CN103804346B - Oxidation thioxanthone analog derivative, preparation method and application thereof - Google Patents

Oxidation thioxanthone analog derivative, preparation method and application thereof Download PDF

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CN103804346B
CN103804346B CN201210444090.4A CN201210444090A CN103804346B CN 103804346 B CN103804346 B CN 103804346B CN 201210444090 A CN201210444090 A CN 201210444090A CN 103804346 B CN103804346 B CN 103804346B
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base
beautiful jade
phenanthrene coughs
amido
oxidation
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CN103804346A (en
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汪鹏飞
王会
刘卫敏
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Technical Institute of Physics and Chemistry of CAS
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Abstract

The invention discloses a kind of oxidation thioxanthone analog derivative, its structural formula is as follows:In formula (1) and formula (2), R1、R2、R3、R4、R5、R6、R7、R8It is respectively selected from the one in hydrogen atom, alkoxyl, alkylthio group, alkylamino radical, aryl amine, aryloxy group, arylthio, aryl, heteroaromatic group and R1、R2、R3、R4、R5、R6、R7、R8In have at least one for aromatic group.The invention also discloses the preparation method and application of this oxidation thioxanthone analog derivative, this oxidation thioxanthone analog derivative can be used as the organic luminous layer of organic electroluminescence device.

Description

Oxidation thioxanthone analog derivative, preparation method and application thereof
Technical field
The present invention relates to oxidation thioxanthone analog derivative and preparation method thereof and the application that described oxidation thioxanthone analog derivative is in organic electroluminescence device.
Background technology
From 1987, C.W.Tang of Kodak et al. utilizes vacuum to steam the method for crossing first and is prepared for the device (C.W.Tang of little molecular film sandwich style, S.A.Vanslyke, AppliedPhysicsLetters, 1987,51,913), brand-new epoch have just been stepped in the research of electroluminescent organic material.Organic electroluminescence device is mainly made up of anelectrode, negative electrode, active layer.Wherein, active layer is luminescent layer, is clipped between both positive and negative polarity layer, forms the sandwich structure of similar sandwich.In order to improve injection and transmission, the work efficiency improving device of carrier, generally also to introduce carrier (hole and electronics) implanted layer, carrier blocking layers and exciton barrier-layer.Hole and electronics are injected into organic layer from positive and negative electrode respectively under the effect of extra electric field, and meet in luminescent layer, compound, radioluminescence.
In recent years, high efficiency, low driving voltage, high stability, different emission organic electroluminescence device be in succession seen in report (Xiao, L.X.;Kido, J.J., Adv.Mater.2011,23 (8), 926;Chaskar, A.;Wong, K.-T., Adv.Mater.2011,23 (34), 3876).Organic electroluminescence device, particularly organic electro phosphorescent device, receive general concern.The phosphorescent light-emitting materials being primarily due to such device can effectively utilize the triplet exciton that hole is compounded to form with electronics so that the theoretical internal quantum of such device reaches 100%, for 4 times of fluorescence electroluminescent device.But, phosphorescent devices truly, particularly blue phosphorescent device or few, its basic reason is not have suitable luminescent layer material of main part.
Suitable luminescent layer material of main part must is fulfilled for following requirement: have the triplet energy state higher than phosphorescent light-emitting materials, it is suppressed that energy energy passback from guest dye molecule to host molecule；There is the carrier transmission performance of balance；The film property possessed and chemical stability, to improve the service life of device.Because material of main part to possess the triplet energy state higher than phosphorescent light-emitting materials, this just requires that the band gap of material of main part comparatively wide must produce high triplet energy state.And broad-band gap means material and must possess short conjugated electron system, and short conjugated system is to the injection of carrier and what transmission was clearly disadvantageous.How at wide energy gap to ensure searching equilibrium point between high triplet energy level and good carrier transport, it it is the bottleneck of phosphorescent light body material development.
Summary of the invention
First technical problem that the invention solves the problems that is to provide the assorted anthrone analog derivative of sulfur oxide.
The preparation method that second technical problem that the invention solves the problems that is to provide the assorted anthrone analog derivative of sulfur oxide.
The 3rd technical problem that the invention solves the problems that is to provide the application of the assorted anthrone analog derivative of sulfur oxide.
The present invention provides oxidation thioxanthone analog derivative, and its structural formula is as follows:
In formula (1) and formula (2), R1、R2、R3、R4、R5、R6、R7、R8It is respectively selected from the one in hydrogen atom, alkoxyl, alkylthio group, alkylamino radical, aryl amine, aryloxy group, arylthio, aryl, heteroaromatic group and R1、R2、R3、R4、R5、R6、R7、R8In have at least one for aromatic group；
Further,
Described R1、R2、R3、R4、R5、R6、R7、R8The alkoxyl that alkoxyl is 1 to 20 carbon atom；
Described R1、R2、R3、R4、R5、R6、R7、R8The alkylthio group that alkylthio group is 1 to 20 carbon atom；
Described R1、R2、R3、R4、R5、R6、R7、R8The unsubstituted alkyl amine group that alkylamino radical is 1 to 20 carbon atom or substituted alkylamine base；
Described R1、R2、R3、R4、R5、R6、R7、R8The aryl amine that aryl amine is 6 to 30 carbon atoms；
Described R1、R2、R3、R4、R5、R6、R7、R8Aryloxy group be phenoxy group；
Described R1、R2、R3、R4、R5、R6、R7、R8Arylthio be thiophenyl；
Described R1、R2、R3、R4、R5、R6、R7、R8The aryl that aryl is 6 to 30 carbon atoms or substituted aryl；
Described R1、R2、R3、R4、R5、R6、R7、R8The heteroaromatic that hetero-aromatic ring is 5 to 50 annular atomses or the heteroaromatic of replacement.
Further,
Described R1、R2、R3、R4、R5、R6、R7、R8The alkoxyl of 1 to 20 carbon atom be: methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, amoxy, isoamoxy, neopentyl oxygen, tertiary amoxy, hexyloxy, 2-methyl amoxy；
Described R1、R2、R3、R4、R5、R6、R7、R8The alkylthio group of 1 to 20 carbon atom be: methyl mercapto, ethylmercapto group, rosickyite base, positive butylthio, second butylthio, tertiary butylthio；
Described R1、R2、R3、R4、R5、R6、R7、R8The alkylamino radical of 1 to 20 carbon atom be: methylamino, ethylamino-, Propylamino, butylamine base, amylamine base, isoamyl amido, neopentyl amine base, tertiary amylamine base, hexylamine base, dimethylamino, diethylin, dipropyl amido, dibutyl amino, diamyl amido, diisoamyl amido, two neopentyl amine bases, two tertiary amylamine bases, dihexylamine base；
Described R1、R2、R3、R4、R5、R6、R7、R8The aryl amine of 6 to 30 carbon atoms be: o-, m-, p-aminomethyl phenyl amido, o-, m-, p-ethylphenyl amido, o-, m-, p-propyl group phenyl amido, o-, m-, p-isopropyl phenyl amido, o-, m-, p-methoxyphenyl amido, o-, m-, p-ethoxyl phenenyl amido, o-, m-, p-propoxyphenyl amido, o-, m-, p-difluorophenyl amido, o-, m-, p-chlorophenyl amido, o-, m-, p-bromo phenyl amido, o-, m-, p-iodine substituted phenyl amido, two (o-, m-, p-aminomethyl phenyl) amido, two (o-, m-, p-ethylphenyl) amido, two (o-, m-, p-propyl group phenyl) amido, two (o-, m-, p-isopropyl phenyl) amido, two (o-, m-, p-methoxyphenyl) amido, two (o-, m-, p-ethoxyl phenenyl) amido, two (o-, m-, p-propoxyphenyl) amido, two (o-, m-, p-difluorophenyl) amido, two (o-, m-, p-chlorophenyl) amido, two (o-, m-, p-bromo phenyl) amido, two (o-, m-, p-iodine substituted phenyl) amido；
Described R1、R2、R3、R4、R5、R6、R7、R8The aryl of 6 to 30 carbon atoms be: phenyl, diphenyl, triphenyl, naphthacenyl, pyrenyl, fluorenes, spiral shell fluorenes；
Described R1、R2、R3、R4、R5、R6、R7、R8The substituted aryl of 6 to 30 carbon atoms be: o-, m-, p-tolyl, xylyl, o-, m-, p-cumenyl, trimethylphenyl, 9,9 '-dimethyl fluorenyl, 9,9 '-spiral shell two fluorenyl；
Described R1、R2、R3、R4、R5、R6、R7、R8The heteroaromatic of 5 to 50 annular atomses be: 1-pyrrole radicals, 2-pyrrole radicals, 3-pyrrole radicals, pyridine radicals, 2-pyridine radicals, 3-pyridine radicals, 4-pyridine radicals, 1-indyl, 2-indyl, 3-indyl, 4-indyl, 5-indyl, 6-indyl, 7-indyl, 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl, 7-isoindolyl, 2-furyl, 3-furyl, 2-benzofuranyl, 3-benzofuranyl, 4-benzofuranyl, 5-benzofuranyl, 6-benzofuranyl, 7-benzofuranyl, dibenzofurans-2-base, 1-isobenzofuran-base, 3-isobenzofuran-base, 4-isobenzofuran-base, 5-isobenzofuran-base, 6-isobenzofuran-base, 7-isobenzofuran-base, 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl, 2-quinoxalinyl, 5-quinoxalinyl, 6-quinoxalinyl, 1-carbazyl, 2-carbazyl, 3-carbazyl, 4-carbazyl, 9-carbazyl, 1-coffee pyridine base, 2-coffee pyridine base, 3-coffee pyridine base, 4-coffee pyridine base, 6-coffee pyridine base, 7-coffee pyridine base, 8-coffee pyridine base, 9-coffee pyridine base, 10-coffee pyridine base, 1-acridinyl, 2-acridinyl, 3-acridinyl, 4-acridinyl, 9-acridinyl, 1,7-phenanthrene coughs up beautiful jade-2-base, 1,7-phenanthrene coughs up beautiful jade-3-base, 1,7-phenanthrene coughs up beautiful jade-4-base, 1,7-phenanthrene coughs up beautiful jade-5-base, 1,7-phenanthrene coughs up beautiful jade-6-base, 1,7-phenanthrene coughs up beautiful jade-8-base, 1,7-phenanthrene coughs up beautiful jade-9-base, 1,7-phenanthrene coughs up beautiful jade-10-base, 1,8-phenanthrene coughs up beautiful jade-2-base, 1,8-phenanthrene coughs up beautiful jade-3-base, 1,8-phenanthrene coughs up beautiful jade-4-base, 1,8-phenanthrene coughs up beautiful jade-5-base, 1,8-phenanthrene coughs up beautiful jade-6-base, 1,8-phenanthrene coughs up beautiful jade-7-base, 1,8-phenanthrene coughs up beautiful jade-9-base, 1,8-phenanthrene coughs up beautiful jade-10-base, 1,9-phenanthrene coughs up beautiful jade-2-base, 1,9-phenanthrene coughs up beautiful jade-3-base, 1,9-phenanthrene coughs up beautiful jade-4-base, 1,9-phenanthrene coughs up beautiful jade-5-base, 1,9-phenanthrene coughs up beautiful jade-6-base, 1,9-phenanthrene coughs up beautiful jade-7-base, 1,9-phenanthrene coughs up beautiful jade-8-base, 1,9-phenanthrene coughs up beautiful jade-10-base, 1,10-phenanthrene coughs up beautiful jade-2-base, 1,10-phenanthrene coughs up beautiful jade-3-base, 1,10-phenanthrene coughs up beautiful jade-4-base, 1,10-phenanthrene coughs up beautiful jade-5-base, 2,9-phenanthrolines-1-base, 2,9-phenanthrolines-3-base, 2,9-phenanthrolines-4-base, 2,9-phenanthrolines-5-base, 2,9-phenanthrolines-6-base, 2,9-phenanthrolines-7-base, 2,9-phenanthrolines-8-base, 2,9-phenanthrolines-10-base, 2,8-phenanthrene coughs up beautiful jade-1-base, 2,8-phenanthrene coughs up beautiful jade-3-base, 2,8-phenanthrene coughs up beautiful jade-4-base, 2,8-phenanthrene coughs up beautiful jade-5-base, 2,8-phenanthrene coughs up beautiful jade-6-base, 2,8-phenanthrene coughs up beautiful jade-7-base, 2,8-phenanthrene coughs up beautiful jade-9-base, 2,8-phenanthrene coughs up beautiful jade-10-base, 2,7-phenanthrene coughs up beautiful jade-1-base, 2,7-phenanthrene coughs up beautiful jade-3-base, 2,7-phenanthrene coughs up beautiful jade-4-base, 2,7-phenanthrene coughs up beautiful jade-5-base, 2,7-phenanthrene coughs up beautiful jade-6-base, 2,7-phenanthrene coughs up beautiful jade-8-base, 2,7-phenanthrene coughs up beautiful jade-9-base, 2,7-phenanthrene coughs up beautiful jade-10-base, 1-phenazinyl, 2-phenazinyl, 1-phenothiazinyl, 2-phenothiazinyl, 3-phenothiazinyl, 4-phenothiazinyl, lysivane base, 1-phenazinyl, 2-phenazinyl, 3-phenazinyl, 4-phenazinyl, 10-phenazinyl, 2-azoles base, 4-azoles base, 5-azoles base, 2-di azoly, 5-di azoly, 3-furazanyl, 2-thienyl, 3-thienyl, dibenzothiophenes-2-base, 2-picoline-1-base, 2-methylpyrrole-3-base, 2-methylpyrrole-4-base, 2-methylpyrrole-5-base, 3-methylpyrrole-1-base, 3-methylpyrrole-2-base, 3-methylpyrrole-4-base, 3-methylpyrrole-5-base, 2-tert-butyl group pyrroles's-4-base, 3-(2-phenyl propyl) pyrroles one-1-base, 2-methyl isophthalic acid-indyl, 4-methyl isophthalic acid-indyl, 2-methyl-3-indyl, 4-methyl-3-indyl, the 2-tert-butyl group-1-indyl, the 4-tert-butyl group-1-indyl, the 2-tert-butyl group-3-indyl, the 4-tert-butyl group-3-indyl.
The preparation method that the present invention provides oxidation thioxanthone analog derivative, comprises the following steps:
A, by thioxanthone compounds and concentration, the nitrate solution not higher than 10M is dissolved in acetonitrile with the ratio that mol ratio is 1:0.1 ~ 100, stirring, adds water precipitation, filters, filtrate recrystallization, obtains the oxidation thioxanthone analog derivative shown in formula (1)；
The consumption of acetonitrile is only small on the impact of this reaction system, it is not necessary to special restriction, considers from Applied economy angle, and consumption should be few as much as possible.During stirring, stir speed (S.S.), mixing time etc. can be regulated as required, it should be understood that the formation of final oxidation thioxanthone analog derivative is not affected by these factors.The addition of water is adjusted according to practical situation.Producing the crude product containing the oxidation thioxanthone compound shown in formula (1) after adding water, this reaction is the oxidation reaction that nitrate makes oxidant.Above-mentioned reaction at room temperature carries out.
Or
B, being dissolved in acetic acid by thioxanthone compounds and hydrogen peroxide solution with the ratio that mol ratio is 1:0.1 ~ 100, backflow, cooling precipitates out precipitation, filters, filtrate recrystallization, obtains oxidation thioxanthone analog derivative shown in formula (2)；
It is generally adopted the hydrogen peroxide solution of 30%.The consumption of acetic acid is only small on the impact of this reaction system, it is not necessary to special restriction, considers from Applied economy angle, and consumption should be few as much as possible.The precipitation that cooling precipitates out is the crude product containing the oxidation thioxanthone compound shown in formula (2), and this reaction is the oxidation reaction that nitrate makes oxidant.
Described formula (1) and formula (2) are as follows:
In formula, R1、R2、R3、R4、R5、R6、R7、R8It is respectively selected from the one in hydrogen atom, alkoxyl, alkylthio group, alkylamino radical, aryl amine, aryloxy group, arylthio, aryl, heteroaromatic group and R1、R2、R3、R4、R5、R6、R7、R8In have at least one for aromatic group.
Further, the structural formula of described thioxanthone compounds is:
In formula (5), R1、R2、R3、R4、R5、R6、R7、R8The face that is defined as above " oxidation thioxanthone analog derivative " in definition, be respectively selected from the one in hydrogen atom, alkoxyl, alkylthio group, alkylamino radical, aryl amine, aryloxy group, arylthio, aryl, heteroaromatic group and R1、R2、R3、R4、R5、R6、R7、R8In have at least one for aromatic group；
Described R1、R2、R3、R4、R5、R6、R7、R8The face that is defined as above further " oxidation thioxanthone analog derivative " in definition.
Described nitrate solution is the solution such as sodium nitrate, ammonium nitrate, ferric nitrate or nitrous acid ferrum.
The solvent that described recrystallization is selected is one or more mixed solvents in the organic solvents such as methanol, ethanol, dichloromethane, dimethyl sulfoxide, diformamide.
Described backflow is to reflux 2～12 hours under 25～100 DEG C of conditions.
The present invention provides the application of oxidation thioxanthone analog derivative, and this oxidation thioxanthone analog derivative can be used as the organic luminous layer of organic electroluminescence device.
Generally, this oxidation thioxanthone analog derivative is the main body luminescent material as organic luminous layer, can add other dyestuff as guest emitting material.
Organic electroluminescence device includes negative electrode, anode and organic thin film layer, and organic thin film layer is between negative electrode and anode；Described organic thin film layer includes organic luminous layer, and described oxidation thioxanthone analog derivative is the material of main part as organic luminous layer.This organic electroluminescence device can be used in organic integrated circuits, organic solar batteries, organic laser or organic sensor.
Preferably, this oxidation thioxanthone analog derivative can make electrophosphorescence device by Doping Phosphorus photoinitiator dye.Described phosphorescent coloring is selected from the complex of the metals such as Ir (iridium), Pt (platinum), Os (osmium), Ru (ruthenium).Preferably, described phosphorescent coloring is the complex of Ir.As, double; two (4,6-difluorophenyl pyridinato-N, C2) pyridinecarboxylic of blue light-emitting close iridium (being called for short FIrpic), and three (2-phenylpyridine) iridium of green light (is called for short Ir (ppy)3), three [1-phenyl isoquinolin quinoline-C2, the N] iridium (III) glowed (is called for short Ir (piq)3).
Preferably, the doping content of phosphorescent coloring is 5 ~ 15wt%.
Described organic thin film layer also includes hole injection layer, hole transmission layer and electron transfer layer etc..
Preferably, the structure of organic electroluminescence device is: substrate/anode/hole transmission layer/organic luminous layer/electron transfer layer/negative electrode.
Substrate is transparent, can be glass or flexible substrate.Described flexible substrate can be a kind of material in polyesters, poly-phthalimide compounds.
Anode layer can be inorganic material or organic conductive polymer.Described inorganic material is generally the metal-oxides such as tin indium oxide (ITO), zinc oxide, zinc tin oxide or the metal that the work function such as gold, silver, copper is higher；It most preferably is ITO.Described organic conductive polymer is preferably a kind of material in polythiophene/polyvinylbenzenesulfonic acid sodium (PEDOT:PSS), polyaniline (PANI).
Cathode layer is generally adopted the metal that the work functions such as lithium, magnesium, calcium, strontium, aluminum or indium are relatively low or a kind of and copper in them, golden or silver-colored alloy or the electrode layer that above-mentioned metal or alloy is alternatively formed with metal fluoride.It is preferably LiF layer successively and Mg:Ag alloy-layer.
Hole transmission layer is generally adopted tri-arylamine group material.It is preferably N, N '-two-(1-naphthyl)-N, N '-diphenyl-1,1-xenyl-4,4-diamidogen (NPB).
Electron transfer layer is generally adopted nitrogen heterocycles material.It is preferably 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene (TPBI).
Organic luminous layer is the oxidation thia anthracyclinone derivatives shown in formula (1) or (2).Preferably, the oxidation thia anthracyclinone derivatives that described organic luminous layer represents using formula (1) or (2) is as material of main part, with FIrpic, Ir (ppy)3Or Ir (piq)3As guest emitting material.
Using the oxidation thia anthracyclinone derivatives of the present invention as material of main part prepare the process of organic electroluminescence device for:
1. (methanol is preferentially selected by commercial detergent (preferential selection Decon90 abluent), deionized water and organic solution successively, ethanol, a kind of or two kinds and the above mixed solvent in acetone, acetonitrile, oxolane) divide several steps to clean the glass substrate with anode；
2. by the method for vacuum evaporation, the hole transmission layer of evaporation device；
3. the luminescent layer of device it is deposited with；
4. the electron transfer layer of device it is deposited with；
5. the method again through evaporation or sputtering prepares metallic cathode.
Such as, the preparation process of OLED is:
Glass plate supersound process in commercial detergent of transparent conductive layer will be coated with, rinse in deionized water, ultrasonic oil removing in the mixed solvent of acetone and ethanol, it is baked under clean environment and completely removes moisture content, irradiate 1 ~ 100 minute with ultraviolet rays cleaning machine, and with mental retardation cation bundle bombarded surface；
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 × 10-5～9 × 10-3Pa, is first deposited with CuPc1 ~ 15nm on above-mentioned anode tunic, continues evaporation NPB as hole transmission layer, and it is 50 ~ 75nm that evaporation rate controls to be deposited with thickness at 0.1 ~ 0.5nm/s.；
On hole transmission layer, continue one layer of luminescent layer of evaporation, luminescent layer adulterates with the oxidation thia anthracyclinone derivatives shown in phosphorescent light-emitting materials and formula (1) or (2) and forms, the evaporation rate of oxidation thia anthracyclinone derivatives and phosphorescent light-emitting materials ratio is for 100:1, it is x that phosphorescent light-emitting materials aoxidizes the doping content in thia anthracyclinone derivatives in the present invention, x is 5 ~ 15wt%, and it is deposited with total speed is 0.1nm/s, and evaporation total film thickness is 30nm；
Being further continued for the one layer of TPBI of the evaporation electron transfer layer as device, its evaporation rate is 0.lnm/s, and evaporation total film thickness is 35nm；
Finally, being deposited with LiF layer and the Mg:Ag alloy-layer cathode layer as device on above-mentioned electron transfer layer successively, wherein the thickness of LiF layer is the evaporation rate of 0.5nm, Mg:Ag alloy-layer is 2.0～3.0nm/s, and thickness is 100nm.
It is an advantage of the current invention that:
1, the oxidation thioxanthone analog derivative of the present invention can be used as the emitting layer material in organic electroluminescence device.Its oxidation thioxanthone molecule, owing to introducing multiple electron deficiency group, has certain electron transport ability.Thioxanthone compound is a kind of conventional photosensitizer, and it has high triplet energies and little singlet state triplet energy gap；Thioxanthone after oxidation continues to maintain high triplet energy level, and by the modification of different substituents, can to oxidation after thioxanthone molecule highest occupied molecular orbital (HOMO) energy level and minimum do not occupy track (LUMO) energy level make with change, reduce the energy barrier with adjacent layer material, the injection of carrier of being more convenient for and transmission；Additionally, owing to the present invention aoxidizes, thioxanthone analog derivative introduces big substituent group, improve its film property and chemical stability, be conducive to the device that preparation stability is higher, utilize organic electroluminescence device prepared by derivant of the present invention to have high device efficiency and low cut-in voltage.
2, the present invention adopts the method for simplicity to synthesize a series of oxidation thioxanthone analog derivative with high electron transfer rate.
3, the organic electroluminescence device that the oxidation thioxanthone analog derivative of the present invention is prepared as the material of main part various phosphorescent colorings of doping is utilized to have high brightness, high efficiency superior function.Experiment finds by selecting suitable phosphorescent coloring, it is possible to realize the high efficiency light-emittings such as red, green, blue.
Accompanying drawing explanation
Fig. 1 is the oxidation abosrption spectrogram (a) of thioxanthone analog derivative, fluorescence spectrum figure (b), 77K phosphorescence spectrum figure (c) of the embodiment of the present invention 4.
Fig. 2 is the oxidation abosrption spectrogram (a) of thioxanthone analog derivative, fluorescence spectrum figure (b), 77K phosphorescence spectrum figure (c) of the embodiment of the present invention 14.
Fig. 3 is the structural representation that the present invention aoxidizes the Organic Light Emitting Devices that thioxanthone analog derivative prepares as material of main part.
Fig. 4 be based on the embodiment of the present invention 4 oxidation thioxanthone analog derivative containing 7wt%Ir (ppy)3EL (a) at different brightnesses, L-V curve chart (b).
Detailed description of the invention
In order to be more fully understood that the content of patent of the present invention, further illustrate technical scheme following by specific embodiment.
Herein, thioxanthone compounds all can be prepared by prior art.Such as, the thioxanthone compounds of embodiment 1 ~ 20 is referred to WO2012/063751A1；J.Chem.Soc.Perkintrans.11991;J.Org.Chem., Vol.67, No.22,2002;WO2012/008558A1；WO2006/114966A1 prepares, and the thioxanthone compounds of embodiment 21 ~ 28 is referred to ContributionFromTheChemicalLaboratoryOfIowaStateCollege, vol.24,1914 ~ 1916；WO2012/060234A1.
Fig. 3 is the structural representation that the present invention aoxidizes the Organic Light Emitting Devices that thioxanthone analog derivative prepares as material of main part.
Embodiment 1
Synthesis oxidation thioxanthone analog derivative Comp-1
By the nitrate solution of 2,7-diphenyl thioxanthones and 1M, being dissolved in acetonitrile with the ratio that mol ratio is 1:4, be stirred at room temperature 4 hours, add a large amount of water precipitation, must aoxidize thioxanthone analog derivative Comp-1 with ethyl alcohol recrystallization after filtration, productivity is about 70%；M/z:380.09 (100.0%), 381.09 (28.0%), 382.08 (4.6%), 381.08(4.2%), 382.09(1.7%).M/z is the mass-to-charge ratio of target molecule in Low Resolution Mass Spectra.
Embodiment 2
Synthesis oxidation thioxanthone analog derivative Comp-2:
With embodiment 1, replacing 2,7-diphenyl thioxanthones with 2,7-bis-(2 '-xenyl) thioxanthone, must aoxidize thioxanthone analog derivative Comp-2, productivity is about 70%；M/z:532.15 (100.0%), 533.15 (40.8%), 534.16 (8.0%), 533.14 (4.8%).
Embodiment 3
Synthesis oxidation thioxanthone analog derivative Comp-3:
With embodiment 1, replacing 2,7-diphenyl thioxanthones with 2,7-bis-(3 ', 5 '-terphenyl) thioxanthone, must aoxidize thioxanthone analog derivative Comp-3, productivity is about 70%.M/z:684.21 (100.0%), 685.22 (53.3%), 686.23 (14.6%), 685.21(3.2%), 686.22(1.9%).
Embodiment 4
Synthesis oxidation thioxanthone analog derivative Comp-4:
With embodiment 1, replacing 2,7-diphenyl thioxanthones with 2,7-bis-(9 ', 9 '-dimethyl fluorenyl) thioxanthone, must aoxidize thioxanthone analog derivative Comp-4, productivity is about 70%；M/z:612.21 (100.0%), 613.22 (47.1%), 614.22 (11.6%), 613.21(5.2%), 614.23(2.9%).
Fig. 1 is the optical physics data (abosrption spectrogram (a), fluorescence spectrum figure (b), 77K phosphorescence spectrum figure (c)) of the Comp-4 prepared by the present invention, in absorption spectra caused by the n-π * transition that Weak Absorption band is carbonyl at 325nm place；Fluorescence and phosphorescence spectrogram show that this molecule unstressed configuration and phosphorescence intensity are very strong.According to optical physics data it is estimated that the energy gap of Comp-4 and triplet energy state, in order to assess its performance and application.
Fig. 4 be based on the embodiment of the present invention 4 oxidation thioxanthone analog derivative containing 7wt%Ir (ppy)3EL (a) at different brightnesses, L-V curve chart (b).Green phosphorescent device result prepared by material of main part that to be Comp-4 be, device cut-in voltage is 3.9V, and high-high brightness is 4132cd/m2.Finding out the increase along with brightness from Fig. 4 a, the luminescence of Comp-4 self strengthens gradually.
Embodiment 5
Synthesis oxidation thioxanthone analog derivative Comp-5:
With embodiment 1, replacing 2,7-diphenyl thioxanthones with 2,7-bis-(9 ', 9 '-spiral shell two fluorenes) thioxanthone, must aoxidize thioxanthone analog derivative Comp-5, productivity is about 70%；M/z:872.27 (100.0%), 873.28 (69.8%), 874.28 (24.9%), 873.27(5.2%).
Embodiment 6
Synthesis oxidation thioxanthone analog derivative Comp-6:
With embodiment 1, replacing 2,7-diphenyl thioxanthones with 2,7-bis-(9 ', 10 '-phenyl phenanthryl) thioxanthone, must aoxidize thioxanthone analog derivative Comp-6, productivity is about 70%；M/z:712.24 (100.0%), 713.25 (55.8%), 714.25 (16.0%), 713.27(2.3%).
Embodiment 7
Synthesis oxidation thioxanthone analog derivative Comp-7:
With embodiment 1, replacing 2,7-diphenyl thioxanthones with 3,6-bis-(2 ', 4 ', 6 '-trimethylphenyl) thioxanthone, must aoxidize thioxanthone analog derivative Comp-7, productivity is about 70%；M/z:464.18 (100.0%), 465.17 (34.3%), 466.17 (6.0%), 466.19(5.3%), 465.18(2.5%).
Embodiment 8
Synthesis oxidation thioxanthone analog derivative Comp-8:
With embodiment 1, replacing 2,7-diphenyl thioxanthones with 2,7-bis-(3 '-quinolyl) thioxanthone, must aoxidize thioxanthone analog derivative Comp-8, productivity is about 70%；M/z:482.11 (100.0%), 483.11 (35.1%), 484.12 (5.5%), 483.12(1.3%).
Embodiment 9
Synthesis oxidation thioxanthone analog derivative Comp-9:
With embodiment 1, replacing 2,7-diphenyl thioxanthones with 2,7-bis-(2 '-benzothiazolyl) thioxanthone, must aoxidize thioxanthone analog derivative Comp-9, productivity is about 70%；M/z:592.06 (100.0%), 593.07 (40.2%), 594.06 (13.5%), 593.06(3.5%) 594.06 (1.3%).
Embodiment 10
Synthesis oxidation thioxanthone analog derivative Comp-10:
With embodiment 1, replacing 2,7-diphenyl thioxanthones with 2,7-bis-(2 '-benzofuran) thioxanthone, must aoxidize thioxanthone analog derivative Comp-10, productivity is about 70%；M/z:560.11 (100.0%), 561.11 (41.1%), 562.12 (8.5%), 563.12(1.3%).
Embodiment 11
Synthesis oxidation thioxanthone analog derivative Comp-11:
By the hydrogen peroxide of 2,7-diphenyl thioxanthones and 30%, being dissolved in acetic acid with the ratio that mol ratio is 1:1, in 100 DEG C of backflows, cooling precipitates out precipitation, filters and with ethyl alcohol recrystallization, obtains oxidation thioxanthone analog derivative Comp-11, and productivity is about 90%；M/z:396.08 (100.0%), 397.09 (27.3%), 398.08 (4.6%), 397.08(1.3%).
Embodiment 12
Synthesis oxidation thioxanthone analog derivative Comp-12:
With embodiment 11, replacing 2,7-diphenyl thioxanthones with 3,6-bis-(2 '-xenyl) thioxanthone, obtain oxidation thioxanthone analog derivative Comp-12, productivity is about 90%；M/z:548.14 (100.0%), 549.14 (40.4%), 550.15 (8.9%), 549.13 (4.4%), 550.14 (0.9%).
Embodiment 13
Synthesis oxidation thioxanthone analog derivative Comp-13:
With embodiment 11, replacing 2,7-diphenyl thioxanthones with 2,7-bis-(3 ', 5 '-terphenyl) thioxanthone, obtain oxidation thioxanthone analog derivative Comp-13, productivity is about 90%；M/z:700.21 (100.0%), 701.21 (54.3%), 702.21 (14.9%), 701.23 (5.0%).
Embodiment 14
Synthesis oxidation thioxanthone analog derivative Comp-14:
With embodiment 11, replacing 2,7-diphenyl thioxanthones with 2,7-bis-(9 ', 9 '-dimethyl fluorenyl) thioxanthone, obtain oxidation thioxanthone analog derivative Comp-14, productivity is about 90%；M/z:628.21 (100.0%), 629.21 (47.8%), 630.21 (11.6%), 629.20 (4.7%), 630.22 (1.1%).
Fig. 2 is the optical physics data (abosrption spectrogram (a), fluorescence spectrum figure (b), 77K phosphorescence spectrum figure (c)) of the Comp-14 prepared by the present invention, in absorption spectra caused by the n-π * transition that Weak Absorption band is carbonyl at 330nm place；Fluorescence and phosphorescence spectrogram show that this molecule unstressed configuration and phosphorescence intensity are very strong.According to optical physics data it is estimated that the energy gap of Comp-14 and triplet energy state, in order to assess its performance and application.
Embodiment 15
Synthesis oxidation thioxanthone analog derivative Comp-15:
With embodiment 11, replacing 2,7-diphenyl thioxanthones with 2,7-bis-(9 ', 9 '-spiral shell two fluorenes) thioxanthone, obtain oxidation thioxanthone analog derivative Comp-15, productivity is about 90%；M/z:888.27 (100.0%), 889.27 (70.1%), 890.28 (24.1%), 889.28 (2.7%).
Embodiment 16
Synthesis oxidation thioxanthone analog derivative Comp-16:
With embodiment 11, replacing 2,7-diphenyl thioxanthones with 2,7-bis-(9 ', 10 '-phenyl phenanthryl) thioxanthone, obtain oxidation thioxanthone analog derivative Comp-16, productivity is about 90%；M/z:728.24 (100.0%), 729.24 (70.1%), 730.25 (24.1%), 729.23 (2.7%), 730.25 (1.2%).
Embodiment 17
Synthesis oxidation thioxanthone analog derivative Comp-17:
With embodiment 11, replacing 2,7-diphenyl thioxanthones with 3,6-bis-(2 ', 4 ', 6 '-trimethylphenyl) thioxanthone, obtain oxidation thioxanthone analog derivative Comp-17, productivity is about 90%；M/z:480.18 (100.0%), 481.18 (34.8%), 482.19 (6.4%), 482.18 (1.5%).
Embodiment 18
Synthesis oxidation thioxanthone analog derivative Comp-18:
With embodiment 11, replacing 2,7-diphenyl thioxanthones with 2,7-bis-(3 '-quinolyl) thioxanthone, obtain oxidation thioxanthone analog derivative Comp-18, productivity is about 90%；M/z:498.10 (100.0%), 499.10 (33.9%), 500.11 (6.4%), 499.11 (3.5%), 500.12 (1.3%).
Embodiment 19
Synthesis oxidation thioxanthone analog derivative Comp-19:
With embodiment 11, replacing 2,7-diphenyl thioxanthones with 2,7-bis-(2 '-benzothiazolyl) thioxanthone, obtain oxidation thioxanthone analog derivative Comp-19, productivity is about 90%；M/z:608.06 (100.0%), 609.06 (42.8%), 610.05 (13.7%), 609.05 (4.7%), 610.04.12 (1.7%).
Embodiment 20
Synthesis oxidation thioxanthone analog derivative Comp-20:
With embodiment 11, replacing 2,7-diphenyl thioxanthones with 2,7-bis-(2 '-benzofuran) thioxanthone, obtain oxidation thioxanthone analog derivative Comp-20, productivity is about 90%；M/z:576.10 (100.0%), 577.11 (40.4%), 578.11 (9.3%), 577.10(2.0%).
Embodiment 21
Synthesis oxidation thioxanthone analog derivative Comp-21
Synthesized reference document (McClelland, the Peters of 2-hexylamine base-7-thiophenyl-thioxanthone;J.Am.Chem.Soc.1947, p.1229-123；J.Am.Chem.Soc.1997, vol.93, p.1517-1522).
Nitrate solution by 2-hexylamine base-7-thiophenyl-thioxanthone and 1M, it is dissolved in acetonitrile with the ratio that mol ratio is 1:4, is stirred at room temperature 4 hours, adds a large amount of water precipitation, must aoxidizing thioxanthone analog derivative Comp-21 with ethyl alcohol recrystallization after filtration, productivity is about 70%.M/z:435.13 (100.0%), 436.14 (27.2%), 437.13 (9.4%), 437.14(3.9%).
Embodiment 22
Synthesis oxidation thioxanthone analog derivative Comp-22
Synthesized reference document (McClelland, the Peters of 2-hexylamine base-7-phenoxy group-thioxanthone;J.Am.Chem.Soc.1947, p.1229-123；J.Med.Chem, 1982, vol.25, p.220-227).
Nitrate solution by 2-hexylamine base-7-phenoxy group-thioxanthone and 1M, it is dissolved in acetonitrile with the ratio that mol ratio is 1:4, is stirred at room temperature 4 hours, adds a large amount of water precipitation, must aoxidizing thioxanthone analog derivative Comp-22 with ethyl alcohol recrystallization after filtration, productivity is about 70%.M/z:419.16 (100.0%), 420.15 (27.4%), 421.16 (4.4%), 421.15(1.4%).
Embodiment 23
Synthesis oxidation thioxanthone analog derivative Comp-23
The synthesized reference document of 2-hexyloxy-7-m-ethyl aniline base-thioxanthone (J.Am.Chem.Soc.1997, vol.93, p.1517-1522；WO2006/114966A1).
Nitrate solution by 2-hexyloxy-7-m-ethyl aniline base-thioxanthone and 1M, it is dissolved in acetonitrile with the ratio that mol ratio is 1:4, is stirred at room temperature 4 hours, adds a large amount of water precipitation, must aoxidizing thioxanthone analog derivative Comp-23 with ethyl alcohol recrystallization after filtration, productivity is about 70%.M/z:447.19 (100.0%), 448.19 (30.5%), 449.19 (5.1%), 449.18(2.3%).
Embodiment 24
Synthesis oxidation thioxanthone analog derivative Comp-24
Synthesized reference document (the Patent:GB932494,1958 of 2-own sulfydryl-7-cumic aldehyde amido-thioxanthone;Chem.Abstr.1964, vol.61,9477；WO2006/114966A1).
Nitrate solution by 2-hexyloxy-7-cumic aldehyde amido-thioxanthone and 1M, it is dissolved in acetonitrile with the ratio that mol ratio is 1:4, is stirred at room temperature 4 hours, adds a large amount of water precipitation, must aoxidizing thioxanthone analog derivative Comp-24 with ethyl alcohol recrystallization after filtration, productivity is about 70%.M/z:477.18 (100.0%), 478.19 (32.3%), 479.19 (10.3%), 449.18(1.5%).
Embodiment 25
Synthesis oxidation thioxanthone analog derivative Comp-25
Synthesized reference document (McClelland, the Peters of 2-hexylamine base-7-thiophenyl-thioxanthone;J.Am.Chem.Soc.1947, p.1229-123；J.Am.Chem.Soc.1997, vol.93, p.1517-1522).
By the hydrogen peroxide of 2-hexylamine base-7-thiophenyl-thioxanthone and 30%, it is dissolved in acetic acid with the ratio that mol ratio is 1: 1, in 100 DEG C of backflows, cooling precipitates out precipitation, filtering and use ethyl alcohol recrystallization, must aoxidize thioxanthone analog derivative Comp-25, productivity is about 90%.M/z:451.13 (100.0%), 452.14 (29.1%), 453.14 (9.0%), 453.13(2.3%).
Embodiment 26
Synthesis oxidation thioxanthone analog derivative Comp-26
Synthesized reference document (McClelland, the Peters of 2-hexylamine base-7-phenoxy group-thioxanthone;J.Am.Chem.Soc.1947, p.1229-123；J.Med.Chem, 1982, vol.25, p.220-227).
By the hydrogen peroxide of 2-hexylamine base-7-phenoxy group-thioxanthone and 30%, it is dissolved in acetic acid with the ratio that mol ratio is 1: 1, in 100 DEG C of backflows, cooling precipitates out precipitation, filtering and use ethyl alcohol recrystallization, must aoxidize thioxanthone analog derivative Comp-26, productivity is about 90%.M/z:435.15 (100.0%), 436.15 (28.4%), 437.16 (5.8%), 437.15(1.7%).
Embodiment 27
Synthesis oxidation thioxanthone analog derivative Comp-27
The synthesized reference document of 2-hexyloxy-7-m-ethyl aniline base-thioxanthone (J.Am.Chem.Soc.1997, vol.93, p.1517-1522；WO2006/114966A1).
By the hydrogen peroxide of 2-hexyloxy-7-m-ethyl aniline base-thioxanthone and 30%, it is dissolved in acetic acid with the ratio that mol ratio is 1:1, in 100 DEG C of backflows, cooling precipitates out precipitation, filtering and use ethyl alcohol recrystallization, must aoxidize thioxanthone analog derivative Comp-27, productivity is about 90%.M/z:463.18 (100.0%), 464.19 (29.7%), 465.19 (5.0%), 465.18(0.8%).
Embodiment 28
Synthesis oxidation thioxanthone analog derivative Comp-28
Synthesized reference document (the Patent:GB932494,1958 of 2-own sulfydryl-7-cumic aldehyde amido-thioxanthone;Chem.Abstr.1964, vol.61,9477；WO2006/114966A1).
By the hydrogen peroxide of 2-own sulfydryl-7-cumic aldehyde amido-thioxanthone and 30%, it is dissolved in acetic acid with the ratio that mol ratio is 1: 1, in 100 DEG C of backflows, cooling precipitates out precipitation, filtering and use ethyl alcohol recrystallization, must aoxidize thioxanthone analog derivative Comp-28, productivity is about 90%.M/z:493.17 (100.0%), 494.18 (30.8%), 495.18 (9.3%), 495.19(1.0%).
Embodiment 29
The derivant Comp-1 obtained by embodiment 1 prepares organic electroluminescence device:
Glass plate supersound process in commercial detergent of transparent conductive layer will be coated with, rinse in deionized water, at acetone: ultrasonic oil removing in alcohol mixed solvent, be baked under clean environment and completely remove moisture content, irradiate 10 minutes with ultraviolet rays cleaning machine, and with mental retardation cation bundle bombarded surface；
The above-mentioned glass substrate with anode is placed in vacuum chamber, is evacuated to 1 × 10-5～9 × 10-3Pa, is first deposited with CuPc15nm on above-mentioned anode tunic, continues evaporation NPB as hole transmission layer, and evaporation rate is 0.1nm/s. evaporation thickness is 75nm；
On hole transmission layer, continue the Ir (ppy) of one layer of Comp-1 doping of evaporation3As the organic luminous layer of device, Comp-1 and Ir (ppy)3Evaporation rate than for 1:100, Ir (ppy)3Doping content in Comp-1 is 7wt%, and it is deposited with total speed is 0.1nm/s, and evaporation total film thickness is 30nm；
Being further continued for the one layer of TPBI of the evaporation electron transfer layer as device, its evaporation rate is 0.lnm/s, and evaporation total film thickness is 35nm；
Finally, being deposited with LiF layer and the Mg:Ag alloy-layer cathode layer as device on above-mentioned electron transfer layer successively, wherein the thickness of LiF layer is the evaporation rate of 0.5nm, Mg:Ag alloy-layer is 2.0～3.0nm/s, and thickness is 100nm.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/7wt%Ir (ppy)3Comp-1(30nm)/TPBI(35nm)/LiF(0.5nm)/Mg:Ag(10:1100nm)
Device performance index is as follows: chromaticity coordinate: (X=0.27, Y=0.63)；
Play bright voltage: 3.5V；
High-high brightness: 11786cd/m2(8.2V)；
Luminous efficiency: 14.63cd/A.
Embodiment 30
The derivant Comp-3 that embodiment 3 obtains is selected to prepare organic electroluminescence device:
Replace, beyond Comp-1, according to the step identical with embodiment 29, preparing organic EL device and testing the performance of device except with Comp-3.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/7wt%Ir (ppy)3:Comp-3(30nm)/TPBI(35nm)/LiF(0.5nm)/Mg:Ag(10:1100nm)
Device performance index is as follows:
Chromaticity coordinate: (X=0.28, Y=0.63)；
Play bright voltage: 3.2V；
High-high brightness: 11845cd/m2(9.5V)；
Luminous efficiency: 14.91cd/A.
Embodiment 31
The derivant Comp-5 that embodiment 5 obtains is selected to prepare organic electroluminescence device:
Comp-1, FIrpic is replaced to replace Ir (ppy) except with Comp-53In addition, according to the step identical with embodiment 29, prepare organic EL device and test the performance of device.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/8wt%FIrpic:Comp-5 (30nm)/TPBI (35nm)/LiF (0.5nm)/Mg:Ag (10:1100nm)
Device performance index is as follows:
Chromaticity coordinate: (X=0.15, Y=0.35)；
Play bright voltage: 3.7V；
High-high brightness: 9995cd/m2(9.1V)；
Luminous efficiency: 21.47cd/A.
Embodiment 32
The derivant Comp-6 that embodiment 6 obtains is selected to prepare organic electroluminescence device:
Comp-1, Ir (piq) is replaced except with Comp-63Replace Ir (ppy)3In addition, according to the step identical with embodiment 29, prepare organic EL device and test the performance of device.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/5wt%Ir (piq)3:Comp-6(30nm)/TPBI(35nm)/LiF(0.5nm)/Mg:Ag(10:1100nm)
Device performance index is as follows:
Chromaticity coordinate: (X=0.66, Y=0.33)；
Play bright voltage: 4.2V；
High-high brightness: 8720cd/m2(10.2V)；
Luminous efficiency: 28.39cd/A.
Embodiment 33
The derivant Comp-7 that embodiment 7 obtains is selected to prepare organic electroluminescence device:
Comp-1, FIrpic is replaced to replace Ir (ppy) except with Comp-73In addition, according to the step identical with embodiment 29, prepare organic EL device and test the performance of device.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/8wt%FIrpic:Comp-7 (30nm)/TPBI (35nm)/LiF (0.5nm)/Mg:Ag (10:1100nm)
Device performance index is as follows:
Chromaticity coordinate: (X=0.14, Y=0.33)；
Play bright voltage: 3.5V；
High-high brightness: 8776cd/m2(8.8V)；
Luminous efficiency: 19.82cd/A.
Embodiment 34
The derivant Comp-8 that embodiment 8 obtains is selected to prepare organic electroluminescence device:
Comp-1, FIrpic is replaced to replace Ir (ppy) except with Comp-83In addition, according to the step identical with embodiment 29, prepare organic EL device and test the performance of device.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/8wt%FIrpic:Comp-8 (30nm)/TPBI (35nm)/LiF (0.5nm)/Mg:Ag (10:1100nm)
Device performance index is as follows:
Chromaticity coordinate: (X=0.15, Y=0.34)；
Play bright voltage: 3.7V；
High-high brightness: 8835cd/m2(9.4V)；
Luminous efficiency: 15.43cd/A.
Embodiment 35
The derivant Comp-10 that embodiment 10 obtains is selected to prepare organic electroluminescence device:
Replace, beyond Comp-1, according to the step identical with embodiment 29, preparing organic EL device and testing the performance of device except with Comp-10.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/7wt%Ir (ppy)3:Comp-10(30nm)/TPBI(35nm)/LiF(0.5nm)/Mg:Ag(10:1100nm)
Device performance index is as follows:
Chromaticity coordinate: (X=0.28, Y=0.64)；
Play bright voltage: 3.1V；
High-high brightness: 12642cd/m2(9.6V)；
Luminous efficiency: 25.69cd/A.
Embodiment 36
The derivant Comp-12 that embodiment 12 obtains is selected to prepare organic electroluminescence device:
Replace, beyond Comp-1, according to the step identical with embodiment 29, preparing organic EL device and testing the performance of device except with Comp-12.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/7wt%Ir (ppy)3:Comp-12(30nm)/TPBI(35nm)/LiF(0.5nm)/Mg:Ag(10:1100nm)
Device performance index is as follows:
Chromaticity coordinate: (X=0.27, Y=0.65)；
Play bright voltage: 4.4V；
High-high brightness: 10578cd/m2(8.8V)；
Luminous efficiency: 16.83cd/A.
Embodiment 37
The derivant Comp-14 that embodiment 14 obtains is selected to prepare organic electroluminescence device:
Comp-1, FIrpic is replaced to replace Ir (ppy) except with Comp-143In addition, according to the step identical with embodiment 29, prepare organic EL device and test the performance of device.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/8wt%FIrpic:Comp-14 (30nm)/TPBI (35nm)/LiF (0.5nm)/Mg:Ag (10:1100nm)
Device performance index is as follows:
Chromaticity coordinate: (X=0.15, Y=0.37)；
Play bright voltage: 3.7V；
High-high brightness: 11465cd/m2(8.7V)；
Luminous efficiency: 26.83cd/A.
Embodiment 38
The derivant Comp-16 that embodiment 16 obtains is selected to prepare organic electroluminescence device:
Comp-1, Ir (piq) is replaced except with Comp-163Replace Ir (ppy)3In addition, according to the step identical with embodiment 29, prepare organic EL device and test the performance of device.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/5wt%Ir (piq)3:Comp-16(30nm)/TPBI(35nm)/LiF(0.5nm)/Mg:Ag(10:1100nm)
Device performance index is as follows:
Chromaticity coordinate: (X=0.66, Y=0.32)；
Play bright voltage: 4.5V；
High-high brightness: 8733cd/m2(9.3V)；
Luminous efficiency: 27.23cd/A.
Embodiment 39
The derivant Comp-18 that embodiment 18 obtains is selected to prepare organic electroluminescence device:
Comp-1, FIrpic is replaced to replace Ir (ppy) except with Comp-183In addition, according to the step identical with embodiment 29, prepare organic EL device and test the performance of device.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/8wt%FIrpic:Comp-18 (30nm)/TPBI (35nm)/LiF (0.5nm)/Mg:Ag (10:1100nm)
Device performance index is as follows:
Chromaticity coordinate: (X=0.15, Y=0.33)；
Play bright voltage: 3.5V；
High-high brightness: 8671cd/m2(8.7V)；
Luminous efficiency: 16.37cd/A.
Embodiment 40
The derivant Comp-19 that embodiment 19 obtains is selected to prepare organic electroluminescence device:
Replace, beyond Comp-1, according to the step identical with embodiment 29, preparing organic EL device and testing the performance of device except with Comp-19.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/7wt%Ir (ppy)3:Comp-19(30nm)/TPBI(35nm)/LiF(0.5nm)/Mg:Ag(10:1100nm)
Device performance index is as follows:
Chromaticity coordinate: (X=0.27, Y=0.64)；
Play bright voltage: 3.4V；
High-high brightness: 12575cd/m2(8.3V)；
Luminous efficiency: 23.88cd/A.
Embodiment 41
The derivant Comp-21 that embodiment 21 obtains is selected to prepare organic electroluminescence device:
Comp-1, FIrpic is replaced to replace Ir (ppy) except with Comp-213In addition, according to the step identical with embodiment 29, prepare organic EL device and test the performance of device.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/8wt%FIrpic:Comp-21 (30nm)/TPBI (35nm)/LiF (0.5nm)/Mg:Ag (10:1100nm)
Device performance index is as follows:
Chromaticity coordinate: (X=0.13, Y=0.30)；
Play bright voltage: 3.9V；
High-high brightness: 8327cd/m2(9.3V)；
Luminous efficiency: 17.73cd/A.
Embodiment 42
The derivant Comp-22 that embodiment 22 obtains is selected to prepare organic electroluminescence device:
Comp-1, FIrpic is replaced to replace Ir (ppy) except with Comp-223In addition, according to the step identical with embodiment 29, prepare organic EL device and test the performance of device.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/8wt%FIrpic:Comp-22 (30nm)/TPBI (35nm)/LiF (0.5nm)/Mg:Ag (10:1100nm)
Device performance index is as follows:
Chromaticity coordinate: (X=0.15, Y=0.34)；
Play bright voltage: 4.1V；
High-high brightness: 7548cd/m2(9.9V)；
Luminous efficiency: 15.53cd/A.
Embodiment 43
The derivant Comp-24 that embodiment 24 obtains is selected to prepare organic electroluminescence device:
Comp-1, FIrpic is replaced to replace Ir (ppy) except with Comp-243In addition, according to the step identical with embodiment 29, prepare organic EL device and test the performance of device.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/8wt%FIrpic:Comp-24 (30nm)/TPBI (35nm)/LiF (0.5nm)/Mg:Ag (10:1100nm)
Device performance index is as follows:
Chromaticity coordinate: (X=0.14, Y=0.32)；
Play bright voltage: 3.0V；
High-high brightness: 8376cd/m2(8.1V)；
Luminous efficiency: 18.01cd/A.
Embodiment 44
The derivant Comp-25 that embodiment 25 obtains is selected to prepare organic electroluminescence device:
Comp-1, FIrpic is replaced to replace Ir (ppy) except with Comp-253In addition, according to the step identical with embodiment 29, prepare organic EL device and test the performance of device.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/8wt%FIrpic:Comp-25 (30nm)/TPBI (35nm)/LiF (0.5nm)/Mg:Ag (10:1100nm)
Device performance index is as follows:
Chromaticity coordinate: (X=0.14, Y=0.29)；
Play bright voltage: 3.8V；
High-high brightness: 7970cd/m2(10.3V)；
Luminous efficiency: 17.84cd/A.
Embodiment 45
The derivant Comp-28 that embodiment 28 obtains is selected to prepare organic electroluminescence device:
Comp-1, FIrpic is replaced to replace Ir (ppy) except with Comp-283In addition, according to the step identical with embodiment 29, prepare organic EL device and test the performance of device.
Device architecture: ITO/CuPc (15nm)/NPB (75nm)/8wt%FIrpic:Comp-28 (30nm)/TPBI (35nm)/LiF (0.5nm)/Mg:Ag (10:1100nm)
Device performance index is as follows:
Chromaticity coordinate: (X=0.13, Y=0.31)；
Play bright voltage: 3.8V；
High-high brightness: 8451cd/m2(9.5V)；
Luminous efficiency: 18.26cd/A.
Embodiment 46
The preparation method of oxidation thioxanthone analog derivative, comprises the following steps:
A, the nitrate solution of thioxanthone compounds and concentration 0.001M is dissolved in acetonitrile with the ratio that mol ratio is 1:0.1, stirring, add water precipitation, filter, filtrate recrystallization, obtain the oxidation thioxanthone analog derivative shown in formula (1)；
B, being dissolved in acetic acid by thioxanthone compounds and hydrogen peroxide solution with the ratio that mol ratio is 1:0.1, backflow, cooling precipitates out precipitation, filters, filtrate recrystallization, obtains oxidation thioxanthone analog derivative shown in formula (2)；
The structural formula of described thioxanthone compounds is:
In formula, R1、R2、R3、R4、R5、R6、R7、R8Respectively hydrogen atom, neopentyl oxygen, positive butylthio, diisoamyl amido, o-, m-, p-isopropyl phenyl amido, phenoxy group, thiophenyl, 9,9 '-dimethyl fluorenyl；Described nitrate solution is sodium nitrate solution；The solvent that described recrystallization is selected is methanol；Described backflow is to reflux under 25 DEG C of conditions.
Embodiment 47
With embodiment 46, R1、R2、R3、R4、R5、R6、R7、R8Respectively o-, m-, p-aminomethyl phenyl amido, two (o-, m-, p-isopropyl phenyl) amido, two (o-, m-, p-iodine substituted phenyl) amido, pyrenyl, 9,9 '-spiral shell two fluorenyl, 1-pyrrole radicals, 5-isoindolyl, 1-isobenzofuran-base；
Described nitrate solution is ammonium nitrate solution；The solvent that described recrystallization is selected is the mixed solvent of dichloromethane and dimethyl sulfoxide；Described backflow is to reflux under 50 DEG C of conditions.
Embodiment 48
With embodiment 46, it is distinctive in that: R1、R2、R3、R4、R5、R6、R7、R8Respectively 1,8-phenanthrene coughs up beautiful jade-2-base, 1,9-phenanthrene coughs up beautiful jade-7-base, 1,10-phenanthrene coughs up beautiful jade-5-base, 2,8-phenanthrene coughs up beautiful jade-3-base, lysivane base, 2-methylpyrrole-5-base, 2-tert-butyl group pyrroles's-4-base, 5-di azoly；
Described nitrate solution is iron nitrate solution；The solvent that described recrystallization is selected is diformamide.
Obviously, the above embodiment of the present invention is only for clearly demonstrating example of the present invention, and is not the restriction to embodiments of the present invention.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here cannot all of embodiment be given exhaustive.Every belong to apparent change that technical scheme extended out or the variation row still in protection scope of the present invention.

Claims (8)

1. oxidation thioxanthone analog derivative, it is characterised in that its structural formula is as follows:
In formula (1) and formula (2), R1、R2、R3、R4、R5、R6、R7、R8Be respectively selected from hydrogen atom, the alkoxyl of 1 to 20 carbon atom, the alkylthio group of 1 to 20 carbon atom, the alkylamino radical of 1 to 20 carbon atom, the aryl amine of 6 to 30 carbon atoms, phenoxy group, thiophenyl, the aryl of 6 to 30 carbon atoms, the substituted aryl of 6 to 30 carbon atoms, the heteroaromatic group of 5 to 50 annular atomses, 5 to 50 annular atomses replacement heteroaromatic group in one, and R1、R2、R3、R4、R5、R6、R7、R8In have at least one for aromatic group.
2. oxidation thioxanthone analog derivative, it is characterised in that its structural formula is as follows:
In formula (1) and formula (2), R1、R2、R3、R4、R5、R6、R7、R8Be respectively selected from hydrogen atom, the alkoxyl of 1 to 20 carbon atom, the alkylthio group of 1 to 20 carbon atom, the alkylamino radical of 1 to 20 carbon atom, the substituted aromatic amines base of 6 to 30 carbon atoms, phenoxy group, thiophenyl, the aryl of 6 to 30 carbon atoms, the substituted aryl of 6 to 30 carbon atoms, the heteroaromatic group of 5 to 50 annular atomses, 5 to 50 annular atomses replacement heteroaromatic group in one, and R1、R2、R3、R4、R5、R6、R7、R8In have at least one for aromatic group；
Described R1、R2、R3、R4、R5、R6、R7、R8The alkoxyl of 1 to 20 carbon atom being selected from is: methoxyl group, ethyoxyl, propoxyl group, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, amoxy, isoamoxy, neopentyl oxygen, tertiary amoxy, hexyloxy, 2-methyl amoxy；
Described R1、R2、R3、R4、R5、R6、R7、R8The alkylthio group of 1 to 20 carbon atom being selected from is: methyl mercapto, ethylmercapto group, rosickyite base, positive butylthio, second butylthio, tertiary butylthio；
Described R1、R2、R3、R4、R5、R6、R7、R8The alkylamino radical of 1 to 20 carbon atom being selected from is: methylamino, ethylamino-, Propylamino, butylamine base, amylamine base, isoamyl amido, neopentyl amine base, tertiary amylamine base, hexylamine base, dimethylamino, diethylin, dipropyl amido, dibutyl amino, diamyl amido, diisoamyl amido, two neopentyl amine bases, two tertiary amylamine bases, dihexylamine base；
Described R1、R2、R3、R4、R5、R6、R7、R8The substituted aromatic amines base of 6 to 30 carbon atoms being selected from is: o-, m-, p-aminomethyl phenyl amido, o-, m-, p-ethylphenyl amido, o-, m-, p-propyl group phenyl amido, o-, m-, p-isopropyl phenyl amido, o-, m-, p-methoxyphenyl amido, o-, m-, p-ethoxyl phenenyl amido, o-, m-, p-propoxyphenyl amido, o-, m-, p-difluorophenyl amido, o-, m-, p-chlorophenyl amido, o-, m-, p-bromo phenyl amido, o-, m-, p-iodine substituted phenyl amido, two (o-, m-, p-aminomethyl phenyl) amido, two (o-, m-, p-ethylphenyl) amido, two (o-, m-, p-propyl group phenyl) amido, two (o-, m-, p-isopropyl phenyl) amido, two (o-, m-, p-methoxyphenyl) amido, two (o-, m-, p-ethoxyl phenenyl) amido, two (o-, m-, p-propoxyphenyl) amido, two (o-, m-, p-difluorophenyl) amido, two (o-, m-, p-chlorophenyl) amido, two (o-, m-, p-bromo phenyl) amido, two (o-, m-, p-iodine substituted phenyl) amido；
Described R1、R2、R3、R4、R5、R6、R7、R8The aryl of 6 to 30 carbon atoms being selected from is: phenyl, diphenyl, triphenyl, naphthacenyl, pyrenyl, fluorenes, spiral shell fluorenes, 9,9 '-spiral shell two fluorenyl；
Described R1、R2、R3、R4、R5、R6、R7、R8The substituted aryl of 6 to 30 carbon atoms being selected from is: o-, m-, p-tolyl, xylyl, o-, m-, p-cumenyl, trimethylphenyl, 9,9 '-dimethyl fluorenyl；
Described R1、R2、R3、R4、R5、R6、R7、R8The heteroaromatic of 5 to 50 annular atomses being selected from is: 1-pyrrole radicals, 2-pyrrole radicals, 3-pyrrole radicals, pyridine radicals, 2-pyridine radicals, 3-pyridine radicals, 4-pyridine radicals, 1-indyl, 2-indyl, 3-indyl, 4-indyl, 5-indyl, 6-indyl, 7-indyl, 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl, 7-isoindolyl, 2-furyl, 3-furyl, 2-benzofuranyl, 3-benzofuranyl, 4-benzofuranyl, 5-benzofuranyl, 6-benzofuranyl, 7-benzofuranyl, dibenzofurans-2-base, 1-isobenzofuran-base, 3-isobenzofuran-base, 4-isobenzofuran-base, 5-isobenzofuran-base, 6-isobenzofuran-base, 7-isobenzofuran-base, 2-quinolyl, 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl, 8-quinolyl, 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl, 8-isoquinolyl, 2-quinoxalinyl, 5-quinoxalinyl, 6-quinoxalinyl, 1-carbazyl, 2-carbazyl, 3-carbazyl, 4-carbazyl, 9-carbazyl, 1-coffee pyridine base, 2-coffee pyridine base, 3-coffee pyridine base, 4-coffee pyridine base, 6-coffee pyridine base, 7-coffee pyridine base, 8-coffee pyridine base, 9-coffee pyridine base, 10-coffee pyridine base, 1-acridinyl, 2-acridinyl, 3-acridinyl, 4-acridinyl, 9-acridinyl, 1,7-phenanthrene coughs up beautiful jade-2-base, 1,7-phenanthrene coughs up beautiful jade-3-base, 1,7-phenanthrene coughs up beautiful jade-4-base, 1,7-phenanthrene coughs up beautiful jade-5-base, 1,7-phenanthrene coughs up beautiful jade-6-base, 1,7-phenanthrene coughs up beautiful jade-8-base, 1,7-phenanthrene coughs up beautiful jade-9-base, 1,7-phenanthrene coughs up beautiful jade-10-base, 1,8-phenanthrene coughs up beautiful jade-2-base, 1,8-phenanthrene coughs up beautiful jade-3-base, 1,8-phenanthrene coughs up beautiful jade-4-base, 1,8-phenanthrene coughs up beautiful jade-5-base, 1,8-phenanthrene coughs up beautiful jade-6-base, 1,8-phenanthrene coughs up beautiful jade-7-base, 1,8-phenanthrene coughs up beautiful jade-9-base, 1,8-phenanthrene coughs up beautiful jade-10-base, 1,9-phenanthrene coughs up beautiful jade-2-base, 1,9-phenanthrene coughs up beautiful jade-3-base, 1,9-phenanthrene coughs up beautiful jade-4-base, 1,9-phenanthrene coughs up beautiful jade-5-base, 1,9-phenanthrene coughs up beautiful jade-6-base, 1,9-phenanthrene coughs up beautiful jade-7-base, 1,9-phenanthrene coughs up beautiful jade-8-base, 1,9-phenanthrene coughs up beautiful jade-10-base, 1,10-phenanthrene coughs up beautiful jade-2-base, 1,10-phenanthrene coughs up beautiful jade-3-base, 1,10-phenanthrene coughs up beautiful jade-4-base, 1,10-phenanthrene coughs up beautiful jade-5-base, 2,9-phenanthrolines-1-base, 2,9-phenanthrolines-3-base, 2,9-phenanthrolines-4-base, 2,9-phenanthrolines-5-base, 2,9-phenanthrolines-6-base, 2,9-phenanthrolines-7-base, 2,9-phenanthrolines-8-base, 2,9-phenanthrolines-10-base, 2,8-phenanthrene coughs up beautiful jade-1-base, 2,8-phenanthrene coughs up beautiful jade-3-base, 2,8-phenanthrene coughs up beautiful jade-4-base, 2,8-phenanthrene coughs up beautiful jade-5-base, 2,8-phenanthrene coughs up beautiful jade-6-base, 2,8-phenanthrene coughs up beautiful jade-7-base, 2,8-phenanthrene coughs up beautiful jade-9-base, 2,8-phenanthrene coughs up beautiful jade-10-base, 2,7-phenanthrene coughs up beautiful jade-1-base, 2,7-phenanthrene coughs up beautiful jade-3-base, 2,7-phenanthrene coughs up beautiful jade-4-base, 2,7-phenanthrene coughs up beautiful jade-5-base, 2,7-phenanthrene coughs up beautiful jade-6-base, 2,7-phenanthrene coughs up beautiful jade-8-base, 2,7-phenanthrene coughs up beautiful jade-9-base, 2,7-phenanthrene coughs up beautiful jade-10-base, 1-phenazinyl, 2-phenazinyl, 1-phenothiazinyl, 2-phenothiazinyl, 3-phenothiazinyl, 4-phenothiazinyl, lysivane base, 1-phenazinyl, 2-phenazinyl, 3-phenazinyl, 4-phenazinyl, 10-phenazinyl, 2-azoles base, 4-azoles base, 5-azoles base, 2-di azoly, 5-di azoly, 3-furazanyl, 2-thienyl, 3-thienyl, dibenzothiophenes-2-base；
Described R1、R2、R3、R4、R5、R6、R7、R8The heteroaromatic of the replacement of 5 to 50 annular atomses being selected from is: 2-picoline-1-base, 2-methylpyrrole-3-base, 2-methylpyrrole-4-base, 2-methylpyrrole-5-base, 3-methylpyrrole-1-base, 3-methylpyrrole-2-base, 3-methylpyrrole-4-base, 3-methylpyrrole-5-base, 2-tert-butyl group pyrroles's-4-base, 3-(2-phenyl propyl) pyrroles one-1-base, 2-methyl isophthalic acid-indyl, 4-methyl isophthalic acid-indyl, 2-methyl-3-indyl, 4-methyl-3-indyl, the 2-tert-butyl group-1-indyl, the 4-tert-butyl group-1-indyl, the 2-tert-butyl group-3-indyl, the 4-tert-butyl group-3-indyl.
3. the preparation method of the oxidation thioxanthone analog derivative as described in as arbitrary in claim 1～2, it is characterised in that comprise the following steps:
A, by thioxanthone compounds and concentration, the nitrate solution not higher than 10M is dissolved in acetonitrile with the ratio that mol ratio is 1:0.1～100, stirring, adds water precipitation, filters, filtrate recrystallization, obtains the oxidation thioxanthone analog derivative shown in formula (1)；Or
B, being dissolved in acetic acid by thioxanthone compounds and hydrogen peroxide solution with the ratio that mol ratio is 1:0.1～100, backflow, cooling precipitates out precipitation, filters, filtrate recrystallization, obtains oxidation thioxanthone analog derivative shown in formula (2)；
The structural formula of described thioxanthone compounds is:
In formula, R1、R2、R3、R4、R5、R6、R7、R8Definition such as claim 1 or 2.
4. the preparation method of oxidation thioxanthone analog derivative according to claim 3, it is characterised in that described nitrate solution is sodium nitrate, ammonium nitrate or iron nitrate solution；The solvent that described recrystallization is selected is one or more mixed solvents in methanol, ethanol, dichloromethane, dimethyl sulfoxide, diformamide；Described backflow is to reflux under 25～100 DEG C of conditions.
5. the application of the oxidation thioxanthone analog derivative as described in as arbitrary in claim 1～2, it is characterised in that this oxidation thioxanthone analog derivative is used as the organic luminous layer of organic electroluminescence device.
6. the application of oxidation thioxanthone analog derivative according to claim 5, it is characterised in that described oxidation thioxanthone analog derivative can make electrophosphorescence device by Doping Phosphorus photoinitiator dye.
7. the application of oxidation thioxanthone analog derivative according to claim 6, it is characterised in that the doping content of phosphorescent coloring is 5～15wt%.
8. the application of oxidation thioxanthone analog derivative according to claim 7, it is characterised in that the structure of described organic electroluminescence device is: substrate/anode/hole transmission layer/organic luminous layer/electron transfer layer/negative electrode；Substrate is a kind of material in glass, polyesters, poly-phthalimide compounds；Anode is a kind of material in tin indium oxide, zinc oxide, zinc tin oxide, gold, silver, copper, polythiophene/polyvinylbenzenesulfonic acid sodium, polyaniline；Negative electrode is lithium, magnesium, calcium, strontium, aluminum or indium, or a kind of and copper in them, golden or silver-colored alloy, or the electrode layer that above-mentioned metal or alloy is alternatively formed with metal fluoride；Hole transmission layer is tri-arylamine group material；Electron transfer layer is nitrogen heterocycles material；Organic luminous layer is the oxidation thia anthracyclinone derivatives shown in formula (1) or (2).
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