CN103119125A - Novel organic electroluminescent compounds and organic electroluminescent devices including the same - Google Patents

Novel organic electroluminescent compounds and organic electroluminescent devices including the same Download PDF

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CN103119125A
CN103119125A CN2011800452605A CN201180045260A CN103119125A CN 103119125 A CN103119125 A CN 103119125A CN 2011800452605 A CN2011800452605 A CN 2011800452605A CN 201180045260 A CN201180045260 A CN 201180045260A CN 103119125 A CN103119125 A CN 103119125A
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unsubstituted
replace
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replacement
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李秀镛
李孝姃
罗弘烨
权赫柱
金奉玉
金圣珉
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Rohm and Haas Electronic Materials Korea Ltd
Rohm and Haas Electronic Materials LLC
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Abstract

Provided are a novel organic electroluminescent compound and an organic electroluminescent device including the same. The organic electroluminescent device, which uses the organic electroluminescent compound according to the present invention as a hole transfer material or a hole injection material, has better luminous efficiency and excellent lifespan property of materials than the existing materials. Therefore, an OLED device, which has excellent driving lifespan property and improved power consumption due to an increase of power efficiency, can be manufactured.

Description

New organic electroluminescent compounds and the organic electroluminescence device that comprises this compound
Technical field
The organic electroluminescence device that the present invention relates to new organic electroluminescent compounds and comprise this compound, relate more specifically to as the new organic electroluminescent compounds of hole mobile material or hole-injecting material and the organic electroluminescence device of this compound of use.
Technical background
Nowadays the most widely used liquid-crystal display (LCD) is luminescence type display part not, and its energy consumption is little and lightweight.But, its device drive system complex, time of response and contrast gradient thereof can not reach desired level.Therefore, for organic electroluminescence device, the research as flat-panel monitor of future generation receives publicity and obtains develop actively.
In display device, electroluminescent device (El element) is the self-luminous display part, has wide angle of visibility, the contrast gradient of excellence and the advantage of rapid response speed.Eastman Kodak Co (Eastman Kodak) has at first developed a kind of organic EL device, and this device is used low molecular weight aromatic diamines and aluminum complex as the material [Appl.Phys.Lett.51,913,1987] that forms electroluminescence layer.
Organic EL device has electroluminescent mechanism, and when charge injection arrives in the organic membrane formed between electron injection electrode (negative electrode) and hole injecting electrode (anode), electronics and hole form pairing, then buries in oblivion simultaneously luminous.The advantage of organic EL device is, it can for example, in the upper forming element of flexible transparent base material (plastics), can, comparing lower driving of voltage (10V or lower) that plasma display panel or inorganic EL indicating meter are low, need less power consumption and there is excellent color.
Organic materials for organic EL device can be divided into to electroluminescent material and charge transfer material substantially.Described electroluminescent material is directly involved in electroluminescent color and luminous efficiency, needs following several characteristics, for example low degradation property, uniform thin film formability and the stability when high mobility in solid-state high-fluorescence quantum yield, electronics and hole, vacuum moulding machine.
Simultaneously, copper phthalocyanine CuPc, NPB, TPD, MTDATA (4,4', 4 " tri-(3-methyl phenyl phenyl amino) triphenylamine) and/or analogue can be used as hole and inject and transport material.But efficiency and the life characteristic of device that comprises materials in hole injection layer and transport layer is deteriorated.Reason is to produce thermal stresses between anode and hole injection layer when with high current drives organic EL device, this thermal stresses and then cause the work-ing life of device deteriorated fast.In addition, because the hole mobility in the organic materials used is very high, destroyed hole-elementary charge balance in hole injection layer, this has caused the decline of quantum yield (cd/A).
Reported the weather resistance with respect to organic EL device, the compound with good thin film stability is better with the thin film stability with higher noncrystalline compound.Herein, glass transition point (Tg) is as the amorphism index.The glass transition temp of existing MTDATA is 76 ℃, but this does not show that amorphism is high.Materials can not provide the required characteristic in the weather resistance aspect of organic EL device and due to hole is injected and transport property causes luminous efficiency.
Summary of the invention
technical problem
An object of the present invention is to provide to have than existing hole and inject or the better luminous efficiency of transport material and device endurance life characteristic and there is the organic electroluminescent compounds of excellent backbone structure, and provide and adopt the organic electroluminescence device of this new organic electroluminescent compounds as hole injection layer or hole transmission layer.
technical scheme
The present invention relates to the organic electroluminescent compounds of following Chemical formula 1 statement and the organic electroluminescence device that comprises this compound, in the hole injection layer of organic electroluminescence device or hole transmission layer containing with good grounds organic electroluminescent compounds of the present invention, to reduce driving voltage the improving luminous efficiency of device.
Aspect total, the invention provides the organic electroluminescent compounds with following Chemical formula 1 statement.
Chemical formula 1
In Chemical formula 1:
Mean-O-of X ,-S-,-C (R 11r 12)-or-Si (R 13r 14)-;
R 11and R 14mean that independently hydrogen, deuterium, halogen, replacement or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl, replacement or unsubstituted (C3-C30) heteroaryl, replacement or unsubstituted 5-unit are to 7-unit Heterocyclylalkyl, replacement or unsubstituted (C3-C30) cycloalkyl, or adjacent substituting group can be connected to form ring;
R 1to R 4mean independently hydrogen, deuterium, halogen, replace or unsubstituted (C1-C30) alkyl, replace or unsubstituted (C6-C30) aryl, replace or unsubstituted (C3-C30) heteroaryl, replace or unsubstituted (C3-C30) cycloalkyl, replace or unsubstituted 5-unit to 7-unit Heterocyclylalkyl, replace or unsubstituted (C6-C30) aryl (C1-C30) alkyl, with one or more Cycloalkylfused replacements or unsubstituted (C6-C30) aryl, the 5-unit condensed with one or more replacements or unsubstituted aromatic ring is to 7-unit's Heterocyclylalkyl or (C3-C30) cycloalkyl of condensing with one or more replacements or unsubstituted aromatic ring, replace or unsubstituted (C1-C30) silyl, cyano group, nitro or hydroxyl, and work as R 1to R 4while being plural form respectively, they can be interconnected to form ring structure,
R 5represent hydrogen, deuterium, halogen, replacement or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl, replacement or unsubstituted (C3-C30) heteroaryl or replacement or unsubstituted 5-unit to 7-unit Heterocyclylalkyl;
L 1and L 2mean independently chemical bond, replacement or unsubstituted (C6-C30) arylidene or replacement or unsubstituted (C3-C30) heteroarylidene, only get rid of L 1and L 2the situation that simultaneously means chemical bond;
Ar means to replace or unsubstituted (C6-C30) aryl, replace or unsubstituted (C3-C30) heteroaryl, replace or unsubstituted 5-unit to 7-unit Heterocyclylalkyl, with one or more Cycloalkylfused replacements or unsubstituted (C6-C30) aryl, replacement or unsubstituted (C3-C30) heteroaryl of condensing with one or more replacements or unsubstituted aromatic ring, the 5-unit condensed with one or more replacements or unsubstituted aromatic ring to 7-unit Heterocyclylalkyl, perhaps they can be connected to form alicyclic ring or monocycle or many cyclophanes ring with adjacent substituting group by (C3-C30) alkylidene group that is with or without condensed ring or (C3-C30) alkenylene that is with or without condensed ring,
A to d means the integer of 0-4 independently, when a to d means to be more than or equal to 2 integer independently, and R 1, R 2, R 3and R 4can be mutually identical or different, and adjacent substituting group can be connected to form ring;
The heteroatoms that described Heterocyclylalkyl and heteroaryl contain one or more B of being selected from, N, O, S, P (=O), Si and P; And
Further replace R 1to R 4, R 5, R 11to R 14, L 1, L 2one or more with the substituting group of Ar independently selected from lower group: deuterium, halogen, replaced by halogen or unsubstituted (C1-C30) alkyl, (C6-C30) aryl, quilt (C6-C30) aryl replaces or unsubstituted (C3-C30) heteroaryl, 5-unit to 7-unit Heterocyclylalkyl, 5-unit to the 7-unit Heterocyclylalkyl condensed with one or more aromatic rings, (C3-C30) cycloalkyl, (C6-C30) cycloalkyl, the R that condense with one or more aromatic rings 21r 22r 23si-, (C2-C30) thiazolinyl, (C2-C30) alkynyl, cyano group, carbazyl, NR 24r 25, BR 26r 27, PR 28r 29, P (=O) R 30r 31, (C6-C30) aryl (C1-C30) alkyl, (C1-C30) alkyl (C6-C30) aryl, R 32s-, R 33o-, R 34c (=O)-, R 35c (=O) O-, carboxyl, nitro and hydroxyl, R 21to R 33each is hydrogen independently, deuterium, halogen, replace or unsubstituted (C1-C30) alkyl, replace or unsubstituted (C6-C30) aryl, replace or unsubstituted (C3-C30) heteroaryl, replace or unsubstituted 5-unit to 7-unit Heterocyclylalkyl, perhaps they can be connected to form alicyclic ring with adjacent substituting group by replacement or unsubstituted (C3-C30) alkylidene group that is with or without condensed ring or the replacement that is with or without condensed ring or unsubstituted (C3-C30) alkenylene, perhaps monocycle or many cyclophanes ring, the carbon atom of formed alicyclic ring or monocycle or many cyclophanes ring can be by one or more nitrogen that is selected from, the heteroatoms of oxygen and sulphur replaces, and R 34and R 35mean independently (C1-C30) alkyl, (C1-C30) alkoxyl group, (C6-C30) aryl or (C6-C30) aryloxy.
Term used herein " alkyl " and other substituting groups that contains " alkyl " part comprise straight chain and a chain portion, and " cycloalkyl " can comprise monocyclic hydrocarbon and polynuclear hydrocarbon, for example replace or unsubstituted adamantyl or replacement or unsubstituted (C7-C30) bicyclic alkyl.Term used herein " aryl " refers to by from aromatic hydrocarbon, removing an organic group that hydrogen atom obtains, can comprise containing 4 to 7 suitable annular atomses, the monocycle that is preferably 5 or 6 annular atomses or condensed ring, even can comprise by singly linked a plurality of aryl.Their object lesson includes but not limited to, phenyl, naphthyl, xenyl (biphenyl), anthryl, indenyl, fluorenyl, phenanthryl (phenanthryl), benzo [9,10] phenanthryl (triphenylenyl), pyrenyl, perylene base (perylenyl),
Figure BDA00002942410700041
base (chrysenyl), naphthacenyl (naphthacenyl), fluoranthene base (fluoranthenyl) etc.Described naphthyl comprises 1-naphthyl and 2-naphthyl, and described anthryl comprises 1-anthryl, 2-anthryl and 9-anthryl, and described fluorenyl comprises 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl.Term used herein " heteroaryl " means to comprise 1-4 heteroatoms that is selected from B, N, O, S, P (=O), Si and Se as the aromatic ring frame atom, and other aromatic ring frame atoms aromatic yl group that is carbon.It can be 5 yuan of obtaining with one or more phenyl ring condensations or 6 yuan of bicyclic heteroaryls or polyheteroaromatic, and can be fractional saturation.Described heteroaryl groups comprises the divalent aryl group, and the oxidized or quaternized formation of heteroatoms in wherein encircling is N-oxide compound or quaternary ammonium salt for example.Their object lesson includes, but are not limited to, bicyclic heteroaryl such as furyl, thienyl, pyrryl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl group, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazine base, triazolyl, tetrazyl, furazan base (furazanyl), pyridyl, pyrazinyl, pyrimidyl, pyridazinyl etc., polyheteroaromatic is benzofuryl (benzofuranyl) for example, benzothienyl, isobenzofuran-base, benzimidazolyl-, benzothiazolyl, the benzisothiazole base, the benzoisoxazole base, benzoxazolyl, pseudoindoyl, indyl, indazolyl, the diazosulfide base, quinolyl, isoquinolyl, cinnolines base (cinnolinyl), quinazolyl, quinoline piperazine base (quinolyzinyl), quinoxalinyl (quinoxalinyl), carbazyl, phenanthridinyl (phenanthridinyl), benzo dioxolyl (benzodioxolyl), naphthylidene (naphthylidine), dibenzofuran group, dibenzo thiophenyl etc., and N-oxide compound (for example pyridyl N-oxide compound, quinolyl N-oxide compound), or its quaternary ammonium salt etc.
Alkyl in term used herein " (C1-C30) alkyl or (C6-C30) aryl (C1-C30) alkyl " can comprise (C1-C20) alkyl or (C1-C10) alkyl, and the aryl in term " (C6-C30) aryl and (C6-C30) aryl (C1-C30) alkyl " can comprise (C6-C20) aryl or (C6-C12) aryl." (C3-C30) heteroaryl " group can comprise (C3-C20) heteroaryl or (C3-C12) heteroaryl, and " (C3-C30) cycloalkyl " group can comprise (C3-C20) cycloalkyl or (C3-C7) cycloalkyl." (C3-C30) alkylidene group or alkenylene " group can comprise (C3-C20) alkylidene group or alkenylene or (C3-C10) alkylidene group or alkenylene.
Statement " replacement " in term used herein " replacement or unsubstituted " refers to by unsubstituted substituting group and further replaces.
In addition, organic electroluminescent compounds of the present invention can comprise the compound of Chemical formula 2 and 3 statements.
Chemical formula 2
Figure BDA00002942410700051
Chemical formula 3
Figure BDA00002942410700052
In Chemical formula 2 and 3,
X, R 1to R 4, R 5, L 1, L 2, Ar and a to d definition identical with the definition in Chemical formula 1.
More specifically, Ar can be selected from following structure, but is not limited to this:
Figure BDA00002942410700071
More specifically, organic electroluminescent compounds of the present invention can be enumerated as following compound, but they are not construed as limiting the present invention:
Figure BDA00002942410700081
Figure BDA00002942410700091
Figure BDA00002942410700101
Can, according to for example organic electroluminescent compounds of the present invention of preparation shown in scheme 1, but be not limited to following scheme.
Scheme 1
Figure BDA00002942410700102
In scheme 1, X, R 1to R 4, R 5, L 1, L 2, Ar and a to d definition identical with the definition in Chemical formula 1.
In aspect another is common, the invention provides a kind of organic electroluminescence device.Herein, organic electroluminescent compounds of the present invention can be used as hole-injecting material or hole mobile material.
Organic electroluminescence device can comprise: the first electrode; The second electrode; Be inserted into one or more layers organic layer between described the first electrode and the second electrode.Herein, described organic layer can comprise the organic electroluminescent compounds of one or more Chemical formula 1s.
In organic electronic devices of the present invention, organic layer can comprise the organic electroluminescent compounds of Chemical formula 1, comprises the compound that one or more are selected from aryl amine compound and styryl aryl amine compound simultaneously.The object lesson of described aryl amine compound or styryl aryl amine compound is as described in the 212nd to 224 sections, the specification sheets of No. 10-2008-0060393rd, korean patent application, but is not limited to this.
In addition, in organic electroluminescence device of the present invention, except the organic electroluminescent compounds of Chemical formula 1, described organic layer also can comprise one or more metal or complex compounds of being selected from organo-metallic, period 4 and period 5 transition metal, lanthanide series metal and the d-transition element of the periodic table of elements the 1st family, the 2nd family.Described organic layer can comprise electroluminescence layer and charge generation layer.
The present invention can realize having the organic electroluminescence device of the dot structure of independent light-emitting mode, the organic electroluminescence device that wherein contains the organic electroluminescent compounds of Chemical formula 1 is used as one or more sub-pixels, described sub-pixel comprises one or more metals that is selected from Ir, Pt, Pd, Rh, Re, Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au and Ag, and is pattern parallel simultaneously.
In addition, described organic layer also can comprise the organic electro luminescent layer that one or more layers contains redness, green or blue coloured electroluminous compound, and get rid of is the situation of organic electroluminescent compounds simultaneously, thereby manufactures the organic electroluminescence device of transmitting white.The example of the compound of red-emitting, green glow or blue light is referring to korean patent application 10-2008-0123276,10-2008-0107606 or No. 10-2008-0118428, but is not limited to this.
In organic electroluminescence device of the present invention, preferably will be at least one deck layer (hereinafter referred to as " upper layer ") of being selected from chalcogenide layer, metal halide and metal oxide layer be arranged on the internal surface of at least one side of electrode pair.Particularly, preferably the chalkogenide of silicon and aluminum metal (comprising oxide compound) layer is arranged on the anode surface of electroluminescent medium layer, metal halide or metal oxide layer are arranged on the cathode surface of electroluminescent medium layer.This can access driving stability.The example of chalkogenide can comprise SiO x(1≤X≤2), AlO x(1≤X≤1.5), SiON, SiAlON etc., the example of metal halide can comprise LiF, MgF 2, CaF 2, rare earth metal fluorochemical etc., the example of metal oxide can comprise Cs 2o, Li 2o, MgO, SrO, BaO, CaO etc.
In organic electroluminescence device of the present invention, the mixing zone of electric transmission compound and reductibility doping agent also is set on the surface of preferred at least one in prepared electrode pair, or the mixing zone of hole transport compound and oxidisability doping agent.Therefore, the electric transmission compound is reduced into negatively charged ion, and this contributes to electronics to be injected from mixing zone or be transferred to electroluminescent medium.In addition, the oxidized formation positively charged ion of hole transport compound, this contributes to hole to be injected from mixing zone or be transferred to electroluminescent medium.Preferred oxidisability doping agent comprises various Lewis acids and acceptor compound.Preferred reductibility doping agent comprises basic metal, alkali metal compound, alkaline-earth metal, rare earth metal and composition thereof.In addition, the reductibility dopant layer can be used as charge generation layer, has the white color organic electroluminescence device of two-layer or more multi-layered electroluminescence layer with manufacture.
useful effect
As mentioned above, use the organic electroluminescence device of organic electroluminescent compounds of the present invention to there is higher luminous efficiency and excellent materials'use life characteristic, therefore can manufacture the OLED device with excellent driving endurance life characteristic by it.
Embodiments of the present invention
Further describe organic electroluminescent compounds of the present invention below with reference to representative compound of the present invention, and preparation method thereof with the electroluminescence characters of device, but these embodiment do not limit the scope of the invention only for describing purpose.
[preparation example 1] prepares compound 1
the preparation of compound 1-1
Add the bromo-9-phenyl of 3--9H-carbazole 30g (93.1mmol), aniline 26mL (279.3mmol), Pd (OAc) in reactor 20.63g (2.79mmol), P (t-Bu) 34.3mL (9.31mmol), Cs 2cO 376g (232.8mmol) and toluene 700mL, then heat and stir 12 hours at 120 ℃.After having reacted, with distilled water, clean the gained material, be extracted with ethyl acetate.Use MgSO 4dry organic layer also removes desolventizing with rotatory evaporator, uses afterwards the column chromatography purifying to obtain compound 1-1(20g, 59.8mmol).
the preparation of compound 1-2
Add 4-dibenzothiophene boric acid 10.5g (46mmol), Isosorbide-5-Nitrae-dibromobenzene 32.6g (138mmol), Pd (PPh in reactor 3) 40.53g (0.46mmol), the Na of 1M 2cO 369mL (69mmol) and toluene 600mL, then 70 ℃ of return stirrings 2 hours.After having reacted, with distilled water, clean the gained material, be extracted with ethyl acetate.Use MgSO 4dry organic layer also removes desolventizing with rotatory evaporator, uses afterwards the column chromatography purifying to obtain compound 1-2(6.7g, 19.8mmol).
the preparation of compound 1
Add compound 1-28.0g (20.0mmol), compound 1-18.3g (24mmol), Pd (OAc) in reactor 20.14g (0.6mmol), P (t-Bu) 31.00mL (2.0mmol), NaOt-Bu5.9g (60mmol) and toluene 200mL, then 120 ℃ of return stirrings 12 hours.After having reacted, with distilled water, clean the gained material, be extracted with ethyl acetate.Use MgSO 4dry organic layer also with rotatory evaporator except desolventizing, use afterwards the column chromatography purifying then recrystallization obtain compound 1(4.0g, 6.74mmol, 34%).
1h NMR (CDCl 3, 200MHz) δ=6.63 (2H, m), 6.69～6.81 (5H; m), 7.2～7.25 (3H, m); 7.33～7.38 (2H, m), 7.45～7.58 (10H; m), 7.94～7.98 (2H, m); (8.2 1H, m), 8.41～8.45 (2H; m), 8.55 (1H, m); MS/FAB experimental value 593, calculated value 592.75
[preparation example 2] prepares compound 9
Figure BDA00002942410700131
the preparation of compound 2-1
Add beta naphthal 20.0g (138.8mmol), NaHSO in reactor 328.8g (277.4mmol), distilled water 400mL, 4-bromophenyl hydrazine 31.2mL (166.4mmol), then be heated to 120 ℃.After 12 hours, add wherein distilled water, the solid that then filtration under diminished pressure produces.The solid obtained is put into to aqueous hydrochloric acid, afterwards 100 ℃ of heating.After 1 hour, with dichloromethane extraction gained material, with distilled water and NaOH aqueous cleaning.Then carry out the post separation and obtain compound 2-1(9.2g, 31.0mmol).
the preparation of compound 2-2
Add compound 2-19.2g (31.0mmol), Cu2.0g (31.0mmol), 18-hat-60.4g (1.6mmol), K in reactor 2cO 312.8g (93.2mmol) and 1,2-dichlorobenzene 100mL, then 180 ℃ of return stirrings 12 hours.Cooling and underpressure distillation under gained material room temperature, then clean with dichloromethane extraction and with distilled water.Then use MgSO 4drying, underpressure distillation, then carry out the post separation, thereby obtain compound 2-2(7.6g, 20.4mmol).
the preparation of compound 2-3
Add the bromo-9-phenyl of 3--9H-carbazole 41.5g (128.7mmol), ammoniacal liquor 27mL (772mmol), CuI2.45g (12.87mmol), Acetyl Acetone 12.9mL (128.7mmol), Cs in reactor 2cO 383.9g (257.4mmol) and DMF1000mL, then at 100 ℃, heat and stir 12 hours.After having reacted, with distilled water, clean the gained material, be extracted with ethyl acetate.Use MgSO 4dry organic layer also removes desolventizing with rotatory evaporator, uses afterwards the column chromatography purifying to obtain compound 2-3(11.3g, 43.7mmol).
the preparation of compound 2-4
Add compound 2-234.7g (93.1mmol), compound 2-372.1g (279.3mmol), Pd (OAc) in reactor 20.63g (2.79mmol), P (t-Bu) 34.3mL (9.31mmol), Cs 2cO 376g (232.8mmol) and toluene 1000mL, then heat and stir 12 hours at 120 ℃.After having reacted, with distilled water, clean the gained material, be extracted with ethyl acetate.Use MgSO 4dry organic layer also removes desolventizing with rotatory evaporator, uses afterwards the column chromatography purifying to obtain compound 2-4(10.7g, 19.5mmol).
the preparation of compound 9
Add compound 2-411g (20.0mmol), compound 1-28.3g (24mmol), Pd (OAc) in reactor 20.14g (0.6mmol), P (t-Bu) 31.00mL (2.0mmol), NaOt-Bu5.9g (60mmol) and toluene 200mL, then 120 ℃ of return stirrings 12 hours.After having reacted, with distilled water, clean the gained material, be extracted with ethyl acetate.Use MgSO 4dry organic layer also with rotatory evaporator except desolventizing, use afterwards the column chromatography purifying then recrystallization obtain compound 9(6.3g, 7.8mmol, 39%).
1h NMR (CDCl 3, 200MHz) δ=5.93 (2H, m), 6.69 (2H, m), 7.29 (1H, m); (7.45 2H, m), 7.5～7.58 (23H, m), 7.98 (1H, m); 8.12～8.2 (3H, m), 8.41～8.45 (2H, m), 8.54 (1H, m); MS/FAB experimental value 809, calculated value 808.00
[preparation example 3] prepares compound 27
Figure BDA00002942410700151
the preparation of compound 3-1
Add phenyl-boron dihydroxide 5.4g (44mmol), Isosorbide-5-Nitrae-dibromine naphthalene 18.9g (66mmol), Pd (PPh in reactor 3) 42.0g (1.76mmol), Na 2cO 314.0g (132mmol), toluene 200mL and ethanol 100mL, then 120 ℃ of return stirrings 12 hours.After having reacted, with distilled water, clean the gained material, be extracted with ethyl acetate.Use MgSO 4dry organic layer also removes desolventizing with rotatory evaporator, uses afterwards the column chromatography purifying to obtain compound 3-1(9.1g, 32.14mmol).
the preparation of compound 3-2
Add compound 3-126.4g (93.1mmol), compound 2-372.1g (279.3mmol), Pd (OAc) in reactor 20.63g (2.79mmol), P (t-Bu) 34.3mL (9.31mmol), Cs 2cO 376g (232.8mmol) and toluene 1000mL, then heat and stir 12 hours at 120 ℃.After having reacted, with distilled water, clean the gained material, be extracted with ethyl acetate.Use MgSO 4dry organic layer also removes desolventizing with rotatory evaporator, uses afterwards the column chromatography purifying to obtain compound 3-2(12.0g, 26.1mmol).
the preparation of compound 27
Add compound 3-29.2g (20.0mmol), compound 1-28.3g (24mmol), Pd (OAc) in reactor 20.14g (0.6mmol), P (t-Bu) 31.00mL (2.0mmol), NaOt-Bu5.9g (60mmol) and toluene 100mL, then 120 ℃ of return stirrings 12 hours.After having reacted, with distilled water, clean the gained material, be extracted with ethyl acetate.Use MgSO 4dry organic layer also with rotatory evaporator except desolventizing, use afterwards the column chromatography purifying then recrystallization obtain compound 27(4.4g, 6.12mmol, 31%).
1h NMR (CDCl 3, 200MHz) δ=5.93 (1H, m), 6.69 (2H, m); (7.04 1H, m), 7.29 (1H, m); (7.41 1H, m), 7.45～7.52 (17H, m); (7.69 1H, m), 7.78～7.79 (3H, m); (7.98 1H, m), 8.07～8.12 (2H, m); (8.2 1H, m), 8.41～8.49 (3H, m); MS/FAB experimental value 719, calculated value 718.90
[preparation example 4] prepares compound 31
Figure BDA00002942410700161
the preparation of compound 4-1
Add 4-dibenzothiophene boric acid 10.5g (46mmol), Isosorbide-5-Nitrae-'-dibromobiphenyl 143.1g (138mmol), Pd (PPh in reactor 3) 40.53g (0.46mmol), the Na of 1M 2cO 369mL (69mmol) and toluene 500mL, then 70 ℃ of return stirrings 2 hours.After having reacted, with distilled water, clean the gained material, be extracted with ethyl acetate.Use MgSO 4dry organic layer also removes desolventizing with rotatory evaporator, uses afterwards the column chromatography purifying to obtain compound 4-1(10.1g, 24.3mmol).
the preparation of compound 31
Add compound 4-18.3g (20.0mmol), compound 1-18.3g (24mmol), Pd (OAc) in reactor 20.14g (0.6mmol), P (t-Bu) 31.00mL (2.0mmol), NaOt-Bu5.9g (60mmol) and toluene 100mL, then 120 ℃ of return stirrings 12 hours.After having reacted, with distilled water, clean the gained material, be extracted with ethyl acetate.Use MgSO 4dry organic layer also with rotatory evaporator except desolventizing, use afterwards the column chromatography purifying then recrystallization obtain compound 31(3.5g, 5.23mmol, 26%).
1h NMR (CDCl 3, 200MHz) δ=6.63 (2H, m), 6.69～6.81 (5H; m), 7.2～7.25 (7H, m); 7.33～7.38 (2H, m), 7.45～7.58 (10H; m), 7.94～7.98 (2H, m); (8.2 1H, m), 8.41～8.45 (2H; m), 8.55 (1H, m); MS/FAB experimental value 669, calculated value 668.85
[preparation example 5] prepares compound 43
Figure BDA00002942410700171
the preparation of compound 5-1
Add the bromo-N of 4-in reactor, N-phenylbenzene aniline 41.7g (128.7mmol), ammoniacal liquor 27mL (772mmol), CuI2.45g (12.87mmol), Acetyl Acetone 12.9mL (128.7mmol), Cs 2cO 383.9g (257.4mmol) and DMF1000mL, then at 100 ℃, heat and stir 12 hours.After having reacted, with distilled water, clean the gained material, be extracted with ethyl acetate.Use MgSO 4dry organic layer also removes desolventizing with rotatory evaporator, uses afterwards the column chromatography purifying to obtain compound 5-1(12.2g, 46.9mmol).
the preparation of compound 5-2
Add the bromo-9-phenyl of 3--9H-carbazole 30.0g (93.1mmol), compound 5-172.7g (279.3mmol), Pd (OAc) in reactor 20.63g (2.79mmol), P (t-Bu) 34.3mL (9.31mmol), Cs 2cO 376g (232.8mmol) and toluene 1000mL, then heat and stir 12 hours at 120 ℃.After having reacted, with distilled water, clean the gained material, be extracted with ethyl acetate.Use MgSO 4dry organic layer also removes desolventizing with rotatory evaporator, uses afterwards the column chromatography purifying to obtain compound 5-2(14.5g, 28.9mmol).
the preparation of compound 43
Add compound 1-28.0g (20.0mmol), compound 5-212.0g (24mmol), Pd (OAc) in reactor 20.14g (0.6mmol), P (t-Bu) 31.00mL (2.0mmol), NaOt-Bu5.9g (60mmol) and toluene 150mL, then 120 ℃ of return stirrings 12 hours.After having reacted, with distilled water, clean the gained material, be extracted with ethyl acetate.Use MgSO 4dry organic layer also with rotatory evaporator except desolventizing, use afterwards the column chromatography purifying then recrystallization obtain compound 43(4.3g, 5.66mmol, 28%).
1h NMR (CDCl 3, 200MHz) δ=6.38 (4H, m), 6.63 (4H; m), 6.69～6.81 (6H, m), 7.2～7.25 (5H; m), 7.33～7.38 (2H, m), 7.45～7.58 (10H; m), 7.94～7.98 (2H, m); (8.2 1H, m), 8.41～8.45 (2H; m), 8.55 (1H, m); MS/FAB experimental value 760, calculated value 759.96
[preparation example 6] prepares compound 49
Figure BDA00002942410700181
the preparation of compound 6-1
Add the bromo-9H-carbazole of 3-7.6g (31.0mmol), Cu2.0g (31.0mmol), 18-hat-60.4g (1.6mmol), K in reactor 2cO 312.8g (93.2mmol) and 1,2-dichlorobenzene 100mL, then 180 ℃ of return stirrings 12 hours.Cooling and underpressure distillation under gained material room temperature, then clean with dichloromethane extraction and with distilled water.Then use MgSO 4drying, underpressure distillation, then carry out the post separation, thereby obtain compound 6-1(7.9g, 19.8mmol).
the preparation of compound 6-2
Add compound 6-137g (93.1mmol), aniline 26Ml (279.3mmol), Pd (OAc) in reactor 20.63g (2.79mmol), P (t-Bu) 34.3mL (9.31mmol), Cs 2cO 376g (232.8mmol) and toluene 600mL, then heat and stir 12 hours at 120 ℃.After having reacted, with distilled water, clean the gained material, be extracted with ethyl acetate.Use MgSO 4dry organic layer also removes desolventizing with rotatory evaporator, uses afterwards the column chromatography purifying to obtain compound 6-2(10.3g, 25.1mmol).
the preparation of compound 49
Add compound 1-28.0g (20.0mmol), compound 6-29.9g (24mmol), Pd (OAc) in reactor 20.14g (0.6mmol), P (t-Bu) 31.00mL (2.0mmol), NaOt-Bu5.9g (60mmol) and toluene 100mL, then 120 ℃ of return stirrings 12 hours.After having reacted, with distilled water, clean the gained material, be extracted with ethyl acetate.Use MgSO 4dry organic layer also with rotatory evaporator except desolventizing, use afterwards the column chromatography purifying then recrystallization obtain compound 49(4.7g, 7.02mmol, 35%).
1h NMR (CDCl 3, 200MHz) δ=6.63 (2H, m), 6.69～6.81 (5H; m), 7.2～7.25 (3H, m), 7.33～7.41 (3H; m), 7.5～7.58 (9H, m), 7.68 (2H; m), 7.79 (2H, m), 7.94～7.98 (2H; m), 8.2 (1H, m), 8.41～8.45 (2H; m), 8.55 (1H, m); MS/FAB experimental value 669, calculated value 668.85
[preparation example 7] prepares compound 69
Figure BDA00002942410700191
the preparation of compound 7-1
Add 4-bromo biphenyl 30g (128.7mmol), ammoniacal liquor 27mL (772mmol), CuI2.45g (12.87mmol), Acetyl Acetone 12.9mL (128.7mmol), Cs in reactor 2cO 383.9g (257.4mmol) and DMF600mL, then at 100 ℃, heat and stir 12 hours.After having reacted, with distilled water, clean the gained material, be extracted with ethyl acetate.Use MgSO 4dry organic layer also removes desolventizing with rotatory evaporator, uses afterwards the column chromatography purifying to obtain compound 7-1(15.2g, 88.64mmol).
the preparation of compound 7-2
Add the bromo-9-phenyl of 3--9H-carbazole 30g (93.1mmol), compound 7-147.3g (279.3mmol), Pd (OAc) in reactor 20.63g (2.79mmol), P (t-Bu) 34.3mL (9.31mmol), Cs 2cO 376g (232.8mmol) and toluene 1000mL, then heat and stir 12 hours at 120 ℃.After having reacted, with distilled water, clean the gained material, be extracted with ethyl acetate.Use MgSO 4dry organic layer also removes desolventizing with rotatory evaporator, uses afterwards the column chromatography purifying to obtain compound 7-2(8.8g, 21.4mmol).
the preparation of compound 7-3
Add 2-dibenzothiophene boric acid 10g (44mmol), Isosorbide-5-Nitrae-dibromobenzene 31g (132mmol), Pd (PPh in reactor 3) 42.5g (2.2mmol), the Na of 1M 2cO 3132mL (132mmol), toluene 500mL and ethanol 200mL, then 120 ℃ of return stirrings 12 hours.After having reacted, with distilled water, clean the gained material, be extracted with ethyl acetate.Use MgSO 4dry organic layer also removes desolventizing with rotatory evaporator, uses afterwards the column chromatography purifying to obtain compound 7-3(12.9g, 38.0mmol).
the preparation of compound 69
Add compound 7-36.8g (20.0mmol), compound 7-29.9g (24mmol), Pd (OAc) in reactor 20.14g (0.6mmol), P (t-Bu) 31.00mL (2.0mmol), NaOt-Bu5.9g (60mmol) and toluene 100mL, then 120 ℃ of return stirrings 12 hours.After having reacted, with distilled water, clean the gained material, be extracted with ethyl acetate.Use MgSO 4dry organic layer also with rotatory evaporator except desolventizing, use afterwards the column chromatography purifying then recrystallization obtain compound 69(5.8g, 8.7mmol, 43%).
1H?NMR(CDCl 3,200MHz)δ=6.69～6.77(6H,m),7.25(1H,m),7.33(1H,m),7.38～7.5(17H,m),7.86(1H,m),7.94～8(4H,m),8.45(1H,m),8.55(1H,m)
MS/FAB experimental value 669, calculated value 668.85
[preparation example 8] prepares compound 76
Figure BDA00002942410700201
the preparation of compound 8-1
Add 9.9-dimethyl-9H-fluorenes-2-ylboronic acid 10.5g (44mmol), Isosorbide-5-Nitrae-dibromobenzene 31g (132mmol), Pd (PPh in reactor 3) 42.5g (2.2mmol), the Na of 1M 2cO 3132mL (132mmol), toluene 500mL and ethanol 200mL, then 120 ℃ of return stirrings 12 hours.After having reacted, with distilled water, clean the gained material, be extracted with ethyl acetate.Use MgSO 4dry organic layer also removes desolventizing with rotatory evaporator, uses afterwards the column chromatography purifying to obtain compound 8-1(11.5g, 32.9mmol).
the preparation of compound 76
Add compound 8-17.0g (20.0mmol), compound 1-18.0g (24mmol), Pd (OAc) in reactor 20.14g (0.6mmol), P (t-Bu) 31.00mL (2.0mmol), NaOt-Bu5.9g (60mmol) and toluene 100mL, then 120 ℃ of return stirrings 12 hours.After having reacted, with distilled water, clean the gained material, be extracted with ethyl acetate.Use MgSO 4dry organic layer also with rotatory evaporator except desolventizing, use afterwards the column chromatography purifying then recrystallization obtain compound 76(6.4g, 10.6mmol, 54%).
1h NMR (CDCl 3, 200MHz) δ=1.72 (6H, s), 6.63 (2H, m), 6.69～6.81 (5H; m), 7.2～7.38 (7H, m), 7.45～7.63 (9H, m), 7.77 (1H; m), 7.87～7.94 (3H, m), 8.55 (1H, m); MS/FAB experimental value 603, calculated value 602.76
[preparation example 9] prepares compound 79
the preparation of compound 9-1
2,7-bis-is bromo-9, and 9-dimethyl fluorene 150g (426mmol) is dissolved in THF2.1L, then is cooled to the temperature of-78 ℃.(2.5M, in hexane, 426mmol), stirs 1 hour afterwards slowly to add n-BuLi170mL wherein.Add wherein trimethyl borate 53mL (469mmol), stir afterwards 12 hours.While having reacted, by 2M HCl termination reaction.Then use EA/H 2o extraction gained material, use MgSO 4remove moisture, underpressure distillation afterwards.Then carry out the post separation, thereby obtain compound 9-170g(220.8mmol).
the preparation of compound 9-2
Add compound 9-170g (220mmol), 2-iodonitrobenzene 50g (200mmol), Pd (PPh in reactor 3) 47g (6mmol), Na 2cO 364g (600mmol), toluene 1L, ethanol 0.5L and water 0.3L, then 90 ℃ of return stirrings 7.5 hours.When reaction completes, use EA/H 2o extraction gained material, then use MgSO 4remove moisture, underpressure distillation afterwards, thus obtain compound 9-2.Then without separation and purification, carry out next reaction.
the preparation of compound 9-3
By compound 9-290g and P (OEt) 3750mL is dissolved in 1,2-dichlorobenzene 750mL, and the gained mixture stirs 9 hours at 150 ℃.Use distilled water to remove solvent, then resulting red liquid is carried out to the post separation, thereby obtain compound 9-326g (79.69mmol).
the preparation of compound 9-4
Add chlorobenzene 2.6g (23.28mmol), compound 9-37.0g (19.4mmol), Pd (OAc) in reactor 20.13g (0.58mmol), P (t-Bu) 30.94mL (2.32mmol), NaOt-Bu6.7g (69.84mmol) and toluene 200mL, then 100 ℃ of return stirrings 12 hours.After having reacted, with distilled water, clean the gained material, be extracted with ethyl acetate.Use MgSO 4dry organic layer also with rotatory evaporator except desolventizing, use afterwards the column chromatography purifying then recrystallization obtain compound 9-4(6.8g, 15.5mmol).
the preparation of compound 9-5
Add compound 9-440.8g (93.1mmol), compound 2-372.1g (279.3mmol), Pd (OAc) in reactor 20.63g (2.79mmol), P (t-Bu) 34.3mL (9.31mmol), Cs 2cO 376g (232.8mmol) and toluene 1000mL, then heat and stir 12 hours at 120 ℃.After having reacted, with distilled water, clean the gained material, be extracted with ethyl acetate.Use MgSO 4dry organic layer also removes desolventizing with rotatory evaporator, uses afterwards the column chromatography purifying to obtain compound 9-5(13.8g, 22.4mmol).
the preparation of compound 79
Add compound 1-26.8g (20.0mmol), compound 9-514.8g (24mmol), Pd (OAc) in reactor 20.14g (0.6mmol), P (t-Bu) 31.00mL (2.0mmol), NaOt-Bu5.9g (60mmol) and toluene 100mL, then 120 ℃ of return stirrings 12 hours.After having reacted, with distilled water, clean the gained material, be extracted with ethyl acetate.Use MgSO 4dry organic layer also with rotatory evaporator except desolventizing, use afterwards the column chromatography purifying then recrystallization obtain compound 79(4.2g, 4.8mmol, 24%).
1h NMR (CDCl 3, 200MHz) δ=1.72 (6H, s), 5.93 (1H, m), 6.64～6.69 (3H; m), 6.81 (1H, m), 7.29 (2H, m); 7.45～7.52 (10H, m), 7.54 (3H, s), 7.54～7.63 (8H; m), 7.69 (1H, m), 7.84 (1H, m); (7.98 1H, m), 8.12 (2H, m), 8.2 (1H; m), 8.41～8.45 (2H, m), 8.85 (1H, s); MS/FAB experimental value 874, calculated value 874.10
[embodiment 1] is used organic electroluminescent compounds of the present invention to prepare the OLED device
The electroluminescent material of the application of the invention prepares the OLED device.At first, the ito thin film of the transparency electrode for OLED (15 Ω/) (purchased from SCP company (Samsung-Corning)) that to be made by glass carries out ultrasonic cleaning with trieline, acetone, ethanol and distilled water successively, and be stored in Virahol before using in.Then, the ITO substrate is arranged in the substrate folder of vacuum phase deposition equipment, and by 2-TNATA[4,4', 4 " tri-(N, N-(2-naphthyl)-phenyl amino) triphenylamine] be placed in the cell of vacuum phase deposition equipment; then exhaust, until indoor vacuum tightness reaches 10 -6holder.Then, to described cell, apply electric current with evaporation 2-TNATA, thereby form the hole injection layer that thickness is 60nm on the ITO substrate.Then, compound 1 is put into to another cell of vacuum sediment equipment, by described cell, applying electric current, evaporated compound 1, thereby form the hole transmission layer that thickness is 20nm on described hole injection layer.After forming hole injection layer and hole transmission layer, form in the above electroluminescence layer, specific as follows.Will be as the CBP[4 of main body, 4'-N, N'-bis-carbazoles-biphenyl] be placed in the cell of vacuum phase deposition equipment, will be as (piq) of doping agent 2ir (acac) [two-(1-phenyl isoquinolin quinoline base) iridium (III) acetyl pyruvates] is placed in another chamber of vacuum phase deposition equipment.Bi-material carries out the doping of 4-10 % by weight with different speed evaporations, thereby forms the electroluminescence layer that thickness is 30nm on described hole transmission layer.Afterwards, two (2-methyl-8-quinoline ester (quinolinate)) (the p-phenyl phenol root closes (phenolato)) aluminium (III) (BAlq) is deposited on electroluminescence layer as the hole barrier layer, thickness is 10nm.Then, the Alq[tri-(oxine) that deposit thickness is 20nm-aluminium (III)] as electron transfer layer.Then, the Liq quinoline lithium (lithium quinolate) of deposit thickness 1-2nm, as electron injecting layer, then by using another vacuum phase deposition equipment to form the Al negative electrode that thickness is 150nm, thereby is manufactured the OLED device.
According to material, every kind of compound passes through 10 -6under the holder condition, purifying is carried out in vacuum-sublimation, as the electroluminescent material of OLED.
As a result of, under the voltage of 6.8V, current flowing is 13.5mA/cm 2, confirm to have launched 1060cd/m 2ruddiness.
[embodiment 2] are used organic electroluminescent compounds of the present invention to prepare the OLED device
Same procedure is manufactured the OLED device as described in Example 1, and difference is to use compound 31 of the present invention as hole mobile material.
As a result of, under the voltage of 6.7V, current flowing is 13.8mA/cm 2, confirm to have launched 1055cd/m 2ruddiness.
[embodiment 3] are used organic electroluminescent compounds of the present invention to prepare the OLED device
Same procedure is manufactured the OLED device as described in Example 1, and difference is to use compound 49 of the present invention as hole mobile material.
As a result of, under the voltage of 6.7V, current flowing is 14.3mA/cm 2, confirm to have launched 1070cd/m 2ruddiness.
[embodiment 4] are used organic electroluminescent compounds of the present invention to prepare the OLED device
Same procedure is manufactured the OLED device as described in Example 1, and difference is to use compound 75 of the present invention as hole mobile material.
As a result of, under the voltage of 6.6V, current flowing is 14.2mA/cm 2, confirm to have launched 1065cd/m 2ruddiness.
[embodiment 5] are used organic electroluminescent compounds of the present invention to prepare the OLED device
Same procedure is manufactured the OLED device as described in Example 1, and difference is to use compound 76 of the present invention as hole mobile material.
As a result of, under the voltage of 6.6V, current flowing is 14.4mA/cm 2, confirm to have launched 1080cd/m 2ruddiness.
[embodiment 6] are used organic electroluminescent compounds of the present invention to prepare the OLED device
Same procedure is manufactured the OLED device as described in Example 1, and difference is to use compound 1 of the present invention as hole mobile material, and uses organic iridium complex (Ir (ppy) 3[three (2-phenylpyridine) iridium] is as the electroluminescent doping agent in electroluminescence layer.
As a result of, under the voltage of 6.6V, current flowing is 3.5mA/cm 2, confirm to have launched 1080cd/m 2green glow.
[embodiment 7] are used organic electroluminescent compounds of the present invention to prepare the OLED device
Same procedure is manufactured the OLED device as described in Example 1, and difference is to use compound 31 of the present invention as hole mobile material, and uses organic iridium complex (Ir (ppy) 3[three (2-phenylpyridine) iridium] is as the electroluminescent doping agent in electroluminescence layer.
As a result of, under the voltage of 6.5V, current flowing is 3.5mA/cm 2, confirm to have launched 1085cd/m 2green glow.
[embodiment 8] are used organic electroluminescent compounds of the present invention to prepare the OLED device
Same procedure is manufactured the OLED device as described in Example 1, and difference is to use compound 49 of the present invention as hole mobile material, and uses organic iridium complex (Ir (ppy) 3[three (2-phenylpyridine) iridium] is as the electroluminescent doping agent in electroluminescence layer.
As a result of, under the voltage of 6.6V, current flowing is 3.5mA/cm 2, confirm to have launched 1070cd/m 2green glow.
[embodiment 9] are used organic electroluminescent compounds of the present invention to prepare the OLED device
Same procedure is manufactured the OLED device as described in Example 1, and difference is to use compound 75 of the present invention as hole mobile material, and uses organic iridium complex (Ir (ppy) 3[three (2-phenylpyridine) iridium] is as the electroluminescent doping agent in electroluminescence layer.
As a result of, under the voltage of 6.5V, current flowing is 3.6mA/cm 2, confirm to have launched 1085cd/m 2green glow.
[embodiment 10] are used organic electroluminescent compounds of the present invention to prepare the OLED device
Same procedure is manufactured the OLED device as described in Example 1, and difference is to use compound 76 of the present invention as hole mobile material, and uses organic iridium complex (Ir (ppy) 3[three (2-phenylpyridine) iridium] is as the electroluminescent doping agent in electroluminescence layer.
As a result of, under the voltage of 6.5V, current flowing is 3.5mA/cm 2, confirm to have launched 1065cd/m 2green glow.
[embodiment 11] are used organic electroluminescent compounds of the present invention to prepare the OLED device
Same procedure is manufactured the OLED device as described in Example 1, difference is to use compound 43 of the present invention to replace 2-TNATA[4,4', 4 " tri-(N; N-(2-naphthyl)-phenyl amino) triphenylamine] as hole-injecting material, and use organic iridium complex (Ir (ppy) 3[three (2-phenylpyridine) iridium] is as the electroluminescent doping agent in electroluminescence layer.
As a result of, under the voltage of 6.9V, current flowing is 3.9mA/cm 2, confirm to have launched 1065cd/m 2green glow.
[embodiment 12] are used organic electroluminescent compounds of the present invention to prepare the OLED device
Same procedure is manufactured the OLED device as described in Example 1, difference is to use compound 46 of the present invention to replace 2-TNATA[4,4', 4 " tri-(N; N-(2-naphthyl)-phenyl amino) triphenylamine] as hole mobile material, and use organic iridium complex (Ir (ppy) 3[three (2-phenylpyridine) iridium] is as the electroluminescent doping agent in electroluminescence layer.
As a result of, under the voltage of 6.8V, current flowing is 4.0mA/cm 2, confirm to have launched 1075cd/m 2green glow.
[comparative example 1] used the electroluminescent properties of the OLED device of associated electrical electroluminescent material
Manufacture the OLED device by the method identical with embodiment 1, different is to use NPB[N in the cell of vacuum phase deposition equipment, N'-bis-(Alpha-Naphthyl)-N, N'-phenylbenzene-4,4'-diamines] replace compound of the present invention as hole mobile material.
As a result of, under the voltage of 7.5V, current flowing is 15.3mA/cm 2, confirm to have launched 1000cd/m 2ruddiness.
[comparative example 2] used the electroluminescent properties of the OLED device of conventional electroluminescent material
Manufacture the OLED device by the method identical with embodiment 3, different is to use NPB[N in the cell of vacuum phase deposition equipment, N'-bis-(Alpha-Naphthyl)-N, N'-phenylbenzene-4,4'-diamines] replace compound of the present invention as hole mobile material.
As a result of, under the voltage of 7.5V, current flowing is 3.8mA/cm 2, confirm to have launched 1000cd/m 2green glow.
Can confirm, than conventional material, the organic electroluminescent compounds of the present invention's exploitation has more excellent electroluminescence characters.In addition, according to the organic electroluminescence device that uses organic electroluminescent compounds of the present invention as hole mobile material or hole-injecting material, its lowest unoccupied molecular orbital (LUMO) promotes, three times have been increased to promote iris action, thereby make the OLED device there is better luminous efficiency, phosphorescence luminous efficiency particularly, and because the endurance life characteristic of material excellence can obtain having the device of excellent driving endurance life characteristic.

Claims (10)

1. the organic electroluminescent compounds meaned by following Chemical formula 1:
Chemical formula 1
Figure FDA00002942410600011
In Chemical formula 1:
Mean-O-of X ,-S-,-C (R 11r 12)-or-Si (R 13r 14)-;
R 11and R 14mean that independently hydrogen, deuterium, halogen, replacement or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl, replacement or unsubstituted (C3-C30) heteroaryl, replacement or unsubstituted 5-unit are to 7-unit Heterocyclylalkyl, replacement or unsubstituted (C3-C30) cycloalkyl, or adjacent substituting group can be connected to form ring;
R 1to R 4mean independently hydrogen, deuterium, halogen, replace or unsubstituted (C1-C30) alkyl, replace or unsubstituted (C6-C30) aryl, replace or unsubstituted (C3-C30) heteroaryl, replace or unsubstituted (C3-C30) cycloalkyl, replace or unsubstituted 5-unit to 7-unit Heterocyclylalkyl, replace or unsubstituted (C6-C30) aryl (C1-C30) alkyl, with one or more Cycloalkylfused replacements or unsubstituted (C6-C30) aryl, the 5-unit condensed with one or more replacements or unsubstituted aromatic ring to 7-unit Heterocyclylalkyl, (C3-C30) cycloalkyl perhaps condensed with one or more replacements or unsubstituted aromatic ring, replace or unsubstituted (C1-C30) silyl, cyano group, nitro or hydroxyl, and work as R 1to R 4while being plural form respectively, they can be interconnected to form ring structure,
R 5represent hydrogen, deuterium, halogen, replacement or unsubstituted (C1-C30) alkyl, replacement or unsubstituted (C6-C30) aryl, replacement or unsubstituted (C3-C30) heteroaryl or replacement or unsubstituted 5-unit to 7-unit Heterocyclylalkyl;
L 1and L 2mean independently chemical bond, replacement or unsubstituted (C6-C30) arylidene or replacement or unsubstituted (C3-C30) heteroarylidene, only get rid of L 1and L 2the situation that simultaneously means chemical bond;
Ar means to replace or unsubstituted (C6-C30) aryl, replace or unsubstituted (C3-C30) heteroaryl, replace or unsubstituted 5-unit to 7-unit Heterocyclylalkyl, with one or more Cycloalkylfused replacements or unsubstituted (C6-C30) aryl, replacement or unsubstituted (C3-C30) heteroaryl of condensing with one or more replacements or unsubstituted aromatic ring, the 5-unit condensed with one or more replacements or unsubstituted aromatic ring to 7-unit Heterocyclylalkyl, perhaps they can be connected to form alicyclic ring with adjacent substituting group by (C3-C30) alkylidene group that is with or without condensed ring or (C3-C30) alkenylene that is with or without condensed ring, perhaps monocycle or many cyclophanes ring,
A to d means the integer of 0-4 independently, when a to d means to be more than or equal to 2 integer independently, and R 1, R 2, R 3and R 4can be mutually identical or different, and adjacent substituting group can be connected to form ring;
The heteroatoms that described Heterocyclylalkyl and heteroaryl contain one or more B of being selected from, N, O, S, P (=O), Si and P; And
Further replace R 1to R 4, R 5, R 11to R 14, L 1, L 2one or more with the substituting group of Ar independently selected from lower group: deuterium, halogen, replaced by halogen or unsubstituted (C1-C30) alkyl, (C6-C30) aryl, quilt (C6-C30) aryl replaces or unsubstituted (C3-C30) heteroaryl, 5-unit to 7-unit Heterocyclylalkyl, 5-unit to the 7-unit Heterocyclylalkyl condensed with one or more aromatic rings, (C3-C30) cycloalkyl, (C6-C30) cycloalkyl, the R that condense with one or more aromatic rings 21r 22r 23si-, (C2-C30) thiazolinyl, (C2-C30) alkynyl, cyano group, carbazyl, NR 24r 25, BR 26r 27, PR 28r 29, P (=O) R 30r 31, (C6-C30) aryl (C1-C30) alkyl, (C1-C30) alkyl (C6-C30) aryl, R 32s-, R 33o-, R 34c (=O)-, R 35c (=O) O-, carboxyl, nitro and hydroxyl, R 21to R 33each is hydrogen independently, deuterium, halogen, replace or unsubstituted (C1-C30) alkyl, replace or unsubstituted (C6-C30) aryl, replace or unsubstituted (C3-C30) heteroaryl, replace or unsubstituted 5-unit to 7-unit Heterocyclylalkyl, perhaps they can be connected to form alicyclic ring with adjacent substituting group by replacement or unsubstituted (C3-C30) alkylidene group that is with or without condensed ring or the replacement that is with or without condensed ring or unsubstituted (C3-C30) alkenylene, perhaps monocycle or many cyclophanes ring, the carbon atom of formed alicyclic ring or monocycle or many cyclophanes ring can be by one or more nitrogen that is selected from, the heteroatoms of oxygen and sulphur replaces, and R 34and R 35mean independently (C1-C30) alkyl, (C1-C30) alkoxyl group, (C6-C30) aryl or (C6-C30) aryloxy.
2. organic electroluminescent compounds as claimed in claim 1, described compound is meaned by Chemical formula 2 or chemical formula 3:
Chemical formula 2
Figure FDA00002942410600031
Chemical formula 3
Figure FDA00002942410600032
In Chemical formula 2 and 3,
X, R 1to R 4, R 5, L 1, L 2, Ar and a to d definition identical with the definition in Chemical formula 1.
3. organic electroluminescent compounds as claimed in claim 2, is characterized in that, described Ar is selected from following structure:
Figure FDA00002942410600041
Figure FDA00002942410600042
。
4. organic electroluminescent compounds as claimed in claim 1, is characterized in that, described organic electroluminescent compounds is selected from following compound:
Figure FDA00002942410600051
Figure FDA00002942410600061
Figure FDA00002942410600071
5. an organic electroluminescence device, described device comprises the described organic electroluminescent compounds of any one in claim 1-4.
6. organic electroluminescence device as claimed in claim 5, is characterized in that, described organic electroluminescent compounds is as hole-injecting material or hole mobile material.
7. organic electroluminescence device as claimed in claim 6, is characterized in that, described organic electroluminescence device comprises: the first electrode; The second electrode; And insert one or more layers organic layer between described the first electrode and the second electrode, the organic electroluminescent compounds that described organic layer contains one or more Chemical formula 1s.
8. organic electroluminescence device as claimed in claim 7, it is characterized in that, described organic layer also comprises one or more metals or its title complex of organo-metallic, period 4 and the period 5 transition metal, lanthanide series metal and the d-transition element that are selected from the 1st family, the 2nd family in the periodic table of elements.
9. organic electroluminescence device as claimed in claim 7, is characterized in that, described organic layer comprises electroluminescence layer and charge generation layer simultaneously.
10. organic electroluminescence device as claimed in claim 7, is characterized in that, described organic layer also comprises the organic electro luminescent layer of one or more layers red-emitting, green glow or blue light, to realize transmitting white.
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