CN103554131A - Oxidized thieno-bi-carbazole derivative and applications thereof - Google Patents

Oxidized thieno-bi-carbazole derivative and applications thereof Download PDF

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CN103554131A
CN103554131A CN201310521566.4A CN201310521566A CN103554131A CN 103554131 A CN103554131 A CN 103554131A CN 201310521566 A CN201310521566 A CN 201310521566A CN 103554131 A CN103554131 A CN 103554131A
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thiophene
carbazole
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林存生
郭文波
付文岗
任辉彩
刘英瑞
石宇
董凯
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Yantai Valiant Fine Chemicals Co Ltd
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Abstract

The invention relates to an oxidized thieno-bi-carbazole derivative and applications thereof, which belong to the field of organic photoelectric materials. In a compound, an electron withdrawing group -SO- or -SO2- is introduced at 7- and carbazole derivatives are introduced at two ends so as to form the oxidized thieno-bi-carbazole derivative; the general formula of the oxidized thieno-bi-carbazole derivative is as shown in the specification, wherein -SO- or -SO2- has excellent electron transportation performance, thereby enhancing the electron affinity of the compound and the compound stability in air; simultaneously carbazoles with excellent hole transportation performance are introduced at the two ends, so that a transportation material with double polarity is formed. The oxidized thieno-bi-carbazole derivative can serve as a transportation material and a light emitting material of an OLED (Organic Light Emitting Diode) device, and the prepared OLED device has the effect characteristics of high brightness, high efficiency and low voltage.

Description

A kind of oxidation of thiophene two carbazole derivative and application thereof
Technical field
The present invention relates to organic photoelectrical material field, relate in particular to a kind of oxidation of thiophene two carbazole derivative and application thereof.
Background technology
The research of organic electroluminescence device starts from the '30s of eighties of last century, Destriau in 1936 is dispersed in organic fluorescent compounds in polymkeric substance, to make film, obtained electroluminescent device the earliest, but this device is because film is thicker, cut-in voltage is very high, does not cause at that time everybody attention, but to the people such as nineteen eighty-two P.S.Vincett adopt vacuum-deposited method to prepare the thick anthracene film of 0.6 μ m, the driving voltage of device has been dropped to below 30V, this just starts to have attracted people's attention, 1987, to organic electroluminescence device, be to there is a year of milestone significance, C.W.Tang etc. adopt ultrathin membrane technology, with a kind of diamine derivative N, N,-diphenyl-N, N,-bis (3-methylphe nyl)-1, 1, biphenyl-4, 4, diamine (TPD) is as hole transmission layer, using tris (8-hydrox yquinoline) aluminum (Alq3) as luminescent layer, made double-deck organic electroluminescence device, the brightness under 10V of this device can reach 1000cd/m2, luminous efficiency is 1.51lm/W, life-span is greater than 100 hours, this breakthrough is worldwide carried out rapidly and in depth the research of organic electroluminescence device.
In order to obtain the practical organic electroluminescence device of high brightness, high-level efficiency, long lifetime and low turn-on voltage, people constantly develop novel material and propose new device architecture etc.
The people such as C.Adachi in 1988 have proposed the three-decker that hole transmission layer, electron transfer layer and luminescent layer are separated first, have obtained high brightness and long-life blue-light device; In the organic and inorganic EL international conference that 1994 hold Japanese shore pine, C.W.Tang reported first reach the bilayer structure organic electroluminescence device of 10000 hours work-ing life; 1998, the Forrest group of Princeton university proposes phosphorescent coloring to be applied to organic electroluminescence device first, so just broken through device internal quantum efficiency lower than 25% restriction, make in theory internal quantum efficiency reach 100%, thereby started the frontier of Based on Organic Electrophosphorescence.In the same year, T.R.Hebner etc. have invented the ink-jet printing process that is prepared with organic electroluminescence devices, this for organic electroluminescence device from study direction market, provide larger may.Enter the new millennium, various novel organic luminescent devices emerge in an endless stream especially, more representational: 2004, and lamination (tandem) organic electroluminescence device that the people such as L.S.Liao make, current efficiency is up to 136cd/A.
Luminous efficiency for equilbrium carrier rate of injection and raising device, conventionally in luminescent device, introduce the electron transfer layer that one deck consists of electron transport material and the hole transmission layer being formed by hole mobile material, but the introducing of electronics and hole transmission layer often causes the increase of element manufacturing cost.In order to simplify device architecture, reduce the driving voltage of device, the injection in balance electronic and hole, current research trend is in concentrating on the group of several functions in a molecule, makes them have two or more functions (hole transport, electronic conduction and luminous etc.) simultaneously.
In current present Research, carbazole and derivative thereof belong to electron rich system, and generally acknowledged have a good cavity transmission ability, strong electron-withdrawing group group-SO-or-SO 2-can put forward high molecular electron affinity and electronic mobility, and sulphur atom located the state of oxidation, has oxidation-resistance.In Chinese patent CN1342720A and CN101205336 introducing-SO-or-SO 2-, all obtained having the photoelectric material of superperformance.This patent in oxidation of thiophene, introduced strong electron-withdrawing group-SO-or-SO 2-, electron transport ability obviously increases.Carbazole and oxidation of thiophene are combined in same a part, composition be take the electrogen that oxidation of thiophene two carbazole framework unit are core, form larger conjugated system, show high thermostability and high second-order transition temperature, therefore become class organic photoelectrical material likely.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of oxidation of thiophene two carbazole derivative and application thereof.
The technical scheme that the present invention solves the problems of the technologies described above is as follows: a kind of oxidation of thiophene two carbazole derivative, and the oxidation of thiophene of take also two carbazoles is parent, general structure is as follows:
Figure BDA0000404151990000031
Wherein, X is SO or SO 2in mother nucleus structure 7, the replacement numbering of said structure formula (1) is as follows:
Figure BDA0000404151990000032
；
R 1and R 2independently be selected from the C of hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl, cyano group, nitro, alkylsulfonyl, sulfoxide, acid amides, isothiocyano, straight chain or cladodification 1～C 12containing oxyalkyl, replacement or unsubstituted C 5～C 60polyaromatic conjugated structure group, wherein said R 1, R 2can be identical, also can be different;
R 3and R 4independently be selected from the C of hydrogen, straight chain or cladodification 1～C 30the C of alkyl, straight chain or cladodification 1～C 12containing oxyalkyl and replacement or unsubstituted C 5～C 60polyaromatic conjugated structure group, wherein said R 3, R 4can be identical, also can be different.
The invention provides a kind of oxidation of thiophene two carbazoles derivative preparation methods, concrete steps are as follows:
In above-mentioned steps (1), adopt Ullmann linked reaction; applicable halogenated alkane or halo polycyclic aromatic hydrocarbons and oxidation of thiophene two carbazoles are under nitrogen or protection of inert gas; using cuprous iodide, cuprous bromide, Red copper oxide, copper powder or palladium as catalyzer; with sodium hydride, potassium tert.-butoxide, sodium tert-butoxide, butyllithium (hexane solution), salt of wormwood or cesium carbonate, provide alkaline environment, under the condition of 0～120 ℃, react 5-30 hour.
Figure BDA0000404151990000041
In above-mentioned steps (2), 5,9-bis-replacement oxidation of thiophene two carbazoles are in methylene dichloride, chloroform, ethylene dichloride, acetic acid or sulphuric acid soln, using tosic acid, iron trichloride, ferric bromide, iron powder or aluminum chloride as catalyzer, under the condition of 0～120 ℃, react 5～30 hours.
Figure BDA0000404151990000042
In above-mentioned steps (3), adopt Suzuki linked reaction; 2,12-bis-is bromo-5, and 9-bis-replaces oxidation of thiophene two carbazoles under nitrogen or protection of inert gas; using cuprous iodide, cuprous bromide, Red copper oxide, copper powder or palladium as catalyzer, with Pd (dppf) 2cl 2, Pd (PPh 3) 4and Pd (PPh 3) 2cl 2catalyst ligand, provides alkaline environment with sodium hydride, potassium tert.-butoxide, sodium tert-butoxide, butyllithium (hexane solution), Potassium ethanoate, potassiumphosphate, salt of wormwood or cesium carbonate, reacts 5～30 hours under the condition of 0～120 ℃.
Figure BDA0000404151990000051
In above-mentioned steps (4), adopt Suzuki linked reaction; 2,12-tetramethyl ethylene ketone boric acid ester-5,9-bis-replacement oxidation of thiophene two carbazoles are under nitrogen or protection of inert gas; using cuprous iodide, cuprous bromide, Red copper oxide, copper powder or palladium as catalyzer, with Pd (dppf) 2cl 2, Pd (PPh 3) 4and Pd (PPh 3) 2cl 2catalyst ligand, provides alkaline environment with sodium hydride, potassium tert.-butoxide, sodium tert-butoxide, butyllithium (hexane solution), Potassium ethanoate, potassiumphosphate, salt of wormwood or cesium carbonate, reacts 5～30 hours under the condition of 0～120 ℃.
The oxidation of thiophene that the present invention is synthetic the part-structure of two carbazole derivative are as follows:
Figure BDA0000404151990000071
Figure BDA0000404151990000081
Figure BDA0000404151990000091
The present invention also provides a kind of oxidation of thiophene two carbazole derivative at organic electroluminescence device.
As shown in Figure 1, use the OLED luminescent device structure of material of the present invention, contain at least one luminescent layer 5, hole injection layer 3, hole transmission layer 4, electron transfer layer 6 and/or electron injecting layer 7 are set in this layer according to optional principle.OLED luminescent device comprises layer structure as described below:
(1) anode/organic luminous layer 5/ negative electrode;
(2) anode/hole injection layer 3/ organic luminous layer 5/ negative electrode;
(3) anode/organic luminous layer 5/ electron injecting layer 7/ negative electrode;
(4) anode/hole injection layer 3/ organic luminous layer 5/ electron injecting layer 7/ negative electrode;
(5) anode/hole transmission layer 4/ organic luminous layer 5/ electron injecting layer 7/ negative electrode;
(6) anode/hole injection layer 3/ hole transmission layer 4/ organic luminous layer 5/ electron injecting layer 7/ negative electrode;
(7) anode/hole injection layer 3/ hole transmission layer 4/ organic luminous layer 5/ electron transfer layer 6/ negative electrode.
Make in OLED indicating meter, each layer can be made film by material by methods such as vapour deposition method, spin-coating method or teeming practices and form.The thickness of each layer forming is in this way not particularly limited, and character that can respective material and suitable setting are generally the scope of 2nm～5000nm.Moreover, the method for luminescent material thin-film is easily obtained to uniform rete and the difficult experience that generates pin hole, preferably vapour deposition method.Evaporation condition is general preferred at boat, 50 ℃～400 ℃ of Heating temperatures, vacuum tightness 10 -6pa～10 -3pa, evaporation rate 0.01nm/s～50nm/s, suitable setting in the scope of substrate temperature-150 ℃～300 ℃, thickness 5nm～5um.
Anode has the function that hole is injected into hole transmission layer 4, and anode consists of later material conventionally: as metals such as aluminium, gold and silver, nickel, palladium or platinum; As metal oxides such as Indium sesquioxide, stannic oxide, zinc oxide, indium tin composite oxides, indium zinc composite oxides; As metal halides such as cupric iodides; Carbon black; Or partially conductive polymer etc.
Hole transmission layer is from the high-level efficiency of anode injected hole and can effectively transmits the material of injected holes.Therefore, ionizing potential that need to this material is low, high to the perviousness of visible ray, hole mobility is high, stable in properties, also need to be in preparation or the light that is difficult for producing while using become the impurity of trap (trap).In addition owing to contacting with luminescent layer 5, need hole transmission layer 4 not make the light delustring from luminescent layer 5, and not and between luminescent layer 5, form exciplex and the common hole mobile material that lowers efficiency can enumerate with, N '-phenylbenzene-N, N '-(1-naphthyl)-1, '-biphenyl-4, the aromatic diamine that contains plural tertiary amine that 4 '-diamines (NPB) is representative, the aromatic amine compounds that triphen amine has star radial configuration, carbazoles derivative etc.These compounds can be used alone, but also also mix together two or more.
As at hole-injecting material functional materials, can from material known to the hole transmission layer 4 of OLED luminescent device, select material arbitrarily to use.
Luminescent layer 5 is formed by luminophore, wherein, applying between the electrode of electric field, this luminophore because of hole and electronics again in conjunction with exciting, thereby show luminous by force.Conventionally luminescent layer 5 contains doping type material and the substrate material as luminophore.In order to obtain high-level efficiency OLED luminescent device, the adoptable a kind of dopant material of its luminescent layer 5, or adopt multiple dopant material.Dopant material can be simple fluorescence or phosphor material, or is formed by different fluorescence and phosphorescence matched combined, and luminescent layer can be single luminescent layer material, can be also the recombination luminescence layer material being superimposed.
The material of main part of luminescent layer not only needs to possess ambipolar charge-transporting matter, need appropriate energy rank simultaneously, excitation energy is delivered to object luminescent material effectively, and the material of this class can be enumerated diphenylethyllene aryl derivatives, stibene derivative, carbazole derivative, triarylamine derivatives, anthracene derivant, pyrene derivatives, coronene derivative etc.
With respect to material of main part, more than the incorporation of guest materials is preferably 0.01 % by weight, below 20 % by weight.The material of this class can be enumerated the metal complexes of iridium, nail, platinum, rhenium, palladium etc.
The material that forms the electron transfer layer 6 of above-mentioned OLED luminescent device, can in possessing electronic transport property OLELD material, select to use arbitrarily, such material can be enumerated as 1,3, the benzimidazoles derivatives such as 5-tri-(1-naphthyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), three (oxine) aluminium (Alq 3) etc. metal complexes, 2-(4 '-trimethylphenylmethane base)-5-(4 '-xenyl)-1,3,4-oxadiazole (oxadiazole derivative such as PBD) Deng, 4,7-phenylbenzene-1, the phenanthroline derivatives such as 10-phenanthroline (BPhen), triazole derivative, quinoline, quinoxaline derivatives etc.
Optional metal, alloy, conductive compound and their mixture that is less than 4eV by work function of the spendable cathode material of above-mentioned OLED luminescent device.Its concrete example is aluminium, calcium, magnesium, lithium, magnesium alloy, aluminium alloy etc.In order to obtain efficiently the luminous of OLED, comparatively ideal is that at least one transmitance of electrode is made as more than 10%.Negative electrode can form as vacuum evaporation, vapour deposition or sputter by dry method.
The invention has the beneficial effects as follows:
Oxidation of thiophene two carbazole derivative that the present invention is synthetic are applied to obtain efficient electroluminescent properties in organic electroluminescence device, and its major advantage is as follows:
1, adopt that to take oxidation of thiophene two carbazoles be parent, due in molecular system-SO-or-SO 2-there is good electronic transmission performance, its two ends each and connect a carbazole derivative with good hole transport performance, formation has the photoelectric material of bipolarity transmittability, makes the transmission balance in hole and electronics in luminescent layer, greatly improves luminous efficiency.
2, have good thermostability, second-order transition temperature and decomposition temperature are all very high.
3, such material has applicable molecular entergy level, be applicable to doing blue emitting material material of main part, there are potentiality red and green application simultaneously, therefore can be applicable to red-green-blue doping property material of main part, also can be separately as hole mobile material, electron transport material or luminescent layer.
Accompanying drawing explanation
Fig. 1 is a kind of oxidation of thiophene of the present invention two carbazole derivative OLED luminescent device structural representations;
Fig. 2 is usingd the TGA graphic representation of compound 27 as hole transmission layer in device thermal performance analysis embodiment 1 of the present invention.
In accompanying drawing, the list of parts of each label representative is as follows:
1, transparency carrier layer, 2, transparent electrode layer, 3, hole injection layer, 4, hole transmission layer, 5, luminescent layer, 6, electron transfer layer, 7, electron injecting layer, 8, negative electrode.
Embodiment
Below in conjunction with accompanying drawing, principle of the present invention and feature are described, example, only for explaining the present invention, is not intended to limit scope of the present invention.
Embodiment prepared by compound sample:
Embodiment 15,9-phenylbenzene-5, and 9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide (compound 1) synthetic:
Get also [2,3-b:5,4-b'] two carbazole-7 of 5,9-dihydro-thiophene, 7-dioxide (19.7g, 50.0mmol) and sodium hydride (6.0g, 150mmol, 60% content), with 60mL DMF, dissolve, logical nitrogen gas stirring 1 hour, to remove the oxygen in reaction flask.With below 0 ℃, drip bromobenzene (23.0g, 150mmol), reaction process is followed the tracks of detection by TLC.After reaction 3h, slowly add 150mL deionized water in reaction solution, filter to obtain off-white color pressed powder 26.3g, the 320 ℃ of distillations in chemical gas-phase deposition system of thick product are purified, and obtain 24.6g off-white color pressed powder, and productive rate is 90%).With DEI-MS, identify this compound, molecular formula C 36h 22n 2o 2s, detected value [M+1] +=546.96, calculated value 546.64.
Embodiment 25,9-bis-(naphthalene-1-yl)-5, and 9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide (compound 2)
With 5,9-dihydro-thiophene [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide and 1-bromonaphthalene are that starting raw material is by the synthetic method preparation of compound 1 in embodiment 1.With DEI-MS, identify this compound, molecular formula C 44h 26n 2o 2s, detected value [M+1] +=647.33, calculated value 646.75.
Embodiment 35,9-bis-(naphthalene-1-yl)-5, and 9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazoles-7-oxide compound (compound 3) also
With 5,9-dihydro-thiophene, also [2,3-b:5,4-b'] two carbazoles-7-oxide compound and 1-bromonaphthalene are that starting raw material is by the synthetic method preparation of compound 1 in embodiment 1.With HR-MS, identify this compound, molecular formula C 44h 26n 2oS, detected value [M+1] +=631.29, calculated value 630.76.
Embodiment 45, two (the 4-phenyl-1-naphthyls)-5 of 9-, and 9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazoles 7 also, 7-dioxide (compound 4)
With 5,9-dihydro-thiophene [2,3-b:5,4-b'] two carbazoles 7 also, 7-dioxide and 4-phenyl-1-bromonaphthalene are that starting raw material is by the synthetic method preparation of compound 1 in embodiment 1.With DEI-MS, identify this compound, molecular formula C 56h 34n 2o 2s, detected value [M+1] +=800.07, calculated value 798.95.
Embodiment 55, two (4-(2-naphthyl) phenyl)-5 of 9-, and 9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazoles-7-oxide compound (compound 5) also
With 5,9-dihydro-thiophene, also [2,3-b:5,4-b'] two carbazoles-7-oxide compound and 4-(2-naphthyl) bromobenzene are that starting raw material is by the synthetic method preparation of compound 1 in embodiment 1.With DEI-MS, identify this compound, molecular formula C 56h 34n 2oS, detected value [M+1] +=783.77, calculated value 782.95.
Embodiment 65, two (4-(2-naphthyl) phenyl)-5 of 9-, and 9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide (compound 6)
With 5,9-dihydro-thiophene [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide and 4-(2-naphthyl) bromobenzene is that starting raw material is by the synthetic method preparation of compound 1 in embodiment 1.With DEI-MS, identify this compound, molecular formula C 56h 34n 2o 2s, detected value [M+1] +=799.99, calculated value 798.95.
Embodiment 75,9-di (9-phenanthryl)-5, and 9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide (compound 7)
With 5,9-dihydro-thiophene [2,3-b:5,4-b'] two carbazole-7 also, prepared by the luxuriant and rich with fragrance synthetic method of pressing compound 1 in embodiment 1 for starting raw material of 7-dioxide and 9-bromine.With DEI-MS, identify this compound, molecular formula C 52h 30n 2o 2s, detected value [M+1] +=747.57, calculated value 746.87.
Embodiment 85,9-bis-([1,1':3', 1 " triphenyl]-5'-yl)-5,9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide (compound 8)
With 5,9-dihydro-thiophene [2,3-b:5,4-b'] two carbazole-7 also, the synthetic method preparation that 7-dioxide and 5'-bromine [1,1':3', 1 " triphenyl] are pressed compound 1 in embodiment 1 for starting raw material.With DEI-MS, identify this compound, molecular formula C 60h 38n 2o 2s, detected value [M+1] +=852.12, calculated value 851.02.
Embodiment 95, two (4, the 6-phenylbenzene-1,3,5-triazines-2-yls)-5 of 9-, and 9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide (compound 9)
With 5,9-dihydro-thiophene [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide and 2-are bromo-4, and 6-phenylbenzene-1,3,5-triazines is that starting raw material is by the synthetic method preparation of compound 1 in embodiment 1.With DEI-MS, identify this compound, molecular formula C 54h 32n 8o 2s, detected value [M+1] +=858.09, calculated value 856.95.
Embodiment 105, two (4, the 6-phenylbenzene-1,3,5-triazines-2-yls)-5 of 9-, and 9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazoles-7-oxide compound (compound 10) also
With 5,9-dihydro-thiophene also [2,3-b:5,4-b'] two carbazoles-7-oxide compound and 2-bromo-4,6-phenylbenzene-1,3,5-triazines is that starting raw material is by the synthetic method preparation of compound 1 in embodiment 1.With DEI-MS, identify this compound, molecular formula C 54h 32n 8oS, detected value [M+1] +=841.83, calculated value 840.95.
Embodiment 115, two (4-(hexichol amido) phenyl)-5 of 9-, and 9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide (compound 11)
With 5,9-dihydro-thiophene [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide and 4-(hexichol amido) bromobenzene is that starting raw material is by the synthetic method preparation of compound 1 in embodiment 1.With DEI-MS, identify this compound, molecular formula C 60h 40n 4o 2s, detected value [M+1] +=881.86, calculated value 881.05.
Embodiment 125, two (4-(9H-carbazole-9-yl) phenyl)-5 of 9-, and 9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide (compound 12)
With 5,9-dihydro-thiophene [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide and 4-(9H-carbazole-9-yl) bromobenzene is that starting raw material is by the synthetic method preparation of compound 1 in embodiment 1.With DEI-MS, identify this compound, molecular formula C 60h 36n 4o 2s, detected value [M+1] +=878.19, calculated value 877.02.
Embodiment 135, two (4-(4, the 6-phenylbenzene-1,3,5-triazines-2-yl) phenyl)-5 of 9-, and 9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide (compound 13)
With 5,9-dihydro-thiophene [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide and 4-(4,6-phenylbenzene-1,3,5-triazines-2-yl) bromobenzene is that starting raw material is by the synthetic method preparation of compound 1 in embodiment 1.With DEI-MS, identify this compound, molecular formula C 66h 40n 8o 2s, detected value [M+1] +=1009.86, calculated value 1009.14.
Embodiment 145,9-bis-(4-iso-octyl)-5, and 9-dihydro-thiophene is [2,3-b:5,4-b'] two click-7 also, 7-dioxide (compound 14)
With 5,9-dihydro-thiophene [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide and 4-(4,6-phenylbenzene-1,3,5-triazines-2-yl) bromobenzene is that starting raw material is by the synthetic method preparation of compound 1 in embodiment 1.With DEI-MS, identify this compound, molecular formula C 40h 46n 2o 2s, detected value [M+1] +=619.66, calculated value 618.87.
Embodiment 155, two (methoxyl methyl)-5 of 9-, and 9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazoles-7-oxide compound (compound 15) also
With 5,9-dihydro-thiophene, also [2,3-b:5,4-b'] two carbazoles-7-oxide compound and methoxyl group methyl bromide are that starting raw material is by the synthetic method preparation of compound 1 in embodiment 1.With DEI-MS, identify this compound, molecular formula C 28h 22n 2o 3s, detected value [M+1] +=467.57, calculated value 466.55.
Embodiment 165,9-dibenzyl-5, and 9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazoles-7-oxide compound (compound 16) also
With 5,9-dihydro-thiophene, also [2,3-b:5,4-b'] two carbazoles-7-oxide compound and benzyl bromine are that starting raw material is by the synthetic method preparation of compound 1 in embodiment 1.With DEI-MS, identify this compound, molecular formula C 38h 26n 2oS, detected value [M+1] +=559.79, calculated value 558.69.
Embodiment 175, two (4, the 6-phenylbenzene-1,3,5-triazines-2-yls)-5 of 9-, and 9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-2 also, 12-dicyano-7,7-dioxide (compound 17)
In 100ml there-necked flask, add 10.14g2,12-bis-is bromo-5, and 9-two (4,6-phenylbenzene-1,3,5-triazine-2-yl)-5,9-dihydro-thiophene also [2,3-b:5,4-b'] two carbazole-7,7-dioxide (10.0mmol) and 1.43g potassium cyanide (22.0mmol), dissolve with 60mLDMF, logical nitrogen gas stirring 1 hour, to remove the oxygen in reaction flask.Then add Pd (PPh 3) 40.120g(1.0mmol), under strong stirring, reflux, reaction process is followed the tracks of detection by TLC.After reaction 24h, in reaction solution, add 50mL deionized water, remove by filter insolubles, water is separated with organic phase, and water is extracted with ethyl acetate (30mL is each, 3 times), after organic phase is mixed, underpressure distillation is concentrated to about 5mL, column chromatography carries out separation, eluent ethyl acetate: normal hexane (1:10, v/v).Obtain 6.43g white solid (productive rate is 82.10%).With DEI-MS, identify this compound, molecular formula C 56h 30n 10o 2s, detected value [M+1] +=908.03, calculated value 906.97.
Embodiment 185, two (4, the 6-phenylbenzene-1,3,5-triazines-2-yls)-2 of 9-, and different sulfhedryl-5 of 12-bis-, 9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide (compound 18)
Bromo-5 with 2,12-bis-, two (4, the 6-phenylbenzene-1,3,5-triazines-2-yls)-5 of 9-, 9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, and 7-dioxide and potassium sulfocyanate are that starting raw material is prepared by the synthetic method of compound 17 in embodiment 17.With DEI-MS, identify this compound, molecular formula C 56h 30n 10o 2s 3, detected value [M+1] +=971.93, calculated value 971.10.
Embodiment 192,12-di-t-butyl-5, and 9-phenylbenzene-5,9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide (compound 19)
Bromo-5 with 2,12-bis-, 9-dibenzyl-5,9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, and 7-dioxide and chloro tertiary butyl Grignard reagent are that starting raw material is by the synthetic method preparation of compound 17 in embodiment 17.With DEI-MS, identify this compound, molecular formula C 44h 38n 2o 2s, detected value [M+1] +=660.01, calculated value 658.85.
Embodiment 202,12-di-t-butyl-5, and two (4-(4, the 6-phenylbenzene-1,3,5-triazines-2-chlorine) phenyl)-5 of 9-, 9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide (compound 20)
Bromo-5 with 2,12-bis-, two (4-(4,6-phenylbenzene-1 of 9-, 3,5-triazine-2-chlorine) phenyl)-5,9-dihydro-thiophene also [2,3-b:5,4-b'] two carbazole-7,7-dioxide and chloro tertiary butyl Grignard reagent are that starting raw material is by the synthetic method preparation of compound 17 in embodiment 17.With DEI-MS, identify this compound, molecular formula C 74h 56n 8o 2s, detected value [M+1] +=1122.25, calculated value 1121.35.
Embodiment 212,5,9,12-tetraphenyl-5, and 9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide (compound 21)
Bromo-5 with 2,12-bis-, 9-phenylbenzene-5,9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, and 7-dioxide and phenylo boric acid are that starting raw material is by the synthetic method preparation of compound 17 in embodiment 17.With DEI-MS, identify this compound, molecular formula C 48h 30n 2o 2s, detected value [M+1] +=699.32, calculated value 698.83.
Embodiment 222, two ([1,1'-the biphenyl]-4-yls)-5 of 12-, and 9-phenylbenzene-5,9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide (compound 22)
Bromo-5 with 2,12-bis-, 9-phenylbenzene-5,9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, and 7-dioxide and 4-biphenyl boric acid are that starting raw material is by the synthetic method preparation of compound 17 in embodiment 17.With DEI-MS, identify this compound, molecular formula C 60h 38n 2o 2s, detected value [M+1] +=851.93, calculated value 851.02.
Embodiment 235, two ([1,1'-the biphenyl]-4-yls)-2 of 9-, and 12-phenylbenzene-5,9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide (compound 23)
Bromo-5 with 2,12-bis-, 9-([1,1'-biphenyl]-4-yl)-5,9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, and 7-dioxide and phenylo boric acid are that starting raw material is by the synthetic method preparation of compound 17 in embodiment 17.With DEI-MS, identify this compound, molecular formula C 60h 38n 2o 2s, detected value [M+1] +=851.93, calculated value 851.02.
Embodiment 245,9-di ([1,1':3', 1 " triphenyl]-5'-yl)-2,12-phenylbenzene-5,9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide (compound 24)
Bromo-5 with 2,12-bis-, 9-21,1':3', 1 " triphenyl]-5'-yl)-5,9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, and 7-dioxide and phenylo boric acid are that starting raw material is by the synthetic method preparation of compound 17 in embodiment 17.With DEI-MS, identify this compound, molecular formula C 72h 46n 2o 2s, detected value [M+1] +=1004.31, calculated value 1003.21.
Embodiment 255, two (4, the 6-phenylbenzene-1,3,5-triazines-2-yls)-2 of 9-, and 12-phenylbenzene-5,9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide (compound 25)
Bromo-5 with 2,12-bis-, two (4, the 6-phenylbenzene-1,3,5-triazines-2-yls)-5 of 9-, 9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, and 7-dioxide and phenylo boric acid are that starting raw material is prepared by the synthetic method of compound 17 in embodiment 17.With DEI-MS, identify this compound, molecular formula C 66h 40n 8o 2s, detected value [M+1] +=1009.98, calculated value 1009.14.
Embodiment 262,12-bis-([1,1':3', 1 " triphenyl]-5'-yl)-5,9-phenylbenzene-5,9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide (compound 26)
Bromo-5 with 2,12-bis-, two (4, the 6-phenylbenzene-1,3,5-triazines-2-yls)-5 of 9-, 9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, and 7-dioxide and phenylo boric acid are that starting raw material is prepared by the synthetic method of compound 17 in embodiment 17.With DEI-MS, identify this compound, molecular formula C 72h 46n 2o 2s, detected value [M+1] +=1003.68, calculated value 1003.21.
Embodiment 272, two (4, the 6-phenylbenzene-1,3,5-triazines-2-yls)-5 of 12-, and 9-phenylbenzene-5,9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide (compound 27)
Bromo-5 with 2,12-bis-, 9-phenylbenzene-5,9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, and 7-dioxide and phenylo boric acid are that starting raw material is by the synthetic method preparation of compound 17 in embodiment 17.With DEI-MS, identify this compound, molecular formula C 66h 40n 8o 2s, detected value [M+1] +=1009.99, calculated value 1009.14.
Embodiment 282, two (4, the 6-phenylbenzene-1,3,5-triazines-2-yls)-5 of 12-, and two (4-(1-phenyl-1H-benzimidazolyl-2 radicals-yl) phenyl)-5 of 9-, 9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide (compound 28)
Bromo-5 with 2,12-bis-, 9-phenylbenzene-5,9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, and 7-dioxide and phenylo boric acid are that starting raw material is by the synthetic method preparation of compound 17 in embodiment 17.With DEI-MS, identify this compound, molecular formula C 92h 56n 12o 2s, detected value [M+1] +=1394.39, calculated value 1393.57.
Embodiment 295,9-bis-([1,1':3', 1 " triphenyl]-5'-yl)-2, two (4, the 6-phenylbenzene-1,3,5-triazines-2-yls)-5 of 12-, 9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide (compound 29)
Bromo-5 with 2,12-bis-, 9-bis-([1,1':3', 1 " triphenyl]-5'-yl)-5,9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, and 7-dioxide and phenylo boric acid are that starting raw material is by the synthetic method preparation of compound 17 in embodiment 17.With DEI-MS, identify this compound, molecular formula C 90h 56n 8o 2s, detected value [M+1] +=1314.52, calculated value 1313.53.
Embodiment 302,5,9,12-tetra-(4,6-phenylbenzene-1,3,5-triazines-2-yl)-5, and 9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, 7-dioxide (compound 30)
Bromo-5 with 2,12-bis-, 9-bis-([1,1':3', 1 " triphenyl]-5'-yl)-5,9-dihydro-thiophene is [2,3-b:5,4-b'] two carbazole-7 also, and 7-dioxide and phenylo boric acid are that starting raw material is by the synthetic method preparation of compound 17 in embodiment 17.With DEI-MS, identify this compound, molecular formula C 84h 50n 14o 2s, detected value [M+1] +=1320.33, calculated value 1319.45.
Below, by device embodiment 1～3, describe the effect of the synthetic OLED material of the present invention on device in detail.
Fig. 1 is the device architecture of OLED material application of the present invention, and wherein 1 is transparency carrier layer, and 2 is transparent electrode layer, and 3 is hole injection layer, and 4 is hole transmission layer, and 5 is luminescent layer, and 6 is electron transfer layer, and 7 is electron injecting layer, and 8 is negative electrode.
Device embodiment 1 application of compound 1 in organic electroluminescence device
A) clean the anode on transparency carrier layer: use respectively deionized water, acetone, ethanol ultrasonic cleaning respectively 15 minutes, then in plasma clean device, process 2 minutes;
B) vacuum evaporation or solution film forming hole injection layer NPB(following formula 2 on anode), thickness is 50nm;
Figure BDA0000404151990000201
C) on hole injection layer 3, by vacuum evaporation mode evaporation following formula 3 structural compounds materials (TCTA), its thickness is 10nm, and this layer of organic materials uses as hole transmission layer 4.
Figure BDA0000404151990000202
D) common evaporation luminescent layer 5 on hole transmission layer 4, CBP shown in structural formula (4) is as material of main part, Ir(ppy shown in structural formula (5)) 3as phosphorescence dopant material, phosphor material doping ratio is 5%, and thickness is 30nm;
Figure BDA0000404151990000203
E) on doping type luminescent layer compound, the electron transfer layer 6 of vacuum evaporation is the material shown in the embodiment of the present invention 1, and thickness is 30nm;
F) on electron transfer layer 6, vacuum evaporation electron injecting layer LiF, thickness is 0.5nm, this layer is electron injecting layer 7;
G) on electron injecting layer 7, vacuum evaporation negative electrode Al, thickness is 100nm, this layer is negative electrode 8.
As above-mentioned, complete after OLED luminescent device, the luminous efficiency of measuring element, the I-E characteristic of luminescent spectrum and device, its result is presented at table 1.
Device embodiment 2 application of compound 27 in organic electroluminescence device
The difference of the present embodiment device and device embodiment 1 is: the electron transfer layer 6 of OLED luminescent device becomes shown in structural formula (6) 1,3,5-tri-(1-naphthyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), hole transmission layer becomes the material of structure described in the embodiment of the present invention 27.
Figure BDA0000404151990000211
The result of the OLED luminescent device of device embodiment 2 mades is presented in list 1.
Device embodiment 3 application of compound 21 in organic electroluminescence device
The difference of the present embodiment device and device embodiment 1 is: the electron transfer layer 6 of OLED luminescent device becomes shown in structural formula (6) 1,3,5-tri-(1-naphthyl-1H-benzimidazolyl-2 radicals-yl) benzene (TPBI), hole transmission layer is compound-material shown in structural formula 3 (TCTA), and luminescent layer 5 becomes the material of structure described in the embodiment of the present invention 21.
The result of the OLED luminescent device of device embodiment 3 mades is presented in list 1.
Table 1
Figure BDA0000404151990000221
Device 3 transmitting blue lights, the maximum current efficiency obtaining is 4.5cd/A, that the blue-fluorescence device performance of having reported is at present given prominence to, documents (J.A.C.S, 2012,134,14706) device EL performance, device performance of the present invention has obvious advantage in colour efficiency, brightness and purity, workable.As design philosophy of the present invention, the compound of synthesized has all shown good device performance as electron transfer layer or hole transmission layer (device 1,2) separately.
Thermal performance analysis embodiment 1
Good thermostability has important impact for EL performance and the life-span of device.This compounds thermogravimetric analysis (Thermal gravimetric analysis, TGA) on the DTG-60H of Shimadzu company thermal-analysis instrumentation, carry out, compound 1,21 and 27 heat decomposition temperatures are respectively 405 ℃, 407 ℃ and 428 ℃, all be greater than 400 ℃, illustrate that this compounds has good heat resistanceheat resistant solution ability; Wherein compound 27 only has a main thermal decomposition process in the scope of room temperature to 700 ℃, and its heat decomposition temperature is 428 ℃, and this illustrates that this compounds has good thermostability.In Fig. 2, provided the TGA figure of compound 27.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.

Claims (4)

1. oxidation of thiophene two carbazole derivative, is characterized in that, the oxidation of thiophene of take also two carbazoles is parent, and general structure is as follows:
Figure FDA0000404151980000011
Wherein, X is SO or SO 2;
R 1and R 2independently be selected from the C of hydrogen, methyl, ethyl, sec.-propyl, the tertiary butyl, cyano group, nitro, alkylsulfonyl, sulfoxide, acid amides, isothiocyano, straight chain or cladodification 1～C 12containing oxyalkyl, replacement or unsubstituted C 5～C 60polyaromatic conjugated structure group;
R 3and R 4independently be selected from the C of hydrogen, straight chain or cladodification 1～C 30the C of alkyl, straight chain or cladodification 1～C 12containing oxyalkyl and replacement or unsubstituted C 5～C 60polyaromatic conjugated structure group.
2. oxidation of thiophene two carbazole derivative preparation methods, is characterized in that, comprises the steps:
Figure FDA0000404151980000012
Figure FDA0000404151980000021
3. a kind of oxidation of thiophene two carbazole derivative preparation methods according to claim 2, is characterized in that, step (1) to (4) all, under nitrogen or protection of inert gas, is reacted 5～30 hours at 0～120 ℃ of temperature.
4. oxidation of thiophene two carbazole derivative organic electroluminescence devices, is characterized in that, adopts as arbitrary in claims 1 to 3 as described in oxidation of thiophene also two carbazole derivative can be as luminescent material or the transport material of organic electroluminescence device.
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