CN107501101A - A kind of organic light emission small molecule material of the fluorenes of indenes containing naphtho- unit and preparation method and application - Google Patents

A kind of organic light emission small molecule material of the fluorenes of indenes containing naphtho- unit and preparation method and application Download PDF

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CN107501101A
CN107501101A CN201710766030.7A CN201710766030A CN107501101A CN 107501101 A CN107501101 A CN 107501101A CN 201710766030 A CN201710766030 A CN 201710766030A CN 107501101 A CN107501101 A CN 107501101A
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fluorenes
indenes
layer
light emission
small molecule
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应磊
胡黎文
郭婷
杨伟
彭俊彪
曹镛
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South China University of Technology SCUT
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Abstract

The invention discloses a kind of organic light emission small molecule material of the fluorenes of indenes containing naphtho- unit and preparation method and application.Suzuki coupling reactions of the invention by fragrant ring element and naphtho- indenes fluorenes unit, the organic light emission small molecule material of the fluorenes unit of indenes containing naphtho- is prepared.The organic light emission small molecule material of the fluorenes unit of indenes containing naphtho- of the present invention has high heat endurance, optical stability, excellent electronics and hole transport performance, high fluorescence quantum efficiency, and there are excellent electroluminescent properties, simultaneously the luminescent layer based on the material prepare organic electroluminescence device technique it is simple, in the potential industrialized production applied to organic electroluminescence device.

Description

A kind of organic light emission small molecule material of the fluorenes of indenes containing naphtho- unit and preparation method thereof with Using
Technical field
The invention belongs to technical field of organic electroluminescence, and in particular to a kind of organic light emission of the fluorenes of indenes containing naphtho- unit is small Molecular material and preparation method and application.
Background technology
Relative to liquid crystal display (LCD), organic electroluminescent LED (OLEDs) lights because of its wide viewing angle, actively, is low Operating voltage, it is ultra-thin, flexible can make and obtain the extensive concern of scientific research institution and industrial circle the advantages that low-power consumption.At present, OLEDs displays have been widely used in mobile phone screen, and large-area OLEDs TV has been developed that and launched In market.But OLED due to it is expensive the shortcomings of, so as to limit the use of OLED extensive large area.So exploitation Yields in advanced luminescent material, raising device preparation technology level and device fabrication process etc. is the important side of OLED development To.
In order to realize that OLED lights, fluorescent material and the major class material of phosphor material two can be selected.Wherein, phosphorescence material Material with high quantum efficiency and luminous efficiency due to arousing widespread concern, and still, phosphor material is due to containing weight It is relatively low with the life-span that metal makes its expensive, so as to constrain its use in OLED.Now, in order to realize OLED coloured silk Color shows that research worker mainly focuses on research work the red, green, blue three primary colours fluorescence of high stability and high-luminous-efficiency The exploitation of material.By the development of nearly more than 20 years, some efficient fluorescent small molecule materials were reported out, for example isatin spreads out Biological red light material (Opt.Eng., 2011,50 (4), 044002.), coumarin derivative green light material (Org.Lett., 2004,6 (8), 1241-1244.) and blue light material trimerization diphenylethyllene benzene (Adv.Mater., 2005,17 (22):2710- 2714.) etc..
The naphtho- indenes fluorenes unit plane regularity of terphenyl structure is good, conjugated system is big, fluorescence quantum efficiency is high, structure is easy Modification, the advantages that transmittability is strong, extensive research and application are obtained in organic electronic field.Therefore, by naphtho- indenes fluorenes list Member is incorporated into small molecule emitter material, is expected to obtain the OLED display device of high luminescence energy.
The content of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of organic light emission of the fluorenes of indenes containing naphtho- unit Small molecule material.For the small molecule material using naphtho- indenes fluorenes unit as core, different fragrant ring elements is arm.
The present invention also aims to provide a kind of organic light emission small molecule material of the described fluorenes of indenes containing naphtho- unit Preparation method.Fragrant ring element is introduced into alkyl fluorenes by this method, obtains small point of the organic light emission of the fluorenes unit of indenes containing naphtho- Sub- material.
The present invention also aims to the organic light emission small molecule material for providing a kind of described fluorenes of indenes containing naphtho- unit to exist Prepare the application in the luminescent layer of organic electroluminescence device.
The purpose of the present invention is achieved through the following technical solutions.
A kind of organic light emission small molecule material of the fluorenes of indenes containing naphtho- unit, chemical structural formula are as follows：
Ar1、Ar2、Ar3、Ar4、Ar5、Ar6Structure it is identical or different；Ar1、Ar2、Ar3、Ar4、Ar5And Ar6Independent choosing One kind from following structural formula and its derivative：
Wherein, X O, S, Se, Te or N-R；Y is C, Si or Ge；
R is H, C1~C30Straight chain or branched alkyl,R1For H, C1~C30 Straight chain or branched alkyl.
The method for preparing a kind of organic light emission small molecule material of the described fluorenes of indenes containing naphtho- unit, by fragrant ring element with Naphtho- indenes fluorenes unit is coupled, and obtains the organic light emission small molecule material of the fluorenes unit of indenes containing naphtho-, the synthesis in preparation process Route is as follows：
Ar represents Ar1、Ar2、Ar3、Ar4、Ar5Or Ar6。
The method for preparing a kind of organic light emission small molecule material of the described fluorenes of indenes containing naphtho- unit, comprises the following steps：
(1) under cryogenic, 7,13- dihydrobenzos [g] indenes [1,2-b] fluorenes of alkylation is dissolved in chloroform In, bromine is added dropwise in inert gas environment dropwise, stirring is reacted；After reaction terminates, extracted, concentrated with dichloromethane, done It is dry, column chromatography purification, two bromo- 7 are obtained, 7,13,13- alkyl -7,13- dihydrobenzo [g] indenes [1,2-b] fluorenes；
(2) it is under inert gas environment, two bromo- 7,7,13,13- alkyl -7,13- dihydrobenzo [g] indenes [1,2-b] fluorenes are molten In toluene, Ar is added1~Ar6Aryl-boric acid ester or Ar1~Ar6Aryl boric acid, add TBAB, four fourths Base ammonium bromide, potassium carbonate and tetrakis triphenylphosphine palladium, heating carry out Suzuki coupling reactions；After reaction terminates, room is cooled to Temperature, extract, dry, column chromatography purification, obtain the organic light emission small molecule material of the fluorenes unit of indenes containing naphtho-.
Further, in step (1), the temperature of the low temperature is -20~25 DEG C.
Further, in step (1), 7,13- dihydrobenzos [g] indenes [1, the 2-b] fluorenes of the alkylation and rubbing for bromine You are than being 1:2~6.
Further, in step (1), the inert gas includes argon gas.
Further, in step (1), the time of the reaction is 2~24 hours.
Further, in step (2), the inert gas includes argon gas.
Further, in step (2), described two bromo- 7,7,13,13- alkyl -7,13- dihydrobenzo [g] indenes [1,2-b] Fluorenes, Ar1~Ar6Aryl-boric acid ester or Ar1~Ar6Aryl boric acid, TBAB, potassium carbonate and four (triphenyls Phosphine) palladium mol ratio be 1：2~6：0.05~0.2：5~10：0.02-0.1.
Further, in step (2), the Suzuki coupling reactions are reacted 8~48 hours at 50~120 DEG C.
A kind of organic light emission small molecule material of the described fluorenes of indenes containing naphtho- unit is preparing organic electroluminescence device Application in luminescent layer, the organic light emission small molecule material of the fluorenes unit of indenes containing naphtho- is prepared into film forming by solution processing method, obtained To the luminescent layer of organic electroluminescence device.
Further, the structure of the organic electroluminescence device is substrate, anode layer, the hole note for including stacking gradually Enter layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and cathode layer.
Further, the structure of the organic electroluminescence device is substrate, cathode layer, the electronics note for including stacking gradually Enter layer, electron transfer layer, luminescent layer, hole transmission layer, hole injection layer and anode layer.
Further, the thickness of the luminescent layer is 10~1000nm.
Further, the solution processing method includes spin coating, brushing, spraying, dip-coating, roller coat, silk-screen printing, printing or spray Black Method of printing.
Compared with prior art, the invention has the advantages that with benefit effect：
(1) the invention provides a kind of organic light emission small molecule material of the new fluorenes of indenes containing naphtho- unit, and with excellent Good electroluminescent properties, at the same the luminescent layer based on the material prepare organic electroluminescence device technique it is simple, it is potential should For in the industrialized production of organic electroluminescence device；
(2) the organic light emission small molecule material of the fluorenes unit of indenes containing naphtho- of the invention is naphtho- indenes fluorenes unit and aromatics The micromolecular compound that thing unit is constructed, there is high heat endurance, optical stability, excellent electronics and hole transport ability Energy, high fluorescence quantum efficiency；
(3) the organic light emission small molecule material of the fluorenes unit of indenes containing naphtho- of the invention for donor-acceptor-donor or donor- The small molecule material of acceptor type, due to the interaction between donor and acceptor, intramolecular easily forms electric charge transfer, makes it Highest occupied molecular orbital and the minimum molecular orbit electron cloud that is not occupied separate, and the electron cloud of excitation state and ground state overlaps Reduce, so as to cause radiative transistion probability to reduce, improve the luminous efficiency of material and luminous excitation；
(4) the organic light emission small molecule material of the fluorenes unit of indenes containing naphtho- of the invention is free of electron withdraw group, can effectively keep away Exempt from customs examination body-electric charge transfer caused by receptor structure intramolecular, the efficiency high of obtained luminescent material and the excitation with saturation；
(5) preparation technology of the organic light emission small molecule material of the fluorenes unit of indenes containing naphtho- of the invention is simple, is advantageous to big Technical scale metaplasia is produced.
Brief description of the drawings
Fig. 1 is fluorescence spectras of the small light-emitting molecules material M1 in different solvents；
Fig. 2 is small light-emitting molecules material M2 cyclic voltammetry curve figure；
Fig. 3 is small light-emitting molecules material M3 thermogravimetric curve figure；
Fig. 4 is small light-emitting molecules material M4 differential scanning calorimetric curve figure；
Fig. 5 is the electroluminescent light spectrogram of the electroluminescent device based on small light-emitting molecules material M1 and M2；
Fig. 6 is current efficiency-current density plot figure of the electroluminescent device based on small light-emitting molecules material M1 and M2.
Embodiment
Technical scheme is described further below in conjunction with specific embodiment and accompanying drawing, but it is of the invention and unlimited In this.
Embodiment 1
The synthesis of the bromo- 9,9- n-hexyls fluorenes of 2-
In 500mL there-necked flasks, 2- bromines fluorenes (18.4g, 75mmol) and dimethyl sulfoxide (DMSO) 200mL, room temperature condition are added Under be added dropwise 50wt% sodium hydrate aqueous solution (30g/30ml deionized waters, 0.75mol) dropwise, stirring reaction 2 hours, then With syringe injection bromo n-hexane (27.2g, 165mmol)；Reaction 12 hours, reactant mixture is poured into water, uses dichloro Methane extracts, and after organic layer is washed completely with saline solution, adds anhydrous magnesium sulfate to dry；After solution concentration, thick pale yellow is obtained Shape crude product, (eluant, eluent selection petroleum ether) is purified with silica gel column chromatography, obtains white solid, yield 89%.
Embodiment 2
The synthesis of 2- (4,4,5,5- tetramethyl -1,3,2- dioxaborinate -2- bases) -9,9- n-hexyl fluorenes
Bromo- 9, the 9- n-hexyls fluorenes (20.7g, 50mmol) of 2- are dissolved in refined anhydrous THF (200mL), at -78 DEG C The lower n-BuLi (25ml, 60mmol) that 2.4mol/L is gradually added dropwise, react 2 hours, be then added dropwise 2- isopropoxies -4,4,5, 5- tetramethyls -1,3,2- dioxaborinates (13.0g, 70.0mmol), continue reaction 1 hour at -78 DEG C, it is anti-to be warming up to room temperature Answer 24 hours；Reactant mixture is poured into water, is extracted with ethyl acetate, after organic layer is washed completely with saline solution, is added anhydrous Magnesium sulfate is dried；After solution concentration, obtain thick pale yellow shape crude product, purified with silica gel column chromatography (eluant, eluent select petroleum ether/ Dichloromethane=5/1, v/v), obtain yellow solid, yield 78%.
Embodiment 3
The synthesis of bromo- 2 2-methyl naphthoates of 1-
Bromo- 2 naphthoic acids (15g, 59.8mmol) of 1- are dissolved in 200ml methanol, and toward being added dropwise to 50ml's in reaction solution The concentrated sulfuric acid, after stirring 12 hours under normal temperature, stop reaction, reaction is quenched with water, is extracted with dichloromethane and uses anhydrous sulphur Sour magnesium is dried, and khaki solid is obtained after solution concentration, and (eluant, eluent selection petroleum ether/dichloromethane is purified with silica gel column chromatography Alkane=5/1, v/v), obtain white solid, yield 95%.
Embodiment 4
The synthesis of methyl 1- (9,9- dihexyl -9H- fluorenes -2- bases) -2- naphthoates
Under the conditions of closed, logical argon gas, by 2- (4,4,5,5- tetramethyls -1,3,2- dioxaborinate -2- bases), -9,9- is just Bromo- 2 2-methyl naphthoate (9.0g, 33.9mmol) of hexyl fluorenes (13g, 28.2mmol), 1-, TBAB (0.91g, 2.82mmol)、Pd(PPh3)4(3.3g, 2.82mmol), KCO3 (16.7g, 157.2mmol), organic base (tetraethyl hydroxide Ammonium, 22mL), deionized water 30mL and 200ml toluene in 500ml reaction bulbs, be heated to 110 DEG C react 48 hours；Will be anti- After answering liquid to concentrate, with silica gel column chromatography (eluant, eluent selects petroleum ether/dichloromethane=5/1, v/v), white solid, yield are obtained 60%.
Embodiment 5
The synthesis of 7- (1- (9,9- dihexyl -9H- fluorenes -2- bases) naphthalene -2- bases) tridecane -7- alcohol
Methyl 1- (9,9- dihexyl -9H- fluorenes -2- bases) -2- naphthoates (10.0g, 18.7mmol) are dissolved in refined Anhydrous THF in (100ml), dropwise be added dropwise 1.0mol/L octyls magnesium bromide (93.5ml, 93.5mmol), be warming up to 120 DEG C It is heated to reflux, reacts 16 hours；Room temperature is cooled to, reactant mixture is poured into water, is extracted with ethyl acetate, organic layer food After salt solution washing completely, dried with anhydrous magnesium sulfate；After solution concentration, next step reaction is directly carried out.
Embodiment 6
The synthesis of 7,7,13,13- tetra- n-hexyl -7,13- dihydrobenzos [g] indenes [1,2-b] fluorenes
7- (1- (9,9- dihexyl -9H- fluorenes -2- bases) naphthalene -2- bases) tridecane -7- alcohol (6.60g, 10mmol) is dissolved in In 30mL dichloromethane, 3.5mL Eorontrifluoride etherates solution (concentration 46.5%) is added, is reacted 1 hour；After solution concentration, Purified with silica gel column chromatography method, obtain white solid；With ethyl alcohol recrystallization twice, white crystal, yield 82.6% are filtered to obtain.
Embodiment 7
The synthesis of bromo- n-hexyl -7,13- dihydrobenzos [g] indenes [1,2-b] fluorenes of 7,7,13,13- tetra- of 5,11- bis-
Under the conditions of 0 DEG C, by 7,7,13,13- tetra- n-hexyl -7,13- dihydrobenzo [g] indenes [1,2-b] fluorenes (5.0g, 7.80mmol) it is dissolved in 45ml mL chloroforms, bromine (2.62g, 16.4mmol) is added dropwise in argon gas environment dropwise, Stirring is reacted；After reaction 8 hours, extracted, concentrated with dichloromethane, dried, purified by silica gel column chromatography, eluant, eluent choosing Petroleum ether is selected, obtains 5,11- bis- bromo- 7,7,13,13- tetra- n-hexyl -7,13- dihydrobenzo [g] indenes [1,2-b] fluorenes.
Embodiment 8
Double (9- triphenylamine bases) -7,7,13,13- four n-hexyl -7,13- dihydrobenzos [g] indenes [1,2-b] fluorenes of 5,11- (M1) synthesis：
Under the conditions of closed, logical argon gas, by 5,11- bis- bromo- 7,7,13,13- tetra- n-hexyl -7,13- dihydrobenzo [g] indenes [1,2-b] fluorenes (1.5g, 1.87mmol), 4- (4,4,5,5- tetramethyls -1,3,2- dioxaborinate -2- bases)-triphenylamine (1.74g, 4.69mmol), TBAB (61mg, 0.19mmol) and Pd (PPh3)4(0.22g, 0.19mmol) is dissolved in In toluene (40ml), it is heated to 110 DEG C and produces backflow, the K that then will now match somebody with somebody2CO3The aqueous solution (2mol/L, 9.4ml, Reaction system 18.7mmol) is added, is reacted 48 hours under counterflow condition；Solvent is rotated, carries out column chromatography, eluent is oil Ether：Ethyl acetate=5:1 (v/v), then recrystallized in tetrahydrofuran/ethanol (5/100, v/v), obtain yellow powder The organic light emission small molecule material M1 of 1.37g, i.e. indenes containing naphtho- fluorenes unit, yield 66%.
Photoluminescence spectras of the organic light emission small molecule material M1 of preparation in toluene and chloroform is as shown in figure 1, from figure In as can be seen that maximum emission peaks of the organic light emission small molecule material M1 in toluene be located at 488nm, maximum in chloroform is sent out Penetrate peak and be located at 494nm, the two peak value approaches, and illustrates that Intramolecular electron transfer effect is weak.
Embodiment 9
N-hexyl -7,13- the dihydrobenzos [g] of 5,11- bis- (9,9- dihexyl -9H- fluorenyl -2- bases) -7,7,13,13- four The synthesis of indenes [1,2-b] fluorenes (M2)：
Under the conditions of closed, logical argon gas, by 5,11- bis- bromo- 7,7,13,13- tetra- n-hexyl -7,13- dihydrobenzo [g] indenes [1,2-b] fluorenes (0.97g, 1.21mmol), 2- (4,4,5,5- tetramethyls -1,3,2- dioxaborinate -2- bases) -9,9'- bis- are pungent Base fluorenes (1.56g, 3.03mmol), TBAB (39mg, 0.121mmol) and Pd (PPh3)4(0.14g, 0.121mmol) it is dissolved in toluene (40ml), is heated to 75 DEG C, treats that solid all dissolves, the K that will now match somebody with somebody2CO3The aqueous solution (2mol/ L, 6.1ml, 12.1mmol) reaction system is added, reacted 24 hours at 75 DEG C；Rotate solvent, carry out column chromatography, eluent according to Secondary is petroleum ether：Dichloromethane=5:1 (v/v), petroleum ether：Dichloromethane=1:3 (v/v), then in tetrahydrofuran/ethanol Recrystallize (5/100, v/v), obtain white powder 1.25g, the i.e. fluorenes of indenes containing naphtho- unit organic light emission small molecule material M2, produce Rate 73.1%.
The organic light emission small molecule material M2 of preparation circulation volt curve map is as shown in Fig. 2 during electro-chemical test, Yi Ermao Iron is standard specimen, and its vacuum level is 4.8eV, and under the conditions of same test, the initial value for measuring the oxidizing potential of ferrocene is The initial value of 0.39V, M2 oxidizing potential is 1.74V, and specific data are shown in Table 1 (a：Calculate and obtain from HOMO energy levels and optical band gap ).
The small light-emitting molecules M2 of table 1 electrochemical data
The data measured based on table 1, the calculation formula according to the energy level (HOMO) of the highest occupied molecular orbital of compound are： EHOMO=-e (Eox+ 4.8-0.39) (eV), the HOMO energy levels that can draw small light-emitting molecules M1 are -6.13eV, and according to optical ribbon Gap (Eg) the energy level E of minimum non-occupied orbital (LUMO) can be calculatedLUMO=Eg-EHOMO, it is -3.60eV.
Embodiment 10
7,7,13,13- tetra- n-hexyl -5,11- two (pyrenyl -1- bases) -7,13- dihydrobenzos [g] indenes [1,2-b] fluorenes (M3) Synthesis：
Under the conditions of closed, logical argon gas, by 5,11- bis- bromo- 7,7,13,13- tetra- n-hexyl -7,13- dihydrobenzo [g] indenes [1,2-b] fluorenes (1.45g, 1.82mmol), 2- (1- pyrenyls) -4,4,5,5- tetramethyls -1,3, the ring of 2- dioxies boron penta (1.49g, 4.55mmol), TBAB (59mg, 0.182mmol) and Pd (PPh3)4(0.21g, 0.182mmol) is dissolved in toluene In (40ml), it is heated to 110 DEG C and produces backflow, the K that then will now match somebody with somebody2CO3The aqueous solution (2mol/L, 9.1ml, 18.2mmol) adds Enter reaction system, reacted 48 hours under counterflow condition；Solvent is rotated, carries out column chromatography, eluent is petroleum ether：Ethyl acetate =4:1 (v/v), is then recrystallized in chlorobenzene, obtains yellow powder 1.07g, i.e. the organic light emission of the fluorenes of indenes containing naphtho- unit is small Molecular material M3, yield 56.5%.
The organic light emission small molecule material M3 of preparation thermogravimetric curve is as shown in figure 3, it can be seen that work as chemical combination During thing M3 Mass lost 5%, corresponding temperature is 441 DEG C, i.e. M3 heat decomposition temperature is 441 DEG C, has excellent heat Stability.
Embodiment 11
2,2 "-(7,7,13,13- tetra- n-hexyl -7,13- dihydrobenzos [g] indenes [1,2-b] fluorenes -5,11- bases) -9,9 ' spiral shells The synthesis of fluorenes (M4)：
Under the conditions of closed, logical argon gas, by 5,11- bis- bromo- 7,7,13,13- tetra- n-hexyl -7,13- dihydrobenzo [g] indenes [1,2-b] fluorenes (1.00g, 1.25mmol), 2- (fluorenes -2- bases of 9,9'- spiral shell two) -4,4,5,5- tetramethyls -1,3,2- dioxies boron penta Ring (1.38g, 3.13mmol), TBAB (40mg, 0.125mmol) and Pd (PPh3)4(72.2mg, 62.5 μm of mol) It is dissolved in toluene (40ml), is heated to 75 DEG C, treats that solid all dissolves, the K that will now match somebody with somebody2CO3The aqueous solution (2mol/L, 6.3ml, Reaction system 12.5mmol) is added, is reacted 24 hours under 110 DEG C of counterflow conditions；Solvent is rotated, is extracted with dichloromethane, oil After mutually being dried with anhydrous magnesium sulfate, vacuum rotary steam falls solvent, and column chromatography is carried out in silicagel column, and eluent is petroleum ether：Dichloro Methane=2:1 (v/v), obtained solid recrystallize in tetrahydrofuran/ethanol (5/100, v/v), obtain pale yellow powder The organic light emission small molecule material M4 of 1.07g, i.e. indenes containing naphtho- fluorenes unit, yield 67.5%.
The organic light emission small molecule material M4 of preparation differential scanning calorimetric curve as shown in figure 4, it can be seen that During temperature is by 40 DEG C of 180 DEG C of rises, glass transition only occurs for M4, and the temperature of its glass transition is 136 DEG C, is said Bright small light-emitting molecules M4 heat endurance is good.
Embodiment 12
7,7,13,13- tetra- n-hexyl -5,11- two (naphthyl -1- bases) -7,13- dihydrobenzos [g] indenes [1,2-b] fluorenes (M5) Synthesis：
Under the conditions of closed, logical argon gas, by 5,11- bis- bromo- 7,7,13,13- tetra- n-hexyl -7,13- dihydrobenzo [g] indenes [1,2-b] fluorenes (1.20g, 1.5mmol), β-naphthalene boronic acids (645g, 3.75mmol), TBAB (48mg, 0.15mmol) And Pd (PPh3)4(87mg, 75 μm of mol) are dissolved in toluene (40ml), are heated to 75 DEG C, treat that solid all dissolves, by what is now matched somebody with somebody K2CO3The aqueous solution (2mol/L, 7.5ml, 15mmol) adds reaction system, is reacted 24 hours at 75 DEG C；Solvent is rotated, is carried out Column chromatography, eluent are followed successively by petroleum ether：Dichloromethane=10:1 (v/v), petroleum ether：Dichloromethane=1:1 (v/v), then Recrystallized in tetrahydrofuran/ethanol (5/100, v/v), obtain pale yellow powder 0.78g, i.e., the fluorenes of indenes containing naphtho- unit is organic Small light-emitting molecules material M5, yield 58%.
Embodiment 13
7,7,13,13- tetra- n-hexyl -5,11- two (naphthyl -2- bases) -7,13- dihydrobenzos [g] indenes [1,2-b] fluorenes (M6) Synthesis：
Under the conditions of closed, logical argon gas, by 5,11- bis- bromo- 7,7,13,13- tetra- n-hexyl -7,13- dihydrobenzo [g] indenes [1,2-b] fluorenes (1.20g, 1.5mmol), α-naphthalene boronic acids (645g, 3.75mmol), TBAB (48mg, 0.15mmol) And Pd (PPh3)4(87mg, 75 μm of mol) are dissolved in toluene (40ml), are heated to 75 DEG C, treat that solid all dissolves, by what is now matched somebody with somebody K2CO3The aqueous solution (2mol/L, 7.5ml, 15mmol) adds reaction system, is reacted 24 hours at 75 DEG C；Solvent is rotated, is carried out Column chromatography, eluent are followed successively by petroleum ether：Dichloromethane=10:1 (v/v), petroleum ether：Dichloromethane=1:1 (v/v), then Recrystallized in tetrahydrofuran/ethanol (5/100, v/v), obtain pale yellow powder 0.95g, i.e., the fluorenes of indenes containing naphtho- unit is organic Small light-emitting molecules material M6, yield 70.8%.
Embodiment 14
Double (9- diisooctyl -3- carbazyls) -7,7,13,13- four n-hexyl -7,13- dihydrobenzos [g] indenes of 5,11- [1, 2-b] fluorenes (M7) synthesis：
Under the conditions of closed, logical argon gas, by 5,11- bis- bromo- 7,7,13,13- tetra- n-hexyl -7,13- dihydrobenzo [g] indenes [1,2-b] fluorenes (0.97g, 1.21mmol), 3- (4,4,5,5- tetramethyls -1,3,2- dioxaborinate -2- bases) -9- iso-octyl clicks Azoles (1.23g, 3.03mmol), TBAB (40mg, 0.121mmol) and Pd (PPh3)4(0.14g, 0.121mmol) It is dissolved in toluene (40ml), is heated to 75 DEG C, the K that then will now match somebody with somebody2CO3The aqueous solution (2mol/L, 6.1ml, 12.1mmol) adds Reaction system, react 48 hours under 110 DEG C of counterflow conditions；Solvent is rotated, carries out column chromatography, eluent is petroleum ether：Acetic acid Ethyl ester=4:1 (v/v), then recrystallized in tetrahydrofuran/ethanol (5/100, v/v), obtain yellow powder 0.98g, that is, contain The organic light emission small molecule material M7 of naphtho- indenes fluorenes unit, yield 68%.
Embodiment 15
Double (9- diisooctyl -2- carbazyls) -7,7,13,13- four n-hexyl -7,13- dihydrobenzos [g] indenes of 5,11- [1, 2-b] fluorenes (M8) synthesis：
Under the conditions of closed, logical argon gas, by 5,11- bis- bromo- 7,7,13,13- tetra- n-hexyl -7,13- dihydrobenzo [g] indenes [1,2-b] fluorenes (1.0g, 1.21mmol), 2- (4,4,5,5- tetramethyls -1,3,2- dioxaborinate -2- bases) -9- iso-octyl clicks Azoles (1.23g, 3.03mmol), TBAB (40mg, 0.121mmol) and Pd (PPh3)4(0.14g, 0.121mmol) It is dissolved in toluene (40ml), is heated to 75 DEG C, the K that then will now match somebody with somebody2CO3The aqueous solution (2mol/L, 6.1ml, 12.1mmol) adds Reaction system, react 48 hours under 110 DEG C of counterflow conditions；Solvent is rotated, carries out column chromatography, eluent is petroleum ether：Acetic acid Ethyl ester=4:1 (v/v), then recrystallized in tetrahydrofuran/ethanol (5/100, v/v), obtain yellow powder 1.08g, that is, contain The organic light emission small molecule material M8 of naphtho- indenes fluorenes unit, yield 75%.
Embodiment 16
The conjunction of double n-hexyl -7,13- dihydrobenzos [g] indenes [1,2-b] fluorenes (M9) of (phenyl) -7,7,13,13- four of 5,11- Into：
Under the conditions of closed, logical argon gas, by 5,11- bis- bromo- 7,7,13,13- tetra- n-hexyl -7,13- dihydrobenzo [g] indenes [1,2-b] fluorenes (1.94g, 2.42mmol), phenyl boric acid (0.74g, 6.06mmol) and Pd (PPh3)4(0.28g, 0.242mmol) It is dissolved in toluene (40ml), is heated to 75 DEG C, treats that solid all dissolves, the K that will now match somebody with somebody2CO3The aqueous solution (2mol/L, 12.1ml, Reaction system 24.2mmol) is added, is reacted 24 hours at 75 DEG C；Solvent is rotated, carries out column chromatography, eluent is followed successively by oil Ether：Dichloromethane=10:1 (v/v), petroleum ether：Dichloromethane=1:1 (v/v), then in tetrahydrofuran/ethanol (5/100, v/ V) recrystallized in, obtain white powder 1.19g, the i.e. fluorenes of indenes containing naphtho- unit organic light emission small molecule material M10, yield 63%.
Embodiment 17
The preparation of organic electroluminescence device
Ito glass substrate is placed on film hanger, with low concentration (10-4Mol/L liquid detergent semiconductor cleaning solution ultrasound) Cleaning ten minutes, removing substrate surface can adsorbable metal ion；It is cleaned by ultrasonic twice with deionized water again, each ten minutes, Remove the cleaning solution of residual；Finally it is cleaned by ultrasonic ten minutes with isopropanol, removes moisture easily to dry；It is put into baking oven and dries Dry, temperature is set to 80 DEG C；Before making devices, the ito glass substrate after drying is handled, carved in oxygen plasma Oxygen plasma (O is used in erosion instrument2Plasma) bombard 20 minutes.
By above cleaning step, the impurity of ito glass substrate surface is sufficiently removed, and contact when can improve film forming Angle, O2Plasma processing further removes the organic impurities of substrate surface residual, and further improves contact angle and pattern.
Organic active layer be by high vacuum (<5×10-4Pa thermal evaporation under the conditions of) and be deposited on ito glass base On piece：First, in order to improve injectability of the hole from anode, the cyanogen of hole-injecting material 2,3,6,7,10,11- six thick 5nm The azepine benzophenanthrenes (HATCN) of base -1,4,5,8,9,12- six are deposited on ito glass substrate；Then, the thick skies of 30nm are deposited Hole transport materials N, N'- diphenyl-N, N'- (1- naphthyls) -1,1'- biphenyl -4,4'- diamines (NPB)；Then, luminescent material quilt Deposition forms the thick luminescent layers of 20nm；Finally, electron transport material 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene (TPBI) the thick electron transfer layers of 30nm are deposited as；Negative electrode is made up of the thick Al of thick 1nm LiF and 90nm, and by with The mask plate of 3mm × 3mm sieve aperture arrays is drawn and formed；The sedimentation rate of material is respectively：Organic layer The electroluminescent device of ITO/HATCN/NPB/EML/TPBI/LiF/Al structures is prepared.
Electroluminescent (EL) spectrogram of the electroluminescent device of preparation passes through Photo Research PR705 type optics Analyzer measures；The characteristic of current density and brightness and driving voltage respectively by the source measuring units of Keithley 2400 and Konica Minolta chromascopes CS-200 is measured；External quantum efficiency assumes that Lambertian is distributed, by brightness, current density It is calculated with EL spectrum.
Respectively using organic light emission small molecule material M1 and M2 as luminescent layer, preparation structure ITO/HATCN/NPB/EML/ TPBI/LiF/Al device.
The electroluminescent spectrum of electroluminescent device prepared by luminescent layer based on material M1 and M2 is as shown in figure 5, from figure In as can be seen that be located at 504nm in the maximum emission peak of the device based on material M1, in green emission, chromaticity coordinates be (0.28, 0.48)；The maximum emission peak of device based on material M2 is located at 472nm, and in blue emission, chromaticity coordinates is (0.18,0.25).
The luminous efficiency of device based on material M1, M2 and the graph of a relation of current density are as shown in fig. 6, related data such as table 2(a:Numerical value when luminous intensity is every square metre of 100 candela) shown in.
The performance indications of table 2 organic light emission small molecule material M1, M2 electroluminescent device
From Fig. 6 and table 2, the electroluminescent properties index of the device based on material M1 and M2, it is known that material M1 is most Big luminous efficiency is 3.37cd/A, high-high brightness 10591cd/m2, it is 3.5V to open bright voltage；Material M2 maximum lumen efficiency For 1.35cd/A, high-high brightness 1223cd/m2, it is 4.4V to open bright voltage.

Claims (10)

1. a kind of organic light emission small molecule material of the fluorenes of indenes containing naphtho- unit, it is characterised in that chemical structural formula is as follows：
Ar1、Ar2、Ar3、Ar4、Ar5And Ar6The one kind being independently chosen from following structural formula and its derivative：
Wherein, X O, S, Se, Te or N-R；Y is C, Si or Ge；
R is H, C1~C30Straight chain or branched alkyl,R1For H, C1~C30It is straight Chain or branched alkyl.
2. prepare a kind of method of the organic light emission small molecule material of the fluorenes of indenes containing naphtho- unit described in claim 1, its feature It is, comprises the following steps：
(1) under cryogenic, 7,13- dihydrobenzos [g] indenes [1,2-b] fluorenes of alkylation is dissolved in chloroform, it is lazy Property gaseous environment in be added dropwise bromine dropwise, stirring is reacted；After reaction terminates, extracted, concentrated with dichloromethane, dried, post Chromatographic purification, two bromo- 7 are obtained, 7,13,13- alkyl -7,13- dihydrobenzo [g] indenes [1,2-b] fluorenes；
(2) under inert gas environment, two bromo- 7,7,13,13- alkyl -7,13- dihydrobenzo [g] indenes [1,2-b] fluorenes are dissolved in first In benzene, Ar is added1~Ar6Aryl-boric acid ester or Ar1~Ar6Aryl boric acid, add TBAB, potassium carbonate with And tetrakis triphenylphosphine palladium, heating carry out Suzuki coupling reactions；After reaction terminates, room temperature is cooled to, is extracted, is dried, post layer Analysis purification, obtain the organic light emission small molecule material of the fluorenes unit of indenes containing naphtho-.
3. preparation method according to claim 2, it is characterised in that in step (1), the temperature of the low temperature for -20~ 25℃；7,13- dihydrobenzos [g] indenes [1,2-b] fluorenes of the alkylation and the mol ratio of bromine are 1:2~6.
4. preparation method according to claim 2, it is characterised in that in step (1), the inert gas includes argon gas； The time of the reaction is 2~24 hours.
5. preparation method according to claim 2, it is characterised in that in step (2), the inert gas includes argon gas； Two bromo- 7,7,13,13- alkyl -7,13- dihydrobenzos [g] indenes [1,2-b] fluorenes, Ar1~Ar6Aryl-boric acid ester or Ar1 ~Ar6Aryl boric acid, TBAB, the mol ratio of potassium carbonate and tetrakis triphenylphosphine palladium be 1：2~6：0.05~ 0.2：5~10：0.02-0.1.
6. preparation method according to claim 2, it is characterised in that in step (2), the Suzuki coupling reactions be 50~120 DEG C are reacted 8~48 hours.
7. a kind of organic light emission small molecule material of the fluorenes of indenes containing naphtho- unit described in claim 1 is preparing organic electroluminescent Application in the luminescent layer of device, it is characterised in that the organic light emission small molecule material of the fluorenes unit of indenes containing naphtho- is passed through into vacuum Evaporation coating method or solution processing method prepare film forming, obtain the luminescent layer of organic electroluminescence device.
8. application according to claim 7, it is characterised in that the structure of the organic electroluminescence device is to include successively Substrate, anode layer, hole injection layer, hole transmission layer, luminescent layer, electron transfer layer, electron injecting layer and the cathode layer of stacking, Or it is substrate, cathode layer, electron injecting layer, electron transfer layer, luminescent layer, hole transmission layer, the hole note for including stacking gradually Enter layer and anode layer.
9. application according to claim 7, it is characterised in that the thickness of the luminescent layer is 10~1000nm.
10. application according to claim 7, it is characterised in that the solution processing method includes spin coating, brushing, spraying, leaching Painting, roller coat, silk-screen printing, printing or inkjet printing methods.
CN201710766030.7A 2017-08-30 2017-08-30 A kind of organic light emission small molecule material of the fluorenes of indenes containing naphtho- unit and preparation method and application Pending CN107501101A (en)

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