting of substituted or unsubstituted: phenyl, biphenyl, terphenyl, naphthyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, phenyl-substituted carbazolyl, pyridyl-substituted carbazolyl, naphthyl-substituted carbazolyl, biphenyl-substituted carbazolyl, dibenzofuran-substituted phenyl, dibenzothiophene-substituted phenyl, dimethylfluorenyl, diphenyl-substituted fluorenyl, spirobifluorenyl, benzonaphthofuranyl, benzonaphthothiophenyl, benzocarbazolyl, or dibenzocarbazolyl;

preferably, -L-Ar ¹ Is selected from

Wherein the dotted lines represent L and Ar ³ Is connected into a ring through chemical bond;

more preferably, -L-Ar ¹ Selected from the group consisting of substituted or unsubstituted:

preferably, -L-Ar1 is selected from

Wherein the dotted line represents Ar ² 、Ar ³ Is connected into a ring through chemical bonds,

preferably, -L-Ar1 is selected from the group consisting of substituted or unsubstituted

5. The organic material composition according to any one of claims 1 to 4, wherein Ar is Ar ¹ Is selected from

Wherein X ¹ Selected from N or CR ^X1 ，X ² Selected from N or CR ^X2 ，X ³ Selected from N or CR ^X3 ，X ⁴ Selected from N or CR ^X4 ，X ⁵ Selected from N or CR ^X5 ，

R ^X1 、R ^X2 、R ^X3 、R ^X4 、R ^X5 Each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, C1-C30 alkyl wherein one or more methylene groups are-O-or-S-substituted in such a way that the O atom or S atom is not adjacent, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroaralkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C3-C30 cycloalkenylA substituted or unsubstituted C1-C30 alkoxy group or a substituted or unsubstituted C6-C30 aryloxy group,

R ^X1 、R ^X2 、R ^X3 、R ^X4 、R ^X5 each independently exists or two adjacent rings are connected to form a ring, the ring is a substituted or unsubstituted benzene ring, pyridine ring, naphthalene ring, anthracene ring, phenanthrene ring, naphthooxazole ring, naphthothiazole ring, benzofuran ring or benzothiophene ring,

preferably, ar ¹ Is selected from

Preferably, ar ¹ Is selected from

Wherein X ¹ 、X ² 、X ⁵ Any two of which are selected from the group consisting of N,

Y ¹ selected from N, CR ^Y1 ，Y ² Selected from N, CR ^Y2 ，Y ³ Selected from N, CR ^Y3 ，Y ⁴ Selected from N, CR ^Y4 ，

R ^Y1 、R ^Y2 、R ^Y3 、R ^Y4 Each independently selected from hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1-C30 alkyl, C1-C30 alkyl in which one or more methylene groups are substituted by-O-or-S-in such a way that the O atom or S atom is not adjacent, substituted or unsubstituted C7-C30 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C2-C30 heteroaryl, substituted or unsubstituted C3-C30 heteroaralkyl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted C3-C30 heterocycloalkyl, substituted or unsubstituted C3-C30 cycloalkenyl, substituted or unsubstituted C1-C30 alkoxy, or substituted or unsubstituted C6-C30 aryloxy,

R ^Y1 、R ^Y2 、R ^Y3 、R ^Y4 each independently exists, or two adjacent rings are connected to form a ring, and the ring is a substituted or unsubstituted benzene ring.

More preferably, Y ¹ Selected from the group consisting of CR ^Y1 ，Y ² Selected from the group consisting of CR ^Y2 ，Y ³ Selected from the group consisting of CR ^Y3 ，Y ⁴ Selected from the group consisting of CR ^Y4 ，

More preferably, R ^X1 、R ^X2 、R ^X3 、R ^X4 、R ^X5 、R ^Y1 、R ^Y2 、R ^Y3 、R ^Y4 Each independently selected from hydrogen, substituted or unsubstituted: phenyl, biphenyl, terphenyl, naphthyl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, phenyl-substituted carbazolyl, pyridyl-substituted carbazolyl, naphthyl-substituted carbazolyl, biphenyl-substituted carbazolyl, dibenzofuran-substituted phenyl, dibenzothiophene-substituted phenyl, dimethylfluorenyl, diphenyl-substituted fluorenyl, spirobifluorenyl;

preferably, each of said L is independently selected from the group consisting of phenylene, biphenylene, naphthylene,

preferably, R ¹ -R ⁶ Each independently selected from hydrogen, deuterium, cyano, fluorine, methyl, ethyl, tert-butyl, deuterium-substituted methyl, fluorine-substituted methyl, phenyl, biphenyl, pyridyl, dibenzofuranyl, dibenzothienyl, dimethylfluorenyl, carbazolyl, phenyl-substituted carbazolyl, pyridyl-substituted carbazolyl, naphthyl-substituted carbazolyl, biphenyl-substituted carbazolyl;

preferably, ar ¹ Selected from phenyl, biphenyl, terphenyl, naphthyl, benzophenanthryl, phenyl-substituted naphthyl, naphthyl-substituted phenyl, dibenzofuranyl, dibenzothiophenyl, dibenzofuran-substituted phenyl, dibenzothiophene-substituted phenyl, dimethylfluorenyl, diphenyl-substituted fluorenyl, spirobifluorenyl, 2-phenylphenanthrene [3,4-d ]]Oxazolyl, 2-phenylphenanthrene [3,4-d ]]A thiazolyl group;

preferably, when said group contains a substituent, each of said substituents is independently selected from deuterium, halogen, cyano, unsubstituted or R ' substituted C1-C6 alkyl, unsubstituted or R ' substituted C6-C12 aryl, unsubstituted or R ' substituted C2-C20 heteroaryl; r' is selected from deuterium, halogen, cyano, deuterium substituted methyl, halogen substituted methyl;

more preferably, the C1-C6 alkyl group is selected from methyl, ethyl, tert-butyl;

the aryl of C6-C12 is selected from phenyl, biphenyl and naphthyl;

the heteroaryl of C3-C20 is selected from triazinyl, pyridyl, phenyl-substituted pyridyl, pyridyl-substituted phenyl, dibenzofuranyl and dibenzothiophenyl.

6. The organic material composition according to any one of claims 1 to 5, wherein the compound having the structure represented by formula (1) is any one of the following compounds:

wherein D represents deuterium.

7. The organic material composition according to claim 1, characterized in that the thermal decomposition temperature difference of the organic material composition is not more than 20 ℃, preferably not more than 10 ℃, further preferably not more than 5 ℃.

8. Use of the organic material composition according to any one of claims 1 to 7 for the preparation of an optical device;

preferably, the optical device comprises any one of an organic electroluminescent device, an organic field effect transistor, an organic thin film transistor, an organic light emitting transistor, an organic integrated circuit, an organic solar cell, an organic field quenching device, a light emitting electrochemical cell, an organic laser diode or an organic photoreceptor.

9. An organic electroluminescent device comprising an anode and a cathode, and an organic layer disposed between the anode and the cathode, the organic layer comprising the organic material composition according to any one of claims 1 to 7;

preferably, the organic layer includes a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, which are stacked in this order from the anode side to the cathode side;

preferably, the material of the light-emitting layer comprises a host material and a guest material, the host material comprising the organic material composition of any one of claims 1 to 7;

preferably, the guest material includes a phosphorescent dopant comprising a complex comprising Ir or Pt.

10. An organic electroluminescent device characterized in that it comprises the organic electroluminescent device as claimed in any one of claims 1 to 7.