CN105924438B - A kind of organic photoelectrical material containing indeno ferrosin structure and its preparation method and application - Google Patents

A kind of organic photoelectrical material containing indeno ferrosin structure and its preparation method and application Download PDF

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CN105924438B
CN105924438B CN201610332694.8A CN201610332694A CN105924438B CN 105924438 B CN105924438 B CN 105924438B CN 201610332694 A CN201610332694 A CN 201610332694A CN 105924438 B CN105924438 B CN 105924438B
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CN105924438A (en
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林存生
孙晟源
张善国
付文岗
胡葆华
许琰
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Valiant Co Ltd
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Abstract

The invention discloses a kind of organic photoelectrical material containing indeno ferrosin structure and its preparation method and application, belong to organic photoelectrical material technical field.It has molecular structure shown in formula 1：Wherein, R1For phenyl or dibenzofuran group, R2For one kind in hydrogen, phenyl or dibenzofuran group, R3The conjugated polycyclic aryl for being 10 60 for hydrogen, phenyl, carbon number and contain one kind in the aromatic heterocyclic radical in N, S, O atom.The material of the present invention is due to containing indeno phenanthroline structure, forming bigger rigid planar structure, there is provided high electron mobility and big electron affinity, the transmission of injection electronics is greatly improved.

Description

A kind of organic photoelectrical material containing indeno ferrosin structure and preparation method thereof and Using
Technical field
The present invention relates to a kind of organic photoelectrical material containing indeno ferrosin structure and its preparation method and application, belong to Organic photoelectrical material technical field.
Background technology
In recent years, Organic Light Emitting Diode (organic light emitting diode, OLED) turns into non-both at home and abroad Often popular emerging flat-panel screens, because OLED display has self-luminous, wide viewing angle (up to more than 175 DEG C), short anti- Between seasonable, high luminous efficiency, wide colour gamut, low-work voltage (3~10V), panel is thin, the panel of large scale and deflection can be made and The characteristics such as processing procedure is simple, and it has potentiality of low cost.It is considered as the nova of super-thin plane display device of future generation. Go to research and develop organic electroluminescence although the present whole world has many research institutions and company to put into substantial amounts of energy Part, but compared with the expection of people, its industrialization level also differs greatly, and still has many key issues not solved really Certainly, such as excitation, stability of photoluminescence, have chance with actuation techniques and encapsulation technology etc., also there is it is certain the problem of so that have The short life of organic electroluminescence devices, it is less efficient.
Organic luminescent device mainly has positive and negative two electrode layer, and is clipped in luminescent layer among two electrode layers, hole transport One layer of layer and electron transfer layer etc. several layers of are formed.The corresponding material of functional layer applied to organic electroluminescence device can divide It is also known as luminescent material, hole mobile material and electron transport material.In organic electroluminescent, electronics and hole compound and The organic molecule excited, do not limited by spin selection law, in theory according to statistical distribution, produce excited triplet state and excite The ratio of singlet state is 3:1.Therefore in fluorescence electroluminescent, the excited energy for having 75% is lost.But if utilize phosphorus Photoelectricity electroluminescent material, it is possible to all excitation state is made full use of, so as to promote OLED efficiency to increase substantially.Panchromatic aobvious Show in field, blue light is as one of three primary colours, and the still important component of white light, can also not be used as exciting light green to realize The display of light and feux rouges.But blue phosphorescent luminescent material compare with green and feux rouges phosphorescent light-emitting materials, due to energy band compared with Width, carrier injection is relatively difficult with exciton limitation, causes less efficient.
In order to lift the performance of organic electroluminescence device, the research to electron transport material is particularly significant.Select electronics Transmission material must is fulfilled for following requirement：(1) there are reversible electrochemical reduction and enough reduction potentials, because electric The process that son conducts in organic film is a series of redox reaction；(2) good electron mobility, could so incite somebody to action Charge recombination region；(3) good film forming and heat endurance；(4) good photostability.
Although having there is the electron transport material of many organic luminescent devices at present, the electronics of conditions above can be met Transmission material is also rare.
The content of the invention
An object of the present invention, it is to provide a kind of organic photoelectrical material containing indeno ferrosin structure.The present invention's Material, there is high heat endurance and high glass transition temperature, can be as OLED electron transport material so that OLED's Power efficiency is greatly improved, and also reduces driving voltage, thus significantly improves the life-span of organic electroluminescence.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：A kind of organic photoelectric containing indeno ferrosin structure Material, there is molecular structure shown in formula 1：
Wherein, R1For phenyl or dibenzofuran group, R2For one kind in hydrogen, phenyl or dibenzofuran group, R3For hydrogen, Phenyl, carbon number be 10-60 conjugated polycyclic aryl and contain one kind in the aromatic heterocyclic radical in N, S, O atom.
The organic photoelectrical material of the present invention, has high heat endurance and high glass transition temperature, as OLED's Electron transport material so that OLED power efficiency is greatly improved, and also reduces driving voltage, has thus significantly improved The life-span of organic electro luminescent device.
On the basis of above-mentioned technical proposal, the present invention can also do following improvement.
Further, the R3Concrete structure formula be：
The organic photoelectrical material containing above-mentioned indeno ferrosin structure of the present invention, specific structural formula are as follows：
By test result indicates that, organic photoelectrical material provided by the invention has high heat endurance and high vitrifying Transition temperature, the electron transport material as OLED are applied in OLED, include organic photoelectrical material provided by the invention OLED can obtain good device performance, such as OLED power efficiency is greatly improved；Simultaneously, additionally it is possible to significantly drop Low driving voltage and the life-span for greatly promoting OLED.It is possible thereby to learn：Organic photoelectrical material provided by the invention is in OLED With good application effect, there is good industrialization prospect.
The second object of the present invention, it is to provide the above-mentioned organic photoelectrical material containing indeno ferrosin structure.Preparation side Method.The preparation method of the present invention, it is simple and easy, it is easily operated, and cost is cheap, is advantageous to promote on a large scale.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：A kind of organic photoelectric containing indeno ferrosin structure The preparation method of material, comprises the following steps：
Step 1：Under the protection of inert gas and under -100~0 DEG C of temperature conditionss, 2.0~2.4 moles are worked as The n-BuLi of amount is added in the THF solution of 4, the 7- dibromo phenanthrolines containing 1.0 molar equivalents, is reacted, then is added The trim,ethylchlorosilane for entering 2.0~2.2 molar equivalents is reacted, after obtaining the reaction system containing intermediate one, then will be upper State the reaction system containing intermediate one and be to slowly warm up to room temperature, then pour into water, stirring reaction 10~50min, Ran Houjia Enter ethyl acetate to be layered, washed successively, then desolventizing is depressurized to without cut to organic phase, obtain intermediate one；
Step 2：Under the protection of inert gas and under -100~0 DEG C of temperature conditionss, 1.0~1.1 moles are worked as The n-BuLi of amount is added to the aryl halides R containing 1.0 molar equivalents1In-Br THF solution, first step reaction is carried out, Obtain R1Lithium salt solution, then under -60~10 DEG C of temperature conditionss, by above-mentioned R1Lithium salt solution be added dropwise to and contain step 1 In the organic solution of obtained intermediate one, second step reaction is carried out, then plus water carries out that reaction is quenched, then is extracted with dichloromethane Take, extract is handled with the manganese dioxide of 4~10.0 molar equivalents, after obtaining the reaction system containing intermediate two, then will The above-mentioned reaction system containing intermediate two is filtered under diminished pressure, gained filtrate decompression concentration, then with petroleum ether and dichloromethane Alkane mixed liquor is concentrated under reduced pressure to above-mentioned, and obtained product carries out the volume ratio of column chromatography purifying, wherein petroleum ether and dichloromethane For petroleum ether：Dichloromethane=5~60:1, obtain intermediate two；
Step 3：Under the protection of inert gas and under -100~0 DEG C of temperature conditionss, 1.0~1.1 moles are worked as The n-BuLi of amount is added to the aryl halides R containing 1.0 molar equivalents2- Br organic solution, first step reaction is carried out, Obtain R2Lithium salt solution, then under -60~10 DEG C of temperature conditionss, by above-mentioned R2Lithium salt solution be added dropwise to and contain step 2 In the organic solution of obtained intermediate two, second step reaction is carried out, then plus water carries out that reaction is quenched, then is extracted with dichloromethane Take, extract is handled with the manganese dioxide of 4~10.0 molar equivalents, obtains the reaction system containing intermediate three, will be above-mentioned Reaction system containing intermediate three is filtered under diminished pressure, and the concentration of gained filtrate decompression, is then mixed with petroleum ether and dichloromethane Close liquid to be concentrated under reduced pressure to above-mentioned, obtained product carries out column chromatography purifying, and the wherein volume ratio of petroleum ether and dichloromethane is stone Oily ether：Dichloromethane=5~60:1, obtain intermediate three；
Step 4：Under the protection of inert gas and under 0~60 DEG C of temperature conditionss, by 2.1~3.0 molar equivalents NBS be added in the organic solution of the intermediate three obtained containing step 3, obtain the reaction system containing intermediate four, will The above-mentioned reaction system containing intermediate four, add the solution of sodium bisulfite that mass percent concentration is 2% and be quenched instead Should, chloroform is then added, after layering, adds water washing, after the completion of washing, desolventizing is depressurized to organic phase to without cut, desolventizing Afterwards, recrystallized with toluene alcohol mixed solvent, wherein the volume ratio of toluene and ethanol is 2:3~8；Or with petroleum ether and Dichloromethane mixed liquor carries out the body of column chromatography purifying, wherein petroleum ether and dichloromethane to the residue after above-mentioned be concentrated under reduced pressure Product is than being 5~60:1, obtain intermediate four；
Step 5：Intermediate four, the aryl boric acid R that step 4 is obtained3-B(OH)2And alkaline matter, be added to toluene, In dimethylbenzene, DMF or dimethyl acetamide, under inert gas shielding, catalyst is added, then, 60 After being reacted 2~24 hours at~150 DEG C, the reaction system containing intermediate five is obtained, by the above-mentioned reaction containing intermediate five System layering, it is washed with water, then desolventizing is depressurized extremely without cut to organic phase, is then purified with column chromatography, the purifying Eluted with the mixed liquor or petroleum ether of petroleum ether and dichloromethane and the mixed liquor of ethyl acetate, wherein petroleum ether and two The volume ratio of chloromethanes is 2~60:1, the volume ratio of petroleum ether and ethyl acetate is 2~35:1, obtain intermediate five；
Step 6：By intermediate five, bromophenyl boric acid and alkaline matter that step 5 obtains be added to toluene, dimethylbenzene, In DMF or dimethyl acetamide, under inert gas shielding, catalyst is added, then, at 60~150 DEG C After lower reaction 2~24 hours, the reaction system containing intermediate six is obtained, by the above-mentioned reaction system containing intermediate six point Layer, is washed with water, then depressurizes desolventizing extremely without cut to organic phase, is then purified with column chromatography, above-mentioned purifying oil The mixed liquor or petroleum ether of ether and dichloromethane and the mixed liquor of ethyl acetate are eluted, wherein petroleum ether and dichloromethane Volume ratio be 2~60:1, the volume ratio of petroleum ether and ethyl acetate is 2~35:1, obtain intermediate six；
Step 7：The intermediate six and alkaline matter that are obtained in step 6 are added to toluene, dimethylbenzene, N, N- dimethyl In formamide or dimethyl acetamide, under inert gas shielding, add catalyst, then, at 60~170 DEG C react 2~ After 24 hours, that is, the organic photoelectrical material containing indeno ferrosin structure is obtained, wherein, R1For phenyl or dibenzofurans Base, R2For one kind in hydrogen, phenyl or dibenzofuran group, R3Concrete structure formula be：
The structural formula of intermediate one to the intermediate six is respectively：
The reaction equation of above-mentioned preparation method is as follows：
The preparation method of the present invention, involved course of reaction are conventional organic reaction type, and course of reaction is simple, peace Entirely, it is easily operated, and the prices of raw materials are cheap, are easy to purchase, and are advantageous to promote on a large scale.Wherein, in step 1,4,7- bis- Bromine phenanthroline is dispersed in tetrahydrofuran, and n-BuLi exists in the form of being dispersed in n-hexane, that is to say, that will contain The n-hexane of n-BuLi is added drop-wise to progress lithium halogen exchange in the organic solution containing 4,7- dibromo phenanthrolines.
In step 2, aryl halides R1- Br is dispersed in tetrahydrofuran, and n-BuLi is to be dispersed in the shape in n-hexane Formula is present, that is to say, that the n-hexane containing n-BuLi is added drop-wise to containing aryl halides R1Enter in-Br organic solution Row lithium halogen exchanges.
In step 3, aryl halides R2- Br is dispersed in tetrahydrofuran, and n-BuLi is to be dispersed in the shape in n-hexane Formula is present, that is to say, that the n-hexane containing n-BuLi is added drop-wise to containing aryl halides R2Enter in-Br organic solution Row lithium halogen exchanges.
On the basis of above-mentioned technical proposal, the present invention can also do following improvement.
Further, in step 5, the alkaline matter is one in sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide Kind is a variety of；The catalyst is palladium, four (triphenylphosphines), bi triphenyl phosphorus palladium chloride and three (dibenzalacetones) One or more in two palladiums；The temperature of the reaction is 60~90 DEG C, and the time is 4~8 hours；The alkaline matter and centre The mol ratio of body four is 1.3~3.0:1.
Further, in step 6, the alkaline matter is one in sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide Kind is a variety of；The catalyst is palladium, four (triphenylphosphines), bi triphenyl phosphorus palladium chloride and three (dibenzalacetones) One or more in two palladiums；The temperature of the reaction is 60~90 DEG C, and the time is 4~8 hours；The alkaline matter and centre The mol ratio of body five is 1.3~3.0:1；The mol ratio of the catalyst and intermediate five is 0.001~0.1:1.
It is using above-mentioned further beneficial effect：Alkaline matter provides alkaline environment, is advantageous to the complete of reaction progress.
Further, in step 7, the alkaline matter is the one or more in triethylamine, DBU, caustic alcohol；The catalysis Agent is selected from one kind or more in palladium, four (triphenylphosphines), bi triphenyl phosphorus palladium chloride, three (dibenzalacetone) two palladium Kind；Reaction temperature is preferably 100~170 DEG C, and the reaction time is preferably 6~12 hours；The alkaline matter and intermediate six Mol ratio is 1.3~3.0:1；The mol ratio of the catalyst and intermediate six is 0.001~0.1:1.
Further, in step 5, step 6 and step 7, phosphine system part is added when adding catalyst, phosphine system part is Double (diphenylphosphine) propane of 1,3-, the double diphenylphosphine -9,9- dimethyl xanthenes of 4,5-, 2- dicyclohexyl phosphine -2', 6'- diformazans One or more in epoxide biphenyl or tri-butyl phosphine tetrafluoroborate.
It is using above-mentioned further beneficial effect：While catalyst is added, phosphine system part is added, system matches somebody with somebody due to phosphine Body can preferably be complexed with above-mentioned palladium class catalyst in C-C coupled catalytic reactions, so as to form zero-valence palladium complex, enter one Step participates in intermediate four and aryl boric acid R3-B(OH)2Cross-coupling, so as to improve the purity of intermediate five and yield.
While catalyst is added, phosphine system part is added, can be compared with because phosphine system part is in C-C coupled catalytic reactions It is complexed with above-mentioned palladium class catalyst well, so as to form zero-valence palladium complex, further participates in intermediate five and bromophenyl boric acidCross-coupling, so as to improve the purity of intermediate six and yield.
While catalyst is added, phosphine system part is added, can be compared with because phosphine system part is in C-C coupled catalytic reactions It is complexed with above-mentioned palladium class catalyst well, so as to form zero-valence palladium complex, further participates in the intramolecular cyclization of intermediate six, from And improve to obtain the purity of object and yield.
Further, the catalyst and intermediate four or the mol ratio of intermediate five or intermediate six be 0.001~ 0.1:1。
Further, in step 7, the inert gas is the one or more in nitrogen, argon gas, helium.
Further, the inert gas is nitrogen.
The third object of the present invention, it is to provide the application of the above-mentioned organic photoelectrical material containing indeno ferrosin structure.
The technical scheme that the present invention solves above-mentioned technical problem is as follows：A kind of organic photoelectric containing indeno ferrosin structure The application of material, in organic electroluminescence device, at least one functional layer contains contains indeno ferrosin as described above The organic photoelectrical material of structure.
A kind of organic electroluminescence device, as shown in fig. 1, including at least one luminescent layer 5 and electron transfer layer 6, institute Electron transfer layer 6 is stated to be made up of the material of the organic photoelectrical material of the offer containing the present invention.When in organic electroluminescence device When comprising only luminescent layer 5 and electron transfer layer 6, electron transfer layer 6 is interposed between luminescent layer 5 and negative electrode 8.OLED luminescent devices Structure, contain at least one luminescent layer 5 and electron transfer layer 6.
In above-mentioned organic electroluminescence device, as shown in fig. 1, the one or more in following film layer are may also include： Hole injection layer 3, hole transmission layer 4 and electron injecting layer 7, wherein, hole injection layer 3 and hole transmission layer 4 are arranged at sun Between pole 2 and luminescent layer 5, electron transfer layer 6 and electron injecting layer 7 are arranged between luminescent layer 5 and negative electrode 8.When containing upper When stating the one or more in the film layer mentioned, the structure of organic electroluminescence device can be as follows, but be not limited to following It is several：
(1) negative electrode 8 of 2/ organic luminous layer of anode, 5/ electron transfer layer 6/, that is to say, that set between anode 2 and negative electrode 8 Organic luminous layer 5 and electron transfer layer 6 are equipped with, wherein, organic luminescent layer 5 and electron transfer layer 6 are set gradually on anode 2.
(2) negative electrode 8 of 2/ hole injection layer of anode, 3/ organic luminous layer, 5/ electron transfer layer 6/, that is to say, that in the He of anode 2 Hole injection layer 3, organic luminous layer 5 and electron transfer layer 6 are provided between negative electrode 8, wherein, set gradually sky on anode 2 Cave implanted layer 3, organic luminous layer 5 and electron transfer layer 6.
(3) negative electrode 8 of 2/ hole transmission layer of anode, 4/ organic luminous layer, 5/ electron transfer layer 6/, that is to say, that in the He of anode 2 Hole transmission layer 4, organic luminous layer 5 and electron transfer layer 6 are provided between negative electrode 8, wherein, set gradually sky on anode 2 Cave transport layer 4, organic luminous layer 5 and electron transfer layer 6.
(4) negative electrode 8 of 2/ hole injection layer of anode, 3/ hole transmission layer, 4/ organic luminous layer, 5/ electron transfer layer 6/, that is, Say, hole injection layer 3, hole transmission layer 4, organic luminous layer 5 and electron transfer layer 6 be provided between anode 2 and negative electrode 8, Wherein, hole injection layer 3, hole transmission layer 4, organic luminous layer 5 and electron transfer layer 6 are set gradually on anode 2.
Make in OLED display, each layer can be by being made film the methods of vapour deposition method, spin-coating method or casting method by material To be formed.The thickness of each layer formed in this way is not particularly limited, can respective material property and suitably set, generally For 2~5000nm scope.Furthermore the method for luminescent material thin-film is readily available uniform film layer and is not easy to generate pin For the experience in hole, preferred vapour deposition method.Evaporation condition is generally preferably in boat, 50~400 DEG C of heating-up temperature, vacuum 10-6~ 10-3Pa, 0.01~50nm/s of evaporation rate, suitably set in the range of substrate temperature -150~300 DEG C, 5~5 μm of thickness.
Anode has the function of injecting holes into hole transmission layer 4, and anode is generally made up of later material：As aluminium, gold, The metals such as silver, nickel, palladium or platinum；Such as indium oxide, tin oxide, zinc oxide, indium tin composite oxides, indium zinc composite oxide metal Oxide；Such as cupric iodide metal halide；Carbon black；Or partially electronically conductive macromolecule etc..
Hole transmission layer is the high efficiency from anode injection hole and can effectively transmit the material of injected holes. Therefore, it is necessary to which the ionization potential of the material is low, high to the permeability of visible ray, hole mobility is high, property is stable, it is also necessary to making The light being not likely to produce when for or using turns into the impurity of trap (trap).Additionally, due to be in contact with luminescent layer 5, it is necessary to hole pass Defeated layer 4 does not make the light delustring for carrying out light emitting layer 5, and forms exciplex not between luminescent layer 5 and to reduce efficiency common Hole mobile material can be enumerated with N4, N4'- bis- (naphthalene -1- bases)-N4, N4'- diphenyl-[1,1'- biphenyl] -4,4'- diamines (NPB) aromatic diamine containing more than two tertiary amines, the triphen amine for representative have the aromatic amine of star radial configuration Class compound, carbazole analog derivative etc..These compounds can be used alone, but also also mix together two or more.
As in hole-injecting material functional material, can be selected in material known to the hole transmission layer from OLED luminescent devices Arbitrary material is selected to be used.
Luminescent layer is formed by luminescent substance, wherein, between the electrode of electric field is applied with, this luminescent substance because of hole and Electronics in conjunction with and excite, it is strong luminous so as to show.Usual luminescent layer 5 contain doping type material as luminescent substance with Host material.In order to obtain high efficiency OLED luminescent devices, a kind of adoptable dopant material of its luminescent layer, or mixed using a variety of Miscellaneous material.Dopant material can be simple fluorescence or phosphor material, or be formed by different fluorescence and phosphorescence matched combined, light Layer can be single emitting layer material, or the recombination luminescence layer material being superimposed.
The material of main part of luminescent layer not only needs to have ambipolar charge transport quality, while needs appropriate energy rank, Excitation energy is efficiently transferred to guest emitting material, this kind of material can enumerate diphenylethyllene aryl derivatives, Stibene derivative, carbazole derivates, triarylamine derivatives, anthracene derivant, pyrene derivatives, coronene derivative Deng.
Relative to material of main part, the incorporation of guest materials is preferably more than 0.01% weight, below 20% weight.This The material of class can enumerate the metal complex of iridium, nail, platinum, rhenium, palladium etc..
The material of the electron transfer layer of above-mentioned OLED luminescent devices is formed, using electron transport material of the present invention as OLED The electron transfer layer of device, it can select such as benzo miaows such as 1,3,5- tri- (1- naphthyls -1H- benzimidazolyl-2 radicals-yl) benzene (TPBI) The metal complex such as azole derivative, three (8- hydroxyl quinolines phosphine) aluminium (Al q3), 2- (4, -2-methyl-2-phenylpropane base) -5- (4,-xenyl) - 1,3,4- oxadiazoles (PBD) Deng oxadiazole derivatives, 4,7- diphenyl -1,10- ferrosins (BPhen), 2,9- dimethyl -4,7- The phenanthroline derivatives such as diphenyl -1,10- ferrosin (BCP), triazole derivative, quinoline phosphine-derivatives, quinoline phosphine-derivatives etc..
Metal of the work function less than 4eV, alloy, electric conductivity can be selected in cathode material workable for above-mentioned OLED luminescent devices Compound and their mixture.Its concrete example is aluminium, calcium, magnesium, lithium, magnesium alloy, aluminium alloy etc..In order to efficiently obtain OLED's is luminous, and the transmitance of at least one of electrode preferably is set into more than 10%.Negative electrode can be for example true by dry method Sky evaporation, vapour deposition or sputtering are formed.
The beneficial effects of the invention are as follows：
The organic photoelectrical material containing indeno ferrosin structure that the present invention synthesizes is applied in organic electroluminescence device Efficient electroluminescent properties are obtained, its major advantage is as follows：
1. the material of the present invention is due to containing indeno phenanthroline structure, forming bigger rigid planar structure, there is provided High electron mobility and big electron affinity, the transmission of injection electronics is greatly improved.
2. the material of the present invention has good heat endurance, glass transition temperature and decomposition temperature are all very high, easily Good amorphous thin film is formed, is applied in electroluminescent device, more stable effect and longer use can be obtained Life-span.
3. the material of the present invention has higher excited level, the energy transmission of excitation state can be effectively prevented from, makes to swash Sub- recombination region is formed in luminescent layer, rather than in electron transfer layer.
4. in organic electroluminescence provided by the invention, due to containing organic photoelectrical material provided by the invention, energy The power efficiency of organic electroluminescence is enough greatly improved, at the same time, driving voltage is also reduced, has thus significantly improved The life-span of organic electro luminescent device.
Brief description of the drawings
Fig. 1 is the structural representation of the organic electroluminescence device prepared by the present invention, by lower floor to upper strata, is followed successively by Bright substrate layer (1), anode (2), hole injection layer (3), hole transmission layer (4), luminescent layer (5), electron transfer layer (6), electronics Implanted layer (7) and negative electrode (8), wherein, electron transfer layer (6) is related to the electroluminescent organic material prepared by the present invention.
Embodiment
The principle and feature of the present invention are described below in conjunction with accompanying drawing, the given examples are served only to explain the present invention, and It is non-to be used to limit the scope of the present invention.
Compound prepares embodiment：
Embodiment 1：Prepare the compound E01 being previously mentioned
The preparation of intermediate one (a)：
At -78 DEG C and under the protection of nitrogen, 67.6g 4 is taken, 7- dibromos phenanthroline (200.0mmol) is dispersed in In 500g tetrahydrofurans, 176mL then is added dropwise and concentration is the 2.5mol/L hexane solution containing n-BuLi, drips Bi Hou, insulation reaction 2.0 hours, then at -78 DEG C, 33.0g trim,ethylchlorosilanes are added dropwise, insulation reaction 2.0 hours after finishing are dripped, Then reaction system is to slowly warm up to room temperature, then after system is poured into 200g water, stirring reaction 30min, added afterwards 500g ethyl acetate extracts, and system layering, is washed from water, and most organic phase decompression desolventizing to without cut, obtains at last To 64.7g intermediates one (a), without being further purified.
The preparation of intermediate one (b)：
At -78 DEG C and under the protection of nitrogen, 33.1g bromobenzenes (211.0mmol) are taken to be dispersed in 300g tetrahydrofurans In, the hexane solution containing n-BuLi that 93mL and concentration are 2.5mol/L, after being added dropwise, insulation reaction is then added dropwise 2.0 hours, then be to slowly warm up to preserve at -10 DEG C stand-by.
Take 32.5g intermediates one (100.0mmol) to be dissolved in 300g tetrahydrofurans, at a temperature of -10 DEG C, above-mentioned benzene is added dropwise Base lithium solution, insulation reaction 2.0 hours after finishing are dripped, reaction system are then to slowly warm up to room temperature, then system is poured into After in 200g water, stirring reaction 30min, the extraction of 500g dichloromethane is added afterwards, system layering, is washed from water, nothing Aqueous sodium persulfate is dried.
146.8g manganese dioxide (1.69mol) is added into above-mentioned dichloromethane solution, at 25 DEG C, stirring reaction 5.5 is small When, decompression filters, and filtrate decompression desolventizing is to without cut.Then with petroleum ether and dichloromethane mixed liquor to above-mentioned decompression precipitation The product that agent obtains carries out column chromatography purifying, and the wherein volume ratio of petroleum ether and dichloromethane is petroleum ether：Dichloromethane=20: 1, obtain 28.6g intermediates one (b), yield 71.50%.
The preparation of intermediate one (c)：
At -78 DEG C and under the protection of nitrogen, 16.6g bromobenzenes (105.0mmol) are taken to be dispersed in 150g tetrahydrofurans In, the hexane solution containing n-BuLi that 47mL and concentration are 2.5mol/L, after being added dropwise, insulation reaction is then added dropwise 2.0 hours, then be to slowly warm up to preserve at -10 DEG C stand-by.
Take 20.0g intermediates two (50.0mmol) to be dissolved in 150g tetrahydrofurans, at a temperature of -10 DEG C, above-mentioned benzene is added dropwise Base lithium solution, insulation reaction 2.0 hours after finishing are dripped, reaction system are then to slowly warm up to room temperature, then system is poured into After in 150g water, stirring reaction 30min, the extraction of 300g dichloromethane is added afterwards, system layering, is washed from water, nothing Aqueous sodium persulfate is dried.
73.9g manganese dioxide (850.0mmol) is added into above-mentioned dichloromethane solution, at 25 DEG C, stirring reaction 6 is small When, decompression filters, and filtrate decompression desolventizing is to without cut.Then with petroleum ether and dichloromethane mixed liquor to above-mentioned decompression precipitation The product that agent obtains carries out column chromatography purifying, and the wherein volume ratio of petroleum ether and dichloromethane is petroleum ether：Dichloromethane=15: 1, obtain 17.9g intermediates one (c), yield 75.21%.
The preparation of intermediate one (d)：
At 60 DEG C and under the protection of nitrogen, 14.3g intermediates three (30.0mmol) are taken to be dispersed in 200g chloroforms, Then add 11.7g NBS (66.0mmol), after being added dropwise, insulation reaction 12.0 hours, while using TLC tracking react into Journey.After reaction terminates, it is after reaction is quenched in 2% aqueous solution of sodium bisulfite, to be layered, water to add 200g mass percent concentrations Wash, then depressurize desolventizing to organic phase is extremely recrystallized to give among 13.1g without cut, final choice toluene alcohol mixed solvent Body one (d), yield 89.11%.
The preparation of intermediate one (e)：
Take 12.3g intermediates four (25.0mmol), 2.6g 1- naphthalene boronic acids (15.0mmol), 3.2g potassium carbonate (23.0mmol) and 30g water, dissolved with 60mL toluene and 30mL ethanol, lead to nitrogen gas stirring 1 hour, to remove the oxygen in reaction bulb Gas.Then Pd (PPh are added3)40.115g (1.0mmol), flow back under strong stirring, course of reaction passes through TLC tracing detections.Instead After answering, 200mL ethyl acetate aqueous phase extracteds, organic phase decompression desolventizing is extremely without cut, then with petroleum ether and dichloromethane The product that alkane mixed liquor obtains to above-mentioned decompression desolventizing carries out the volume ratio of column chromatography purifying, wherein petroleum ether and dichloromethane For petroleum ether：Dichloromethane=7:1, obtain 4.5g intermediates one (e), yield 55.6%.
The preparation of intermediate one (f)：
Take 4.3g intermediates five (8.0mmol), 1.8g bromophenyls boric acid (9.0mmol), 1.7g potassium carbonate (12.0mmol) With 15g water, dissolved with 30mL toluene and 15mL ethanol, lead to nitrogen gas stirring 1 hour, to remove the oxygen in reaction bulb.Then plus Enter Pd (PPh3)40.046g (0.04mmol), flow back under strong stirring, course of reaction passes through TLC tracing detections.After completion of the reaction, 100mL ethyl acetate aqueous phase extracteds, organic phase decompression desolventizing is extremely without cut, then with petroleum ether and dichloromethane mixed liquor pair The product that above-mentioned decompression desolventizing obtains carries out column chromatography purifying, and the wherein volume ratio of petroleum ether and dichloromethane is petroleum ether： Dichloromethane=8:1, obtain 3.4g intermediates one (f), yield 69.4%.
E01 preparation：
3.1g intermediates six (5.0mmol), 1.5g DBU (12.0mmol) and 30g DMF are taken, leads to nitrogen gas stirring 1 hour, To remove the oxygen in reaction bulb.Then Pd (PPh are added3)2Cl20.35g (0.05mmol), flow back under strong stirring, reacted Journey passes through TLC tracing detections.After completion of the reaction, pour into 100g frozen water, 200mL ethyl acetate aqueous phase extracteds are organic to subtract each other To without cut, the product then obtained with pure toluene to above-mentioned decompression desolventizing carries out column chromatography and purified pressure-off solvent, obtains 1.9g compound E01, yield 71.4%.Further crude product 300 DEG C of sublimation purifications in chemical gas-phase deposition system, are obtained 1.7g white solid powders, yield 90.0%.The compound, molecular formula C are identified using DEI-MS40H24N2, detected value [M+1]+=533.17, calculated value 532.19.
Embodiment 2：Prepare the compound E26 being previously mentioned
The preparation of intermediate two (a)：
At -78 DEG C and under the protection of nitrogen, 52.1g 4- bromines dibenzofurans (211.0mmol) is taken to be dispersed in In 400g tetrahydrofurans, 93mL then is added dropwise and concentration is the 2.5mol/L hexane solution containing n-BuLi, drips Bi Hou, insulation reaction 2.0 hours, then be to slowly warm up to preserve at -10 DEG C stand-by.
32.5g intermediates one (c) (100.0mmol) are taken to be dissolved in 300g tetrahydrofurans, at a temperature of -10 DEG C, in dropwise addition Phenyl lithium solution is stated, insulation reaction 2.0 hours after finishing is dripped, reaction system is then to slowly warm up to room temperature, then system is toppled over After entering in 200g water, stirring reaction 30min, the extraction of 500g dichloromethane is added afterwards, system layering, is washed from water, Anhydrous sodium sulfate drying.
146.8g manganese dioxide (1.69mol) is added into above-mentioned dichloromethane solution, at 25 DEG C, stirring reaction 4.5 is small When, decompression filters, and filtrate decompression desolventizing is to without cut.Then with petroleum ether and dichloromethane mixed liquor to above-mentioned decompression precipitation The product that agent obtains carries out column chromatography purifying, and the wherein volume ratio of petroleum ether and dichloromethane is petroleum ether：Dichloromethane=10: 1, obtain 33.4g intermediates two (a), yield 68.06%.
The preparation of intermediate two (b)：
At -78 DEG C and under the protection of nitrogen, 25.9g 4- bromines dibenzofurans (105.0mmol) is taken to be dispersed in In 180g tetrahydrofurans, 47mL then is added dropwise and concentration is the 2.5mol/L hexane solution containing n-BuLi, drips Bi Hou, insulation reaction 2.0 hours, then be to slowly warm up to preserve at -10 DEG C stand-by.
Take 24.5g intermediates two (a) (50.0mmol) to be dissolved in 120g tetrahydrofurans, at a temperature of -10 DEG C, be added dropwise above-mentioned Phenyl lithium solution, insulation reaction 2.0 hours after finishing are dripped, reaction system are then to slowly warm up to room temperature, then system is poured into After in 150g water, stirring reaction 30min, the extraction of 300g dichloromethane is added afterwards, system layering, is washed from water, nothing Aqueous sodium persulfate is dried.
73.9g manganese dioxide (850.0mmol) is added into above-mentioned dichloromethane solution, at 25 DEG C, stirring reaction 6 is small When, decompression filters, and filtrate decompression desolventizing is to without cut.Then with petroleum ether and dichloromethane mixed liquor to above-mentioned decompression precipitation The product that agent obtains carries out column chromatography purifying, and the wherein volume ratio of petroleum ether and dichloromethane is petroleum ether：Dichloromethane=5: 1, obtain 23.0g intermediates two (b), yield 70.0%.
The preparation of intermediate two (c)：
At 60 DEG C and under the protection of nitrogen, 19.7g intermediates two (b) (30.0mmol) are taken to be dispersed in 250g chloroforms In, 11.7g NBS (66.0mmol) are then added, after being added dropwise, insulation reaction 12.0 hours, and meanwhile it is anti-using TLC tracking Answer process.After reaction terminates, it is layering after reaction is quenched in 2% aqueous solution of sodium bisulfite to add 200g mass percent concentrations, Washing, desolventizing then is depressurized to organic phase and is extremely recrystallized to give without cut, final choice toluene alcohol mixed solvent in 17.0g Mesosome two (c), yield 84.58%.
The preparation of intermediate two (d)：
Take 16.7g intermediates two (c) (25.0mmol), 1.8g phenyl boric acids (15.0mmol), 3.2g potassium carbonate (23.0mmol) and 30g water, dissolved with 60mL toluene and 30mL ethanol, lead to nitrogen gas stirring 1 hour, to remove the oxygen in reaction bulb Gas.Then Pd (PPh are added3)40.115g (1.0mmol), flow back under strong stirring, course of reaction passes through TLC tracing detections.Instead After answering, 200mL ethyl acetate aqueous phase extracteds, organic phase decompression desolventizing is extremely without cut, then with petroleum ether and dichloromethane The product that alkane mixed liquor obtains to above-mentioned decompression desolventizing carries out the volume ratio of column chromatography purifying, wherein petroleum ether and dichloromethane For petroleum ether：Dichloromethane=15:1, obtain 5.4g intermediates two (d), yield 53.95%.
The preparation of intermediate two (e)：
Take 5.3g intermediates two (d) (8.0mmol), 1.8g bromophenyls boric acid (9.0mmol), 1.7g potassium carbonate (12.0mmol) and 15g water, dissolved with 30mL toluene and 15mL ethanol, lead to nitrogen gas stirring 1 hour, to remove the oxygen in reaction bulb Gas.Then Pd (PPh are added3)40.046g (0.04mmol), flow back under strong stirring, course of reaction passes through TLC tracing detections.Instead After answering, 100mL ethyl acetate aqueous phase extracteds, organic phase decompression desolventizing is extremely without cut, then with petroleum ether and dichloromethane The product that alkane mixed liquor obtains to above-mentioned decompression desolventizing carries out the volume ratio of column chromatography purifying, wherein petroleum ether and dichloromethane For petroleum ether：Dichloromethane=20:1, obtain 3.8g intermediates two (e), yield 64.3%.
E26 preparation：
3.7g intermediates two (e) (5.0mmol), 1.5g DBU (12.0mmol) and 30g DMF are taken, it is small to lead to nitrogen gas stirring 1 When, to remove the oxygen in reaction bulb.Then Pd (PPh are added3)2Cl20.35g (0.05mmol), flow back under strong stirring, instead Process is answered to pass through TLC tracing detections.After completion of the reaction, pour into 100g frozen water, 200mL ethyl acetate aqueous phase extracteds are organic Subtract each other pressure-off solvent to without cut, the product then obtained with pure toluene to above-mentioned decompression desolventizing carries out column chromatography and purified, and obtains Obtain 2.2g compound E26, yield 66.67%.Further crude product 320 DEG C of sublimation purifications in chemical gas-phase deposition system, are obtained To 2.0g white solid powders, yield 90.91%.The compound, molecular formula C are identified using DEI-MS48H26N2O2, inspection Measured value [M+1]+=663.86, calculated value 662.75.
Embodiment 3：Prepare the compound E38 being previously mentioned
The preparation of intermediate three (a)：
At -78 DEG C and under the protection of nitrogen, 16.6g bromobenzenes (105.0mmol) are taken to be dispersed in 150g tetrahydrofurans In, the hexane solution containing n-BuLi that 47mL and concentration are 2.5mol/L, after being added dropwise, insulation reaction is then added dropwise 2.0 hours, then be to slowly warm up to preserve at -10 DEG C stand-by.
Take 24.5g intermediates two (a) (50.0mmol) to be dissolved in 120g tetrahydrofurans, at a temperature of -10 DEG C, be added dropwise above-mentioned Phenyl lithium solution, insulation reaction 2.0 hours after finishing are dripped, reaction system are then to slowly warm up to room temperature, then system is poured into After in 150g water, stirring reaction 30min, the extraction of 300g dichloromethane is added afterwards, system layering, is washed from water, nothing Aqueous sodium persulfate is dried.
73.9g manganese dioxide (850.0mmol) is added into above-mentioned dichloromethane solution, at 25 DEG C, stirring reaction 6 is small When, decompression filters, and filtrate decompression desolventizing is to without cut.Then with petroleum ether and dichloromethane mixed liquor to above-mentioned decompression precipitation The product that agent obtains carries out column chromatography purifying, and the wherein volume ratio of petroleum ether and dichloromethane is petroleum ether：Dichloromethane=12: 1, obtain 21.5g intermediates three (a), yield 75.97%.
The preparation of intermediate three (b)：
At 60 DEG C and under the protection of nitrogen, 17.0g intermediates three (a) (30.0mmol) are taken to be dispersed in 200g chloroforms In, 11.7g NBS (66.0mmol) are then added, after being added dropwise, insulation reaction 10.0 hours, and meanwhile it is anti-using TLC tracking Answer process.After reaction terminates, it is layering after reaction is quenched in 2% aqueous solution of sodium bisulfite to add 200g mass percent concentrations, Washing, desolventizing then is depressurized to organic phase and is extremely recrystallized to give without cut, final choice toluene alcohol mixed solvent in 15.3g Mesosome three (b), yield 87.93%.
The preparation of intermediate three (c)：
Take 14.5g intermediates three (b) (25.0mmol), 1.8g phenyl boric acids (15.0mmol), 3.2g potassium carbonate (23.0mmol) and 30g water, dissolved with 60mL toluene and 30mL ethanol, lead to nitrogen gas stirring 1 hour, to remove the oxygen in reaction bulb Gas.Then Pd (PPh are added3)40.115g (1.0mmol), flow back under strong stirring, course of reaction passes through TLC tracing detections.Instead After answering, 200mL ethyl acetate aqueous phase extracteds, organic phase decompression desolventizing is extremely without cut, then with petroleum ether and dichloromethane The product that alkane mixed liquor obtains to above-mentioned decompression desolventizing carries out the volume ratio of column chromatography purifying, wherein petroleum ether and dichloromethane For petroleum ether：Dichloromethane=22:1,4.5g intermediates three (c) are obtained, yield 31.25%, obtain 3.0g intermediates three (d), Yield 20.83%.
The preparation of intermediate three (e)：
Take 3.5g intermediates three (c) (6.0mmol), 1.4g bromophenyls boric acid (7.0mmol), 1.7g potassium carbonate (12.0mmol) and 15g water, dissolved with 30mL toluene and 15mL ethanol, lead to nitrogen gas stirring 1 hour, to remove the oxygen in reaction bulb Gas.Then Pd (PPh are added3)40.035g (0.03mmol), flow back under strong stirring, course of reaction passes through TLC tracing detections.Instead After answering, 100mL ethyl acetate aqueous phase extracteds, organic phase decompression desolventizing is extremely without cut, then with petroleum ether and dichloromethane The product that alkane mixed liquor obtains to above-mentioned decompression desolventizing carries out the volume ratio of column chromatography purifying, wherein petroleum ether and dichloromethane For petroleum ether：Dichloromethane=20:1, obtain 2.7g intermediates three (e), yield 69.23%.
E38 preparation：
3.3g intermediates three (d) (5.0mmol), 1.5g DBU (12.0mmol) and 30g DMF are taken, it is small to lead to nitrogen gas stirring 1 When, to remove the oxygen in reaction bulb.Then Pd (PPh are added3)2Cl20.35g (0.05mmol), flow back under strong stirring, instead Process is answered to pass through TLC tracing detections.After completion of the reaction, pour into 100g frozen water, 200mL ethyl acetate aqueous phase extracteds are organic Subtract each other pressure-off solvent to without cut, the product then obtained with pure toluene to above-mentioned decompression desolventizing carries out column chromatography and purified, and obtains Obtain 2.2g compound E38, yield 76.92%.Further crude product 300 DEG C of sublimation purifications in chemical gas-phase deposition system, are obtained To 1.9g white solid powders, yield 86.36%.The compound, molecular formula C are identified using DEI-MS42H24N2O, inspection Measured value [M+1]+=573.43, calculated value 572.67.
Embodiment 4：Prepare the compound E53 being previously mentioned
The preparation of intermediate four (a)：
Take 2.4g intermediates three (d) (4.0mmol), 0.9g bromophenyls boric acid (4.4mmol), 1.1g potassium carbonate (8.0mmol) and 10g water, dissolved with 30mL toluene and 15mL ethanol, lead to nitrogen gas stirring 1 hour, to remove the oxygen in reaction bulb Gas.Then Pd (PPh are added3)40.023g (0.02mmol), flow back under strong stirring, course of reaction passes through TLC tracing detections.Instead After answering, 100mL ethyl acetate aqueous phase extracteds, organic phase decompression desolventizing is extremely without cut, then with petroleum ether and dichloromethane The product that alkane mixed liquor obtains to above-mentioned decompression desolventizing carries out the volume ratio of column chromatography purifying, wherein petroleum ether and dichloromethane For petroleum ether：Dichloromethane=15:1, obtain 1.9g intermediates four (a), yield 73.08%.
E53 preparation：
1.6g intermediates four (a) (2.5mmol), 0.9g DBU (5.5mmol) and 30g DMF are taken, it is small to lead to nitrogen gas stirring 1 When, to remove the oxygen in reaction bulb.Then Pd (PPh are added3)2Cl20.18g (0.025mmol), flow back under strong stirring, instead Process is answered to pass through TLC tracing detections.After completion of the reaction, pour into 100g frozen water, 200mL ethyl acetate aqueous phase extracteds are organic Subtract each other pressure-off solvent to without cut, the product then obtained with pure toluene to above-mentioned decompression desolventizing carries out column chromatography and purified, and obtains Obtain 1.0g compound E53, yield 71.43%.Further crude product 320 DEG C of sublimation purifications in chemical gas-phase deposition system, are obtained To 0.9g white solid powders, yield 90.0%.The compound, molecular formula C are identified using DEI-MS42H24N2O, detection It is worth [M+1]+=573.62, calculated value 572.67.
The method prepare compound 1-60 described in embodiment 1-4 prepared according to compound sample, is come using DE I-MS Detection compound, then detect the detected value [M+1] that each compound obtains+And calculated value is as shown in Table 1 below.
The part of compounds mass spectrometric data of the present invention of table 1
From the data of above-mentioned table 1 it is known that the present invention have successfully been obtained the organic photoelectrical material shown in formula I.
The compounds of this invention uses in luminescent device, as hole blocking layer or electron transport layer materials.To the present invention Compound E01, compound E26, compound E38, compound E53 and current material BPhen carry out the test of hot property, test knot Fruit is as shown in table 2.
The heat stability testing of table 2
Note：Glass transition temperature Tg is by differential scanning calorimetry (DSC, German Nai Chi companies DSC204F1 differential scanning calorimetries Instrument) measure, 10 DEG C/min of heating rate；Thermal weight loss temperature Td is the temperature of the weightlessness 0.5% in nitrogen atmosphere, in Japanese Shimadzu It is measured on the TGA-50H thermogravimetric analyzers of company, nitrogen flow 20mL/min；Highest occupied molecular orbital HOMO energy levels And minimum occupied molecular orbital lumo energy is by photoelectron emissions spectrometer (AC-2 type PESA) and ultraviolet specrophotometer (UV) obtained by measuring and calculation, test as atmospheric environment.
From upper table data, there is compound provided by the invention suitable HOMO, lumo energy to be suitable as OLED Hole blocking layer or electron transport layer materials are used as in device；Compound provided by the invention has higher heat steady in upper table It is qualitative so that the made OLED life-span upgrading containing the compounds of this invention.
Organic electroluminescence device embodiment：
The embodiment of organic electroluminescence device is prepared following, used reagent material is as follows：
In organic electroluminescence device embodiment, pass through PR655 spectral scan radiancy meters and U.S. Keithley The test system that Soure Meter 2400 are formed synchronizes measurement detection to the device of gained and obtains the driving of all devices Voltage, quantum efficiency, current efficiency, power efficiency and brightness, wherein above-mentioned all measurements are carried out in atmosphere at room temperature.
Embodiment 1：The preparation of device 1
(a) anode cleaned on transparent substrate layer：Each 15 minutes are cleaned with deionized water, acetone, EtOH Sonicate, so respectively Handled 2 minutes in plasma cleaner afterwards；
(b) the vacuum evaporation hole injection layer on anode, material therefor Hat-CN, thickness 50nm；
(c) on hole injection layer 3, NPB is deposited by vacuum evaporation mode, its thickness is 10nm, this layer of organic material Material uses as hole transmission layer 4；
(d) the co-evaporation luminescent layer 5 on hole transmission layer 4, material selection Alq3, thickness 30nm；
(e) on luminescent layer compound, the electron transfer layer 6 of vacuum evaporation is compound E01 provided by the present invention, thick Spend for 30nm；
(f) on electron transfer layer 6, vacuum evaporation electron injecting layer LiF, thickness 0.5nm, the layer is electron injection Layer 7；
(g) on electron injecting layer 7, vacuum evaporation negative electrode Al, thickness 100nm, the layer is negative electrode 8.
After electroluminescent device accomplished as described above, the driving voltage of measurement device, quantum efficiency, current efficiency, power effect Rate and brightness, its result is in table 3.
Embodiment 2：The preparation of device 2
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E02 of invention is material.The result of organic electroluminescence device made by device 2 is in table 3.
Embodiment 3：The preparation of device 3
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E03 of invention is material.The result of organic electroluminescence device made by device 3 is in table 3.
Embodiment 4：The preparation of device 4
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E04 of invention is material.The result of organic electroluminescence device made by device 4 is in table 3.
Embodiment 5：The preparation of device 5
The difference of the present embodiment device and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation Using compound E05 provided by the present invention as material.The result of organic electroluminescence device made by device 5 is in table 3.
Embodiment 6：The preparation of device 6
The difference of the present embodiment device and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation Using compound E06 provided by the present invention as material.The result of organic electroluminescence device made by device 6 is in table 3.
Embodiment 7：The preparation of device 7
The difference of the present embodiment device and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation Using compound E07 provided by the present invention as material.The result of organic electroluminescence device made by device 7 is in table 3.
Embodiment 8：The preparation of device 8
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E08 of invention is material.The result of electroluminescent device made by device 8 is in table 3.
Embodiment 9：The preparation of device 9
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E09 of invention is material.The result of electroluminescent device made by device 9 is in table 3.
Embodiment 10：The preparation of device 10
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E10 of invention is material.The result of electroluminescent device made by device 10 is in table 3.
Embodiment 11：The preparation of device 11
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E11 of invention is material.The result of electroluminescent device made by device 11 is in table 3.
Embodiment 12：The preparation of device 12
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E12 of invention is material.The result of electroluminescent device made by device 12 is in table 3.
Embodiment 13：The preparation of device 13
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E13 of invention is material.The result of electroluminescent device made by device 13 is in table 3.
Embodiment 14：The preparation of device 14
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E14 of invention is material.The result of electroluminescent device made by device 14 is in table 3.
Embodiment 15：The preparation of device 15
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E15 of invention is material.The result of electroluminescent device made by device 15 is in table 3.
Embodiment 16：The preparation of device 16
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E16 of invention is material.The result of electroluminescent device made by device 16 is in table 3.
Embodiment 17：The preparation of device 17
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E17 of invention is material.The result of electroluminescent device made by device 17 is in table 3.
Embodiment 18：The preparation of device 18
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E18 of invention is material.The result of electroluminescent device made by device 18 is in table 3.
Embodiment 19：The preparation of device 19
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E19 of invention is material.The result of electroluminescent device made by device 19 is in table 3.
Embodiment 20：The preparation of device 20
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E20 of invention is material.The result of electroluminescent device made by device 20 is in table 3.
Embodiment 21：The preparation of device 21
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E21 of invention is material.The result of electroluminescent device made by device 21 is in table 3.
Embodiment 22：The preparation of device 22
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E22 of invention is material.The result of electroluminescent device made by device 22 is in table 3.
Embodiment 23：The preparation of device 23
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E23 of invention is material.The result of electroluminescent device made by device 23 is in table 3.
Embodiment 24：The preparation of device 24
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E24 of invention is material.The result of electroluminescent device made by device 24 is in table 3.
Embodiment 25：The preparation of device 25
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E25 of invention is material.The result of electroluminescent device made by device 25 is in table 3.
Embodiment 26：The preparation of device 26
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E26 of invention is material.The result of electroluminescent device made by device 26 is in table 3.
Embodiment 27：The preparation of device 27
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E27 of invention is material.The result of electroluminescent device made by device 27 is in table 3.
Embodiment 28：The preparation of device 28
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E28 of invention is material.The result of electroluminescent device made by device 28 is in table 3.
Embodiment 29：The preparation of device 29
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E29 of invention is material.The result of electroluminescent device made by device 29 is in table 3.
Embodiment 30：The preparation of device 30
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E30 of invention is material.The result of electroluminescent device made by device 30 is in table 3.
Embodiment 31：The preparation of device 31
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E31 of invention is material.The result of electroluminescent device made by device 31 is in table 3.
Embodiment 32：The preparation of device 32
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E32 of invention is material.The result of electroluminescent device made by device 32 is in table 3.
Embodiment 33：The preparation of device 33
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E33 of invention is material.The result of electroluminescent device made by device 33 is in table 3.
Embodiment 34：The preparation of device 34
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E34 of invention is material.The result of electroluminescent device made by device 34 is in table 3.
Embodiment 35：The preparation of device 35
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E35 of invention is material.The result of electroluminescent device made by device 35 is in table 3.
Embodiment 36：The preparation of device 36
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E36 of invention is material.The result of electroluminescent device made by device 36 is in table 3.
Embodiment 37：The preparation of device 37
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E37 of invention is material.The result of electroluminescent device made by device 37 is in table 3.
Embodiment 38：The preparation of device 38
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E38 of invention is material.The result of electroluminescent device made by device 39 is in table 3.
Embodiment 39：The preparation of device 39
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E39 of invention is material.The result of electroluminescent device made by device 39 is in table 3.
Embodiment 40：The preparation of device 40
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E40 of invention is material.The result of electroluminescent device made by device 40 is in table 3.
Embodiment 41：The preparation of device 41
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E41 of invention is material.The result of electroluminescent device made by device 41 is in table 3.
Embodiment 42：The preparation of device 42
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E42 of invention is material.The result of electroluminescent device made by device 42 is in table 3.
Embodiment 43：The preparation of device 43
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E43 of invention is material.The result of electroluminescent device made by device 43 is in table 3.
Embodiment 44：The preparation of device 44
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E44 of invention is material.The result of electroluminescent device made by device 44 is in table 3.
Embodiment 45：The preparation of device 45
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E45 of invention is material.The result of electroluminescent device made by device 45 is in table 3.
Embodiment 46：The preparation of device 46
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E46 of invention is material.The result of electroluminescent device made by device 46 is in table 3.
Embodiment 47：The preparation of device 47
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E47 of invention is material.The result of electroluminescent device made by device 47 is in table 3.
Embodiment 48：The preparation of device 48
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E48 of invention is material.The result of electroluminescent device made by device 48 is in table 3.
Embodiment 49：The preparation of device 49
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E49 of invention is material.The result of electroluminescent device made by device 49 is in table 3.
Embodiment 50：The preparation of device 50
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E50 of invention is material.The result of electroluminescent device made by device 50 is in table 3.
Embodiment 51：The preparation of device 51
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E51 of invention is material.The result of electroluminescent device made by device 51 is in table 3.
Embodiment 52：The preparation of device 52
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E52 of invention is material.The result of electroluminescent device made by device 52 is in table 3.
Embodiment 53：The preparation of device 53
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E53 of invention is material.The result of electroluminescent device made by device 53 is in table 3.
Embodiment 54：The preparation of device 54
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E54 of invention is material.The result of electroluminescent device made by device 54 is in table 3.
Embodiment 55：The preparation of device 55
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E55 of invention is material.The result of electroluminescent device made by device 55 is in table 3.
Embodiment 56：The preparation of device 56
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E56 of invention is material.The result of electroluminescent device made by device 56 is in table 3.
Embodiment 57：The preparation of device 57
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E57 of invention is material.The result of electroluminescent device made by device 57 is in table 3.
Embodiment 58：The preparation of device 58
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E58 of invention is material.The result of electroluminescent device made by device 58 is in table 3.
Embodiment 59：The preparation of device 59
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E59 of invention is material.The result of electroluminescent device made by device 59 is in table 3.
Embodiment 60：The preparation of device 60
The difference of the present embodiment and device 1 is：The electron transfer layer of the organic electroluminescence device of preparation is with this The there is provided compound E60 of invention is material.The result of electroluminescent device made by device 60 is in table 3.
Comparative example 1：Device 1# preparation
Unlike device comparative example 1 and device 1：The electron transfer layer of organic electroluminescence device is used as electricity using BPhen Sub- transferable material.
Comparative example 2：Device 2# preparation
Unlike device comparative example 2 and device 1：The electron transfer layer of organic electroluminescence device is used as electronics using BCP Transferable material.
Detect to obtain correlated results as shown in Table 3 below to device 1-60 and device 1# and device 2#：
The device data of table 3
As shown in Table 3, photoelectric material of the present invention can be applied to electroluminescent device making, and can obtain good Performance.Material of the present invention uses as the electron transport material of electroluminescent device, and its driving voltage is below using Device 1#s and device 2# of the existing conventional BPhen and BCP as electron transport material.In addition, with device 1# and device 2# phases Than device embodiments 1-60 power and life-span are obviously improved.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.

Claims (7)

1. a kind of organic photoelectrical material containing indeno ferrosin structure, it is characterised in that there is molecular structure shown in formula 1：
Wherein, R1For phenyl or dibenzofuran group, R2For one kind in hydrogen, phenyl or dibenzofuran group, R3Concrete structure Formula is：
2. a kind of preparation method of the organic photoelectrical material containing indeno ferrosin structure, it is characterised in that comprise the following steps：
Step 1：Under the protection of inert gas and under -100~0 DEG C of temperature conditionss, by 2.0~2.4 molar equivalents N-BuLi is added in the THF solution of 4, the 7- dibromo phenanthrolines containing 1.0 molar equivalents, is reacted, adds 2.0 The trim,ethylchlorosilane of~2.2 molar equivalents is reacted, after obtaining the reaction system containing intermediate one, then by it is above-mentioned containing The reaction system of intermediate one is to slowly warm up to room temperature, then pours into water, stirring reaction 10~50mi n, then adds acetic acid Ethyl ester is layered, washed successively, then depressurizes desolventizing to without cut to organic phase, obtains intermediate one；
Step 2：Under the protection of inert gas and under -100~0 DEG C of temperature conditionss, by 1.0~1.1 molar equivalents N-BuLi is added to the aryl halides R containing 1.0 molar equivalents1In-Br THF solution, first step reaction is carried out, is obtained R1Lithium salt solution, then under -60~10 DEG C of temperature conditionss, by above-mentioned R1Lithium salt solution be added dropwise to and obtained containing step 1 Intermediate one organic solution in, carry out second step reaction, then plus water carries out that reaction is quenched, then is extracted with dichloromethane, Extract is handled with the manganese dioxide of 4~10.0 molar equivalents, after obtaining the reaction system containing intermediate two, then will be above-mentioned Reaction system containing intermediate two is filtered under diminished pressure, and the concentration of gained filtrate decompression, is then mixed with petroleum ether and dichloromethane Close liquid to be concentrated under reduced pressure to above-mentioned, obtained product carries out column chromatography purifying, and the wherein volume ratio of petroleum ether and dichloromethane is stone Oily ether：Dichloromethane=5~60:1, obtain intermediate two；
Step 3：Under the protection of inert gas and under -100~0 DEG C of temperature conditionss, by 1.0~1.1 molar equivalents N-BuLi is added to the aryl halides R containing 1.0 molar equivalents2- Br organic solution, first step reaction is carried out, obtains R2 Lithium salt solution, then under -60~10 DEG C of temperature conditionss, by above-mentioned R2Lithium salt solution be added dropwise to and obtained containing step 2 Intermediate two organic solution in, carry out second step reaction, then plus water carries out that reaction is quenched, then is extracted with dichloromethane, Extract is handled with the manganese dioxide of 4~10.0 molar equivalents, obtains the reaction system containing intermediate three, by it is above-mentioned containing The reaction system of intermediate three is filtered under diminished pressure, gained filtrate decompression concentration, then with petroleum ether and dichloromethane mixed liquor It is concentrated under reduced pressure to above-mentioned, obtained product carries out column chromatography purifying, and the wherein volume ratio of petroleum ether and dichloromethane is petroleum ether： Dichloromethane=5~60:1, obtain intermediate three；
Step 4：Under the protection of inert gas and under 0~60 DEG C of temperature conditionss, by the NBS of 2.1~3.0 molar equivalents It is added in the organic solution of the intermediate three obtained containing step 3, obtains the reaction system containing intermediate four, contains above-mentioned There is the reaction system of intermediate four, add the solution of sodium bisulfite that mass percent concentration is 2% and carry out that reaction is quenched, then Chloroform is added, after layering, adds water washing, after the completion of washing, desolventizing is depressurized to organic phase to without cut, after desolventizing, is used Toluene alcohol mixed solvent is recrystallized, and wherein the volume ratio of toluene and ethanol is 2:3~8；Or with petroleum ether and dichloromethane Alkane mixed liquor carries out column chromatography purifying to the residue after above-mentioned be concentrated under reduced pressure, and the volume ratio of wherein petroleum ether and dichloromethane is 5~60:1, obtain intermediate four；
Step 5：Intermediate four, the aryl boric acid R that step 4 is obtained3-B(OH)2And alkaline matter, it is added to toluene, diformazan In benzene, DMF or dimethyl acetamide, under inert gas shielding, catalyst is added, then, 60~ After being reacted 2~24 hours at 150 DEG C, the reaction system containing intermediate five is obtained, by the above-mentioned reactant containing intermediate five System's layering, is washed with water, then desolventizing is depressurized to organic phase to without cut, is then purified with column chromatography, the purifying is used The mixed liquor or petroleum ether of petroleum ether and dichloromethane and the mixed liquor of ethyl acetate are eluted, wherein petroleum ether and dichloro The volume ratio of methane is 2~60:1, the volume ratio of petroleum ether and ethyl acetate is 2~35:1, obtain intermediate five；
Step 6：Intermediate five, bromophenyl boric acid and alkaline matter that step 5 obtains are added to toluene, dimethylbenzene, N, N- In dimethylformamide or dimethyl acetamide, under inert gas shielding, catalyst is added, it is then, anti-at 60~150 DEG C After answering 2~24 hours, the reaction system containing intermediate six is obtained, the above-mentioned reaction system containing intermediate six is layered, used Water washing, then desolventizing is depressurized extremely without cut to organic phase, then purified with column chromatography, above-mentioned purifying petroleum ether and two The mixed liquor or petroleum ether of chloromethanes and the mixed liquor of ethyl acetate are eluted, wherein the volume of petroleum ether and dichloromethane Than for 2~60:1, the volume ratio of petroleum ether and ethyl acetate is 2~35:1, obtain intermediate six；
Step 7：The intermediate six and alkaline matter that are obtained in step 6 are added to toluene, dimethylbenzene, N, N- dimethyl formyls In amine or dimethyl acetamide, under inert gas shielding, catalyst is added, then, it is small that 2~24 are reacted at 60~170 DEG C Shi Hou, that is, the organic photoelectrical material containing indeno ferrosin structure is obtained, wherein, R1For phenyl or dibenzofuran group, R2 For one kind in hydrogen, phenyl or dibenzofuran group, R3Concrete structure formula be：
The structural formula of intermediate one to the intermediate six is respectively：
3. a kind of preparation method of organic photoelectrical material containing indeno ferrosin structure according to claim 2, it is special Sign is, in step 5, the alkaline matter is one kind or more in sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide Kind；The catalyst is in palladium, four (triphenylphosphines), bi triphenyl phosphorus palladium chloride and three (dibenzalacetone) two palladium One or more；The temperature of the reaction is 60~90 DEG C, and the time is 4~8 hours；The alkaline matter and intermediate four Mol ratio is 1.3~3.0:1.
4. a kind of preparation method of organic photoelectrical material containing indeno ferrosin structure according to claim 3, it is special Sign is, in step 6, the alkaline matter is one kind or more in sodium carbonate, potassium carbonate, sodium hydroxide and potassium hydroxide Kind；The catalyst is in palladium, four (triphenylphosphines), bi triphenyl phosphorus palladium chloride and three (dibenzalacetone) two palladium One or more；The temperature of the reaction is 60~90 DEG C, and the time is 4~8 hours；The alkaline matter and intermediate five Mol ratio is 1.3~3.0:1；The mol ratio of the catalyst and intermediate five is 0.001~0.1:1.
5. a kind of preparation method of organic photoelectrical material containing indeno ferrosin structure according to claim 3, it is special Sign is, in step 7, the alkaline matter is the one or more in triethylamine, DBU, caustic alcohol；The catalyst is selected from vinegar One or more in sour palladium, four (triphenylphosphines), bi triphenyl phosphorus palladium chloride, three (dibenzalacetone) two palladium；Reaction Temperature is preferably 100~170 DEG C, and the reaction time is preferably 6~12 hours；The mol ratio of the alkaline matter and intermediate six is 1.3~3.0:1；The mol ratio of the catalyst and intermediate six is 0.001~0.1:1.
6. a kind of preparation method of organic photoelectrical material containing indeno ferrosin structure according to claim 3, it is special Sign is, in step 5, step 6 and step 7, phosphine system part is added when adding catalyst, phosphine system part is 1,3- double Double diphenylphosphine -9,9- dimethyl the xanthenes of (diphenylphosphine) propane, 4,5-, 2- dicyclohexyl phosphine -2', 6'- dimethoxy connection One or more in benzene or tri-butyl phosphine tetrafluoroborate.
7. a kind of application of the organic photoelectrical material containing indeno ferrosin structure, it is characterised in that in organic electroluminescence In part, at least one functional layer contains the organic photoelectrical material containing indeno ferrosin structure described in claim 1.
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