CN104797571A - Organic electroluminescent compounds and organic electroluminescent device comprising the same - Google Patents

Organic electroluminescent compounds and organic electroluminescent device comprising the same Download PDF

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CN104797571A
CN104797571A CN201380059780.0A CN201380059780A CN104797571A CN 104797571 A CN104797571 A CN 104797571A CN 201380059780 A CN201380059780 A CN 201380059780A CN 104797571 A CN104797571 A CN 104797571A
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substituted
yuan
unsubstituted
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alkyl
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H-J·康
D-H·文
H-R·康
S-K·尹
N-K·金
S-W·李
H-J·权
K-J·李
B-O·金
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Rohm and Haas Electronic Materials Korea Ltd
Rohm and Haas Electronic Materials LLC
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Abstract

The present invention relates to a novel organic electroluminescent compound and an organic electroluminescent device comprising the same. Using the organic electroluminescent compound according to the present invention, an organic electroluminescent device can have a long lifespan, a low driving voltage, high current efficiency and high power efficiency.

Description

Organic electroluminescent compounds and the Organnic electroluminescent device comprising described compound
Technical field
The present invention relates to organic electroluminescent compounds and the Organnic electroluminescent device comprising described compound.
Background technology
Electroluminescent (EL) device is a kind of selfluminous device, and its advantage is that it provides wider visual angle, larger contrast ratio and time of response faster.Organic El device develops [Applied Physics journal (Appl.Phys.Lett.) 51 by Eastman Kodak Company (Eastman Kodak) by using little aromatic diamine molecule and aluminium complex at first as the material for the formation of luminescent layer, 913,1987].
The most important factor of the luminous efficiency in decision organic El device is luminescent material.Up to now, fluorescent material is widely used as luminescent material.But in view of electroluminescent mechanism, because phosphor material makes luminous efficiency strengthen four (4) doubly in theory compared with fluorescent material, phosphorescent light-emitting materials is extensively studied.Iridium (III) complex compound is called as phosphor material widely; comprise two (2-(2 '-benzothienyl)-pyridine root-N, C3 ') iridium (acetyl-pyruvate) ((acac) Ir (btp) 2), three (2-phenylpyridine) iridium (Ir (ppy) 3) and two (4,6-difluorophenyl pyridinato root-N, C2) pyridine carboxylic acid iridium (Firpic) respectively as glowing, the material of green glow and blue light.
At present, 4,4 '-N, N '-two carbazoles-diphenyl (CBP) is the most known material of main part for phosphor material.Recently, send people such as Neil (Pioneer) (Japan) by using bathocuproine (bathocuproine, BCP) and two (2-methyl-8-quinoline) (4-phenylphenol) aluminium (III) (BAlq) etc. develop efficient organic El device as material of main part, it is called as hole barrier materials.
Although these materials provide good luminous feature, it has following shortcoming: (1), owing to its lower glass transition temp and undesirable heat stability, its degraded may occur in a vacuum during high-temperature deposition process.(2) power efficiency of organic El device is provided by [(π/voltage) × current efficiency], and described power efficiency and voltage are inversely proportional to.Although the organic El device comprising phosphorescent light body material provides the current efficiency (cd/A) higher than the organic El device comprising fluorescent material, significantly high driving voltage is required.Therefore, there is not the advantage about power efficiency (lm/W).(3) in addition, the work-ing life of organic El device is shorter, and still needs to improve luminous efficiency.
The special permission of korean patent application case discloses No. 2011-0013220, No. 2005-0100694 and No. 2007-0073868 compound disclosed for organic El device, and wherein aryl or nitrogen-containing hetero aryl are connected on the nitrogen-atoms of benzo carbazole or dibenzo-carbazole main chain.But above reference fails specifically to disclose the compound for organic El device, wherein on phenyl and the nitrogen-containing hetero aryl carbon atom that is connected respectively to benzo carbazole and nitrogen-atoms.
Summary of the invention
Technical problem
Target of the present invention is to provide a kind of organic electroluminescent compounds, and it can provide has compared with the long life and compared with the el light emitting device operating to strengthen electric current and power efficiency under low driving voltage.
The solution of problem
The present inventor finds that above target can be realized by the compound represented by following formula 1:
Wherein
L 1represent singly-bound, substituted or unsubstituted (C6-C30) arylidene or substituted or unsubstituted (3 yuan to 30 yuan) inferior heteroaryl, Ar 1to Ar 4represent hydrogen independently of one another, deuterium, halogen, cyano group, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3 yuan to 30 yuan) heteroaryl, substituted or unsubstituted (C1-C30) alkylamino, substituted or unsubstituted (C6-C30) arylamino, or substituted or unsubstituted (C1-C30) alkyl (C6-C30) arylamino, maybe can be connected to adjacent substituents to form alicyclic ring or the aromatic ring of substituted or unsubstituted (3 yuan to 30 yuan) monocycle or many rings, its carbon atom can be selected from nitrogen by least one, the heteroatoms displacement of oxygen and sulphur, A ring represents substituted or unsubstituted (C6-C30) aryl or substituted or unsubstituted (3 yuan to 30 yuan) heteroaryl, X 1represent-N-or-CR 1-, X 2represent-N-or-CR 2-, X 3represent-N-or-CR 3-, at X 1to X 3expression-CR respectively 1-,-CR 2-and-CR 3-when, A ring represents nitrogenous (3 yuan to 30 yuan) heteroaryl, R 1to R 3represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C13-C30) Spirofluorene-based or substituted or unsubstituted (3 yuan to 30 yuan) heteroaryl independently of one another, 1 represents 0 or 1, m represents the integer of 0 to 5, n represents the integer of 0 to 2, when m or n is the integer of two or more, Ar 1or Ar 2in each can be identical or different, and described (Asia) heteroaryl contains the heteroatoms that at least one is selected from B, N, O, S, P (=O), Si and P.
Advantageous effect of the present invention
By using according to organic electroluminescent compounds of the present invention, Organnic electroluminescent device can have comparatively long life and with the operation of comparatively low driving voltage to strengthen electric current and power efficiency.
Embodiment
Hereinafter, will describe the present invention.But, below describe and be intended to explain the present invention, and mean never in any form and limit the scope of the invention.
The invention provides with the organic electroluminescent compounds of above formula 1, comprise the electroluminescent organic material of described compound and comprise the Organnic electroluminescent device of described material.
Formula 1 compound of the present invention is described in detail.
Herein, " alkyl " comprises methyl, ethyl, n-propyl, sec.-propyl, normal-butyl, isobutyl-, the tertiary butyl etc." thiazolinyl " comprises vinyl, 1-propenyl, 2-propenyl, 1-butylene base, crotyl, 3-butenyl, 2-methyl but-2-ene base etc." alkynyl " comprises ethynyl, 1-proyl, 2-propynyl, ethyl acetylene base, 2-butyne base, 3-butynyl, 1-methylpent-2-alkynyl etc." cycloalkyl " representative ring propyl group, cyclobutyl, cyclopentyl, cyclohexyl etc." 5 yuan to 7 yuan Heterocyclylalkyls " instruction has 5 to 7 ring backbone atoms and (comprises at least one and be selected from B, N, O, S, P (=O), Si and P, the preferably heteroatoms of O, S and N) cycloalkyl, and comprise tetrahydrofuran (THF), tetramethyleneimine, thiacyclopentane, tetrahydropyrans etc.In addition, " (Asia) aryl " instruction derived from the monocycle of aromatic hydrocarbons or condensed ring, and comprises phenyl, diphenyl, terphenyl, naphthyl, dinaphthalene, phenyl napthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzo fluorenyl, dibenzo fluorenyl, phenanthryl, phenyl phenanthryl, anthryl, indenyl, connection sub-triphenyl, pyrenyl, naphthacenyl, perylene base, Qu Ji, thick tetraphenyl, fluoranthene base etc." (3 yuan to 30 yuan) (Asia) heteroaryl " instruction have 3 to 30 ring backbone atoms (comprise at least one, preferably 1 to 4 be selected from the heteroatoms of the group be made up of B, N, O, S, P (=O), Si and P) aryl, the condensed ring that can be monocycle or condense with at least one phenyl ring, it can be fractional saturation, can be by making at least one heteroaryl or aryl be connected to via singly-bound the group that heteroaryl formed, and comprise monocyclic heteroaryl, as furyl, thienyl, pyrryl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl group, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazine base, triazolyl, tetrazyl, furan a word used for translation base, pyridyl, pyrazinyl, pyrimidyl, pyridazinyl etc., with condensed ring type heteroaryl, as benzofuryl, benzothienyl, isobenzofuran-base, dibenzofuran group, dibenzothiophene base, benzimidazolyl-, benzothiazolyl, benzisothiazole base, benzoisoxazole base, benzoxazolyl, pseudoindoyl, indyl, indazolyl, diazosulfide base, quinolyl, isoquinolyl, cinnolines base, quinazolyl, quinoxalinyl, carbazyl, Fei oxazinyl, coffee pyridine base, benzodioxole group etc.In addition, " halogen " comprises F, Cl, Br and I.
Herein, " being substituted " of stating in " substituted or unsubstituted " means that the hydrogen atom in a certain functional group is replaced by another atom or group (i.e. substituting group).With the L of above formula 1 1, Ar 1to Ar 4, A ring and R 1to R 3in, the alkyl be substituted, (Asia) aryl be substituted, (Asia) heteroaryl be substituted, the alkylamino be substituted, the arylamino be substituted is that at least one is selected from by the substituting group of the following group formed: deuterium with the substituting group of the alkyl aryl amino be substituted independently of one another, halogen, (C1-C30) alkyl not being substituted or being optionally substituted by halogen, (C1-C30) alkoxyl group, (C6-C30) aryl, (3 yuan to the 30 yuan) heteroaryl not being substituted or being replaced by (C6-C30) aryl, (C3-C30) cycloalkyl, (5 yuan to 7 yuan) Heterocyclylalkyl, three (C1-C30) alkyl tin groups, alkyl silane groups, three (C6-C30) aryl-silane base, two (C1-C30) alkyl (C6-C30) aryl-silane base, (C1-C30) alkyl two (C6-C30) aryl-silane base, (C2-C30) thiazolinyl, (C2-C30) alkynyl, cyano group, two (C1-C30) alkylamino, two (C6-C30) arylamino, (C1-C30) alkyl (C6-C30) arylamino, two (C6-C30) aryl boryl, two (C1-C30) alkyl boryl, (C1-C30) alkyl (C6-C30) aryl boryl, (C6-C30) aryl (C1-C30) alkyl, (C1-C30) alkyl (C6-C30) aryl, carboxyl, nitro and hydroxyl, and preferably at least one is selected from the substituting group of the group be made up of (C1-C6) alkyl and (C6-C21) aryl.
Preferably, formula 1 compound can be represented by following formula 1a or 1b:
Wherein
L 1, Ar 1to Ar 4, A ring, X 1, X 2, X 3, R 2, R 3, 1, m and n as with in above formula 1 define.
According to an aspect of the present invention, L 1represent singly-bound, substituted or unsubstituted (C6-C30) arylidene or substituted or unsubstituted (3 yuan to 30 yuan) inferior heteroaryl; Preferably represent singly-bound or substituted or unsubstituted (C6-C21) arylidene; More preferably represent singly-bound or unsubstituted (C6-C21) arylidene; And even more preferably represent singly-bound or phenylene.
Ar 1to Ar 4represent hydrogen independently of one another, deuterium, halogen, cyano group, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3 yuan to 30 yuan) heteroaryl, substituted or unsubstituted (C1-C30) alkylamino, substituted or unsubstituted (C6-C30) arylamino, or substituted or unsubstituted (C1-C30) alkyl (C6-C30) arylamino, maybe can be connected to adjacent substituents to form alicyclic ring or the aromatic ring of substituted or unsubstituted (3 yuan to 30 yuan) monocycle or many rings, and preferably represent hydrogen, unsubstituted (C1-C6) alkyl, substituted or unsubstituted (C6-C21) aryl or unsubstituted (5 yuan to 21 yuan) heteroaryl.More preferably, Ar 1, Ar 3and Ar 4represent hydrogen or unsubstituted (C6-C12) aryl independently of one another; Ar 2represent hydrogen, (C1-C4) alkyl, be not substituted or by (C1-C4) alkyl replace (C6-C18) aryl or unsubstituted (5 yuan to 18 yuan) heteroaryl.Even more preferably, Ar 1represent hydrogen, phenyl or naphthyl; Ar 2the benzo fluorenyl representing the fluorenyl that hydrogen, (C1-C4) alkyl, phenyl, naphthyl, dibenzofuran group, dibenzothiophene base, quilt (C1-C4) alkyl replace or replaced by (C1-C4) alkyl; Ar 3represent hydrogen; And Ar 4represent hydrogen or phenyl.
A ring represents substituted or unsubstituted (C6-C30) aryl or substituted or unsubstituted (3 yuan to 30 yuan) heteroaryl; Preferably represent substituted or unsubstituted (C6-C21) aryl or substituted or unsubstituted (5 yuan to 21 yuan) heteroaryl; More preferably represent (C6-C12) aryl; Or (5 yuan to the 15 yuan) heteroaryl not being substituted or being replaced by (C6-C12) aryl; And the pyridyl even more preferably representing phenyl, diphenyl, naphthyl, quinolyl, isoquinolyl, naphthyridinyl, phenanthryl, coffee pyridine base, benzoquinoline base, Benzoquinazole base (benzoquinazolyl), benzisoquinoline base, coffee quinoline base, pyridyl, pyrimidyl or be substituted by phenyl.
X 1represent-N-or-CR 1-; X 2represent-N-or-CR 2-; And X 3represent-N-or-CR 3-.At X 1to X 3expression-CR respectively 1-,-CR 2-and-CR 3-when, A ring represents nitrogenous (3 yuan to 30 yuan) heteroaryl, preferably represents nitrogenous (5 yuan to 21 yuan) heteroaryl, and more preferably represents nitrogenous (5 yuan to 15 yuan) heteroaryl.
R 1to R 3represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C13-C30) Spirofluorene-based or substituted or unsubstituted (3 yuan to 30 yuan) heteroaryl independently of one another; And preferably represent hydrogen, substituted or unsubstituted (C6-C21) aryl, substituted or unsubstituted (C15-C25) Spirofluorene-based or substituted or unsubstituted (5 yuan to 21 yuan) heteroaryl.More preferably, R 1to R 3represent hydrogen independently of one another; (C6-C18) aryl not being substituted or being replaced by (C1-C4) alkyl or (C6-C12) aryl; (C15-C25) Spirofluorene-based; Or (5 yuan to the 15 yuan) heteroaryl not being substituted or being replaced by (C6-C12) aryl.Even more preferably, R 1to R 3represent hydrogen independently of one another; Phenyl; Diphenyl; Terphenyl; Naphthyl; Naphthylphenyl; By the phenyl that (C1-C4) alkyl replaces; Fluorenyl; By the fluorenyl that (C1-C4) alkyl or phenyl replaces; Spiral shell di-fluorenes; Spiral shell [ring penta-1,9 '-fluorenes] base; Spiral shell [hexamethylene-1,9 '-fluorenes] base; Dibenzofuran group; Dibenzothiophene base; Or the carbazyl be substituted by phenyl.Exactly, R 1represent hydrogen; R 2represent hydrogen or phenyl; And R 3the carbazyl representing the phenyl of hydrogen, phenyl, diphenyl, terphenyl, naphthyl, quilt (C1-C4) alkyl replacement, dibenzofuran group, dibenzothiophene base or be substituted by phenyl.
1 represents 0 or 1; M represents the integer of 0 to 5, preferably represents the integer of 0 to 2; N represents the integer of 0 to 2, preferably represents 0 or 1; When m or n is the integer of two or more, Ar 1or Ar 2in each can be identical or different.
According to one embodiment of present invention, with in above formula 1, L 1represent singly-bound or substituted or unsubstituted (C6-C21) arylidene; Ar 1to Ar 4represent hydrogen, unsubstituted (C1-C6) alkyl, substituted or unsubstituted (C6-C21) aryl or unsubstituted (5 yuan to 21 yuan) heteroaryl independently of one another; A ring represents substituted or unsubstituted (C6-C21) aryl or substituted or unsubstituted (5 yuan to 21 yuan) heteroaryl; X 1represent-N-or-CR 1-; X 2represent-N-or-CR 2-; X 3represent-N-or-CR 3-; At X 1to X 3expression-CR respectively 1-,-CR 2-and-CR 3-when, A ring represents nitrogenous (5 yuan to 21 yuan) heteroaryl; R 1to R 3represent hydrogen, substituted or unsubstituted (C6-C21) aryl, substituted or unsubstituted (C15-C25) Spirofluorene-based or substituted or unsubstituted (5 yuan to 21 yuan) heteroaryl independently of one another; 1 represents 0 or 1; M represents the integer of 0 to 2; N represents 0 or 1; And when m is 2, Ar 2in each can be identical or different.
According to another embodiment of the invention, with in above formula 1, L 1represent singly-bound or unsubstituted (C6-C12) arylidene; Ar 1, Ar 3and Ar 4represent hydrogen or unsubstituted (C6-C12) aryl independently of one another; Ar 2represent hydrogen; (C1-C4) alkyl; (C6-C18) aryl not being substituted or being replaced by (C1-C4) alkyl; Or unsubstituted (5 yuan to 18 yuan) heteroaryl; A ring represents (C6-C12) aryl; Or (5 yuan to 15 yuan) that are not substituted or replaced by (C6-C12) aryl; X 1represent-N-or-CR 1-; X 2represent-N-or-CR 2-; X 3represent-N-or-CR 3-; At X 1to X 3expression-CR respectively 1-,-CR 2-and-CR 3-when, A ring represents nitrogenous (5 yuan to 15 yuan) heteroaryl; R 1to R 3represent hydrogen independently of one another; (C6-C18) aryl not being substituted or being replaced by (C1-C4) alkyl or (C6-C12) aryl; (C15-C25) Spirofluorene-based; Or (5 yuan to the 15 yuan) heteroaryl not being substituted or being replaced by (C6-C12) aryl; 1 represents 0 or 1; M represents the integer of 0 to 2; N represents 0 or 1; And when m is 2, Ar 2in each can be identical or different.
The organic electroluminescent compounds of formula 1 of the present invention comprises following, but is not limited thereto:
The compounds of this invention can be prepared by the synthetic method that those skilled in the art is known.For example, it can be prepared according to following reaction process 1 or 2.
[reaction process 1]
[reaction process 2]
The invention provides the electroluminescent organic material of the organic electroluminescent compounds of contained 1, and comprise the Organnic electroluminescent device of described material.
Described material can be made up of the organic electroluminescent compounds of formula 1.In other side, except formula 1 compound, described material can comprise the Conventional compounds be included in electroluminescent organic material further.
Organnic electroluminescent device can comprise the first electrode, the second electrode and at least one be placed in organic layer between first and second electrode described.Organic layer can comprise the organic electroluminescent compounds of at least one formula 1.
One in first and second electrodes can be anode, and another one can be negative electrode.Organic layer can comprise luminescent layer, and can comprise at least one further and be selected from following layer: hole injection layer, hole transmission layer, electron transfer layer, electron injecting layer, interlayer, hole blocking layer and electronic barrier layer.
In addition, organic layer can comprise luminescent layer, wherein can contained 1 organic electroluminescent compounds as material of main part.
In addition, the phosphorescent dopants being used from Organnic electroluminescent device with material of main part one according to the present invention can be selected from the compound represented by following formula 2:
M 1L 101L 102L 103---------------------(2)
Wherein M 1be selected from the group be made up of Ir, Pt, Pd and Os; L 101, L 102and L 103be selected from following structure independently of one another:
R 201to R 203(C1-C30) alkyl represent hydrogen, deuterium independently of one another, not being substituted or being optionally substituted by halogen, be not substituted or by (C1-C30) alkyl replace (C6-C30) aryl or halogen;
R 204to R 219represent hydrogen independently of one another, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C1-C30) alkoxyl group, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C2-C30) thiazolinyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted single or two (C1-C30) alkylamino, substituted or unsubstituted single or two (C6-C30) arylamino, SF 5, substituted or unsubstituted three (C1-C30) alkyl tin groups, alkyl silane groups, substituted or unsubstituted two (C1-C30) alkyl (C6-C30) aryl-silane base, substituted or unsubstituted three (C6-C30) aryl-silane base, cyano group or halogen, maybe can be connected to adjacent substituents to form alicyclic ring or the aromatic ring of (C5-C30) monocycle or many rings,
R 220to R 223(C1-C30) alkyl represent hydrogen, deuterium independently of one another, not being substituted or being optionally substituted by halogen, (C6-C30) aryl not being substituted or being replaced by (C1-C30) alkyl;
R 224and R 225represent hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl or halogen independently of one another, maybe can be connected to each other the alicyclic ring or the aromatic ring that form (C5-C30) monocycle or many rings;
R 226represent substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (5 yuan or 30 yuan) heteroaryl or halogen;
R 227to R 229represent hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl or halogen independently of one another;
R 230represent hydrogen, substituted or unsubstituted (C1-C30) alkyl or substituted or unsubstituted (C3-C30) cycloalkyl;
F and g represents the integer of 1 to 3 independently of one another; When f or g is the integer of two or more, R 230in each can be identical or different;
Q represents r 231to R 242(C1-C30) alkyl represent hydrogen, deuterium independently of one another, not being substituted or being optionally substituted by halogen, (C1-C30) alkoxyl group, halogen, substituted or unsubstituted (C6-C30) aryl, cyano group or substituted or unsubstituted (C5-C30) cycloalkyl, or adjacent substituents can be connected to form volution or condensed ring via alkylidene group or alkenylene, or R can be connected to via alkylidene group or alkenylene 207or R 208to form saturated or unsaturated condensed ring.
Exactly, the doping agent of formula 2 preferably below, but to be not limited thereto:
Except the organic electroluminescent compounds of formula 1, Organnic electroluminescent device of the present invention can also comprise at least one further and be selected from by the compound of the group formed based on the compound of arylamines and the compound of styrene-based base arylamines.
In Organnic electroluminescent device of the present invention, except the organic electroluminescent compounds of formula 1, organic layer can also comprise at least one further and be selected from by the metal of the following group formed: the organo-metallic of the 1st race's metal of periodictable, group II metal, the 4th row transition metals, the 5th row transition metals, lanthanon and d-transition element, or comprises at least one complex compound of described metal.Organic layer can comprise luminescent layer and charge generation layer further.
In addition, Organnic electroluminescent device of the present invention can by comprising at least one luminescent layer and transmitting white further, and described luminescent layer also comprises blue light electroluminescent compounds known in affiliated field, ruddiness electroluminescent compounds or green glow electroluminescent compounds except the compounds of this invention.
In Organnic electroluminescent device of the present invention, at least one layer (below is " upper layer ") can be positioned on the internal surface of one or two electrode, and described layer is selected from chalcogenide layer, metal halide and metal oxide layer.Exactly, chalcogenide (the comprising oxide compound) layer of silicon or aluminium is preferably located on the anode surface in electroluminescent middle layer, and metal halide or metal oxide are preferably located on the cathode surface in electroluminescent middle layer.This type of upper layer provides operational stability for Organnic electroluminescent device.Preferably, chalcogenide comprises SiOx (1≤X≤2), AlOx (1≤X≤1.5), SiON, SiAlON etc.; Metal halide comprises LiF, MgF 2, CaF 2, rare earth metal fluorochemical etc.; And metal oxide comprises Cs 2o, Li 2o, MgO, SrO, BaO, CaO etc.
In Organnic electroluminescent device of the present invention, the mixing zone of the mixing zone of electric transmission compound and reductibility doping agent or hole transport compound and oxidisability doping agent can be positioned at pair of electrodes at least one on the surface.In the case, electric transmission compound is reduced to negatively charged ion, and therefore become easier from mixing zone inject and transmission electronic to electroluminescent medium.In addition, hole transport compound is oxidized to positively charged ion, and therefore become easier from mixing zone inject and transporting holes to electroluminescent medium.Preferably, oxidisability doping agent comprises various Lewis acid (Lewisacid) and acceptor compound; And originality doping agent comprises basic metal, alkali metal compound, alkaline-earth metal, rare earth metal and its mixture.Reductibility dopant layer can be used as charge generation layer has two or more electroluminescence layers and transmitting white el light emitting device with preparation.
In order to form every one deck of Organnic electroluminescent device of the present invention, dry type film can be used, as vacuum-evaporation, sputtering, plasma body and ion plating method; Or wet type film, as spin coating, dip-coating and flow coating processes.
When using wet type film, film can by being formed the material dissolves or be diffused in any suitable solvent forming every one deck, and described solvent is as ethanol, chloroform, tetrahydrofuran (THF), diox etc.
Hereinafter, the preparation method of the compounds of this invention, described compound and the characteristics of luminescence of described device is explained in detail with reference to following instance.
example 1: preparation Compound C-12
prepare compound 2 [(4-phenylnaphthalene-1-base) boric acid]
By bromo-for 1-4-phenylnaphthalene (compound 1) (50g, after 176mmol) being dissolved in anhydrous tetrahydro furan (THF) (1L) in flask, stir the mixture at-78 DEG C and slowly drip n-BuLi (2.5M in hexane, 132mL) wherein.At room temperature stirred reaction mixture 1 hour.Being cooled to after-78 DEG C by reaction mixture, slowly drip triisopropyl borate ester (61mL, 264mmol) wherein.At room temperature stirred reaction mixture 3 hours subsequently.When the reactions are completed, mixture is extracted with ethyl acetate.The organic layer MgSO extracted 4drying, and with hexane solidification, obtain compound 2 (30g, 68%).
prepare compound 4 [1-(the bromo-2-nitrophenyl of 4-)-4-phenylnaphthalene]
By bromo-for Isosorbide-5-Nitrae-two 2-oil of mirbane (compound 3) (14.2g, 50.38mmol), compound 2 (15g, 60.46mmol) and tetrakis triphenylphosphine palladium (0) (Pd (PPh 3) 4) (1.7g, 1.51mmol) be dissolved in 2M Na in flask 2cO 3(125mL), in toluene (250mL) and ethanol (125mL) after, mixture is refluxed 5 hours at 120 DEG C.After being extracted with ethyl acetate reaction mixture, organic layer MgSO 4drying, and with purification by column chromatography, obtain compound 4 (13g, 64%).
prepare compound 5 [1-(3-nitro [1,1 '-diphenyl]-4-base)-4-phenylnaphthalene]
In the mode identical with preparing compound 4, obtain compound 5 (12g, 98%) by using compound 4 (13g, 33.87mmol) and phenyl-boron dihydroxide (3.9g, 32.26mmol).
prepare compound 7 [5,9-phenylbenzene-7H-benzo [c] carbazole]
After compound 5 (12g, 32mmol) being dissolved in triethyl phosphate (130mL), mixture being refluxed 6 hours at 150 DEG C, and uses methyl alcohol wet-milling subsequently, obtain compound 7 (6.8g, 62%).
preparation Compound C-12 [5,9-phenylbenzene-7-(4-phenylquinazoline-2-base)-7H-benzo [c] carbazole]
By chloro-for 2-4-phenylquinazoline (compound 9) (4g, 10.83mmol) with compound 7 (3.2g, after 12.99mmol) being dissolved in dimethyl formamide (DMF) (55mL), add NaH (0.4g wherein, 16.4mmol, 60% in mineral oil).At room temperature stir the mixture 12 hours.Methyl alcohol and distilled water is added in mixture.Under reduced pressure filter gained solid, and with purification by column chromatography, obtain Compound C-12 (2g, 33%).
UV:384nm, PL:515nm, fusing point: 178 DEG C
MS/EIMS experimental value 573.7; Calculated value 573.23
[example 2-24]
Following compound is prepared in the mode similar with above example 1.
example 25: preparation Compound C-56
preparation Compound C-56 [5,9-phenylbenzene-7-(2-phenylquinoline-7-base)-7H-benzo [c] carbazole]
By chloro-for 7-2-phenylquinoline (3g, 11.91mmol) with compound 7 (4g, after 10.83mmol) being dissolved in dimethyl formamide (DMF) (60mL), add NaH (0.4g wherein, 16.4mmol, 60% in mineral oil).At room temperature stir the mixture 12 hours.Methyl alcohol and distilled water is added in mixture.Under reduced pressure filter gained solid, and with purification by column chromatography, obtain Compound C-56 (2g, 33%).
The feature of the compound of example 1 to 25 is shown in the following table 1.
[table 1]
example 26: preparation Compound C-66
prepare compound 2-5
Compound 2-5 (12g, 76%) is obtained in the mode identical with the compound 7 preparing example 1.
prepare compound 2-6
In the round-bottomed flask of 250mL size, the mixture of bromo-to compound 2-5 (12g), 1-4-iodobenzene (8g), CuI (500mg), quadrol (EDA) (4mL) and toluene (100mL) is stirred 13 hours under reflux.After cooling to room temperature, handling procedure is carried out to reaction mixture, and uses purification by column chromatography subsequently, obtain compound 2-6 (14g, 87%).
prepare compound 2-7
By compound 2-6 (14g), B in the round-bottomed flask of 250mL size 2(Pin) 2(15g), molybdenyl dichloride (triphenyl phosphine) palladium (II) (PdCl 2(PPh 3) 2) (1.2mg), potassium acetate (KOAc 2) mixture of (10g) and Isosorbide-5-Nitrae-diox (100mL) stirs 13 hours under reflux.After cooling to room temperature, handling procedure is carried out to reaction mixture, and uses purification by column chromatography subsequently, obtain compound 2-7 (15g, 82%).
prepare compound 2-9
By compound 2-8 (50g), phenyl-boron dihydroxide (26g), Pd (PPh in round-bottomed flask 3) 4(3g), K 2cO 3(26g), the mixture of ethanol (EtOH) (50mL), purified water (100mL) and toluene (400mL) stirs 4 hours under reflux.After cooling to room temperature, handling procedure is carried out to reaction mixture, and uses purification by column chromatography subsequently, obtain compound 2-9 (25g).
preparation Compound C-66
By compound 2-7 (11g), compound 2-9 (4g), Pd (PPh in round-bottomed flask 3) 4(1g), K 2cO 3(5g), the mixture of EtOH (30mL), purified water (60mL) and toluene (200mL) stirs 20 hours under reflux.After cooling to room temperature, handling procedure is carried out to reaction mixture, and uses purification by column chromatography subsequently, obtain Compound C-66 (1.5g).
example 27: preparation Compound C-65
Except use 1-bromonaphthalene but not the bromo-4-phenylnaphthalene of 1-as except compound 1, obtain compound 3-1 in the mode identical with the compound 2 to 7 preparing example 1.By compound 2-9 (6.8g, 28.41mmol), compound 3-1 (10g, 34.09mmol), K 2cO 3the mixture of (4.7g, 34.09mmol), DMAP (2.1g, 17.05mmol) and DMF (170mL) stirs 5 hours under reflux.By reaction mixture cool to room temperature, and subsequently to wherein adding distilled water.Reaction mixture methylene dichloride (MC) extraction, uses MgSO 4drying, under reduced pressure distills, and uses ethyl acetate (EA) and methyl alcohol recrystallize subsequently, obtains Compound C-65 (3.5g, 22%).
[device example 1] uses the compounds of this invention to manufacture OLED device
The compounds of this invention is used to manufacture OLED device.To for Organic Light Emitting Diode (OLED) device (SCP (Samsung Corning), Republic of Korea (Republic of Korea)) transparency electrode tin indium oxide (ITO) film (15 Ω/sq) on a glass substrate sequentially carry out using the ultrasonic washing of trieline, acetone, ethanol and distilled water, and to be stored in subsequently in Virahol.Subsequently ITO substrate is arranged on the substrate holder of vacuum phase deposition equipment.By N 1, N 1 'two (the N in-([1,1 '-diphenyl]-4,4 '-two base) 1-(naphthalene-1-base)-N 4, N 4-diphenyl benzene-Isosorbide-5-Nitrae-diamines) be incorporated in the unit of described vacuum phase deposition equipment, and be 10 by the pressure-controlling in the chamber of described equipment subsequently -6holder.After this, electric current is applied to described unit to make the materials vaporize of above introducing, on ITO substrate, forms the hole injection layer that thickness is 60nm thus.Subsequently by N, N '-two (4-diphenyl)-N, N '-two (4-diphenyl)-4,4 '-diamino diphenyl is incorporated in another unit of described vacuum phase deposition equipment, and make it vaporization by electric current is applied to described unit, on hole injection layer, form the hole transmission layer that thickness is 20nm thus.After this, Compound C-12 is incorporated in a unit of vacuum phase deposition equipment as material of main part, and Compound D-7 is incorporated in another unit as doping agent.With different rates, bi-material is vaporized, to make described doping agent with the doping of the total amount 4wt% by main body and doping agent deposition to form the luminescent layer that thickness is 30nm on hole transmission layer.Subsequently 2-(4-(9,10-bis-(naphthalene-2-base) anthracene-2-base) phenyl)-1-phenyl-1H-benzo [d] imidazoles is incorporated in a unit, and is incorporated in another unit by quinolyl lithium.With phase same rate, bi-material is vaporized, deposit to form the electron transfer layer that thickness is 30nm on luminescent layer with the doping of 50wt% respectively to make it.Electron supplying layer depositing after quinolyl lithium as thickness is the electron injecting layer of 2nm, is the Al negative electrode of 150nm subsequently by another vacuum phase deposition equipment deposit thickness on described electron injecting layer.Thus, OLED device is manufactured.All material for the manufacture of OLED device is all by 10 -6hold in the palm those materials of lower vacuum-sublimation and purifying.Manufactured OLED device showing luminance under the driving voltage of 3.4V is 980cd/m 2red emission and current density is 5.9mA/cm 2.The time needed for 90% being reduced to brightness under 5,000nit is 160 hours or more.
[device example 2 to 27] uses the compounds of this invention to manufacture OLED devicedivided by those of following table 2 as beyond material of main part and doping agent, manufacture OLED device in the mode identical with device example 1.
[comparison unit example 1] manufactures OLED device by using Conventional compounds
Except use 4,4 '-N, N '-two carbazoles-diphenyl (CBP) as material of main part and Compound D-11 as doping agent to form the luminescent layer that thickness is 30nm on hole transmission layer; And use two (2-methyl-8-quinoline foundation)-4-phenylphenol aluminium (III) to be formed beyond the hole blocking layer that thickness is 10nm, manufacture OLED device in the mode identical with device example 1.Manufactured OLED device showing luminance under the driving voltage of 8.2V is 1,000cd/m 2red emission and current density is 20.0mA/cm 2.The time needed for 90% being reduced to brightness under 5,000nit is 10 hours or more.
The result of device example and comparison unit example is shown in table 2 below.
[table 2]
Can provide according to organic electroluminescent compounds of the present invention and have compared with the long life and the Organnic electroluminescent device that electric current and power efficiency strengthen under the driving voltage reduced.In addition, although use the OLED device of conventional organic electroluminescent compounds to need hole blocking layer, hole blocking layer is using according to dispensable in the OLED device of compound of the present invention.

Claims (7)

1. the organic electroluminescent compounds represented by following formula 1,
Wherein
L 1represent singly-bound, substituted or unsubstituted (C6-C30) arylidene or substituted or unsubstituted (3 yuan to 30 yuan) inferior heteroaryl;
Ar 1to Ar 4represent hydrogen independently of one another, deuterium, halogen, cyano group, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3 yuan to 30 yuan) heteroaryl, substituted or unsubstituted (C1-C30) alkylamino, substituted or unsubstituted (C6-C30) arylamino, or substituted or unsubstituted (C1-C30) alkyl (C6-C30) arylamino, maybe can be connected to adjacent substituents to form alicyclic ring or the aromatic ring of substituted or unsubstituted (3 yuan to 30 yuan) monocycle or many rings, its carbon atom can be selected from nitrogen by least one, the heteroatoms displacement of oxygen and sulphur,
A ring represents substituted or unsubstituted (C6-C30) aryl or substituted or unsubstituted (3 yuan to 30 yuan) heteroaryl;
X 1represent-N-or-CR 1-;
X 2represent-N-or-CR 2-;
X 3represent-N-or-CR 3-;
At X 1to X 3expression-CR respectively 1-,-CR 2-and-CR 3-when, A ring represents nitrogenous (3 yuan to 30 yuan) heteroaryl;
R 1to R 3represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C13-C30) Spirofluorene-based or substituted or unsubstituted (3 yuan to 30 yuan) heteroaryl independently of one another;
L represents 0 or 1;
M represents the integer of 0 to 5;
N represents the integer of 0 to 2;
When m or n is the integer of two or more, Ar 1or Ar 2in each can be identical or different; And
Described (Asia) heteroaryl contains the heteroatoms that at least one is selected from B, N, O, S, P (=O), Si and P.
2. organic electroluminescent compounds according to claim 1, wherein said compound is represented by following formula 1a or 1b:
Wherein
L 1, Ar 1to Ar 4, A ring, X 1, X 2, X 3, R 2, R 3, l, m and n as in claim 1 determine
Justice.
3. organic electroluminescent compounds according to claim 1, wherein at L 1, Ar 1to Ar 4, A ring and R 1to R 3in, the alkyl be substituted, (Asia) aryl be substituted, (Asia) heteroaryl be substituted, the alkylamino be substituted, the arylamino be substituted is that at least one is selected from by the substituting group of the following group formed: deuterium with the substituting group of the alkyl aryl amino be substituted independently of one another, halogen, (C1-C30) alkyl not being substituted or being optionally substituted by halogen, (C1-C30) alkoxyl group, (C6-C30) aryl, (3 yuan to the 30 yuan) heteroaryl not being substituted or being replaced by (C6-C30) aryl, (C3-C30) cycloalkyl, (5 yuan to 7 yuan) Heterocyclylalkyl, three (C1-C30) alkyl tin groups, alkyl silane groups, three (C6-C30) aryl-silane base, two (C1-C30) alkyl (C6-C30) aryl-silane base, (C1-C30) alkyl two (C6-C30) aryl-silane base, (C2-C30) thiazolinyl, (C2-C30) alkynyl, cyano group, two (C1-C30) alkylamino, two (C6-C30) arylamino, (C1-C30) alkyl (C6-C30) arylamino, two (C6-C30) aryl boryl, two (C1-C30) alkyl boryl, (C1-C30) alkyl (C6-C30) aryl boryl, (C6-C30) aryl (C1-C30) alkyl, (C1-C30) alkyl (C6-C30) aryl, carboxyl, nitro and hydroxyl.
4. organic electroluminescent compounds according to claim 1, wherein L 1represent singly-bound or substituted or unsubstituted (C6-C21) arylidene;
Ar 1to Ar 4represent hydrogen, unsubstituted (C1-C6) alkyl, substituted or unsubstituted (C6-C21) aryl or unsubstituted (5 yuan to 21 yuan) heteroaryl independently of one another;
A ring represents substituted or unsubstituted (C6-C21) aryl or substituted or unsubstituted (5 yuan to 21 yuan) heteroaryl;
X 1represent-N-or-CR 1-;
X 2represent-N-or-CR 2-;
X 3represent-N-or-CR 3-;
At X 1to X 3expression-CR respectively 1-,-CR 2-and-CR 3-when, A ring represents nitrogenous (5 yuan to 21 yuan) heteroaryl;
R 1to R 3represent hydrogen, substituted or unsubstituted (C6-C21) aryl, substituted or unsubstituted (C15-C25) Spirofluorene-based or substituted or unsubstituted (5 yuan to 21 yuan) heteroaryl independently of one another;
L represents 0 or 1;
M represents the integer of 0 to 2;
N represents 0 or 1; And
When m is 2, Ar 2in each can be identical or different.
5. organic electroluminescent compounds according to claim 1, wherein L 1represent singly-bound or unsubstituted (C6-C12) arylidene;
Ar 1, Ar 3and Ar 4represent hydrogen or unsubstituted (C6-C12) aryl independently of one another;
Ar 2represent hydrogen; (C1-C4) alkyl; (C6-C18) aryl not being substituted or being replaced by (C1-C4) alkyl; Or unsubstituted (5 yuan to 18 yuan) heteroaryl;
A ring represents (C6-C12) aryl; Or (5 yuan to 15 yuan) that are not substituted or replaced by (C6-C12) aryl;
X 1represent-N-or-CR 1-;
X 2represent-N-or-CR 2-;
X 3represent-N-or-CR 3-;
At X 1to X 3expression-CR respectively 1-,-CR 2-and-CR 3-when, A ring represents nitrogenous (5 yuan to 15 yuan) heteroaryl;
R 1to R 3represent hydrogen independently of one another; (C6-C18) aryl not being substituted or being replaced by (C1-C4) alkyl or (C6-C12) aryl; (C15-C25) Spirofluorene-based; Or (5 yuan to the 15 yuan) heteroaryl not being substituted or being replaced by (C6-C12) aryl;
L represents 0 or 1;
M represents the integer of 0 to 2;
N represents 0 or 1; And
When m is 2, Ar 2in each can be identical or different.
6. organic electroluminescent compounds according to claim 1, the wherein said compound represented by formula 1 is selected from by the following group formed:
7. an Organnic electroluminescent device, it comprises compound according to claim 1.
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