CN104650041B - Fluorine-containing phenanthroimidazole derivative, synthetic method and application thereof - Google Patents
Fluorine-containing phenanthroimidazole derivative, synthetic method and application thereof Download PDFInfo
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- CN104650041B CN104650041B CN201310589113.5A CN201310589113A CN104650041B CN 104650041 B CN104650041 B CN 104650041B CN 201310589113 A CN201310589113 A CN 201310589113A CN 104650041 B CN104650041 B CN 104650041B
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Abstract
The invention provides a fluorine-containing phenanthroimidazole derivative, a synthetic method and an application thereof. In particularly, the invention provides a compound represented as the formula I, wherein the R is defined as the specification. The compound can be used for preparing a luminescent material or preparing an electroluminescent device, is high in stability, performance and efficiency, and is especially used for preparing the electroluminescent device emitting a red light, a green light, a blue light and a yellow light.
Description
Technical field
The invention belongs to electroluminescent organic material and light emitting device field, and in particular to phenanthro- imidazole derivative and its
Preparation method, and the organic electroluminescence device of the series material.
Background technology
Organic electroluminescence device has the advantages that low driving voltage, fast response time, angular field of view width, high resolution,
Become the focus of the area researches such as material, information, physicss.Different according to principle of luminosity, electroluminescent organic material is divided into glimmering
Luminescent material and the big class of phosphor material two.Compared with fluorescent material, phosphor material can be using triplet and singlet excitons, interior amount
Sub- efficiency is in theory up to 100%.Therefore, it is a kind of important of acquisition high efficiency organic electroluminescence device using phosphor material
Means.
In order to obtain higher electrophosphorescence efficiency, generally heavy metal phosphor material is doped in material of main part to reduce
Concentration quenching and triplet state-triplet state annihilation.Preferably material of main part must is fulfilled for following requirements：(1) three lines of material of main part
State energy level (ET) it is more than guest triplets energy level；(2) with good carrier transmission performance；(3) with good thermally-stabilised
Property and morphological stability.At present, HONGGUANG and yellow phosphor device have obtained gratifying luminous efficiency.And efficient blue light
But seldom, main cause is a lack of the charge transport properties having had simultaneously and high triplet (E to phosphorescent devicesT) master
Body material.
In recent years some research groups developed a series of bipolar host materials with excellent charge transport properties, took
Preferable device performance was obtained, with the increase efficiency decay very little of electric current density.But these materials all also exist certain
The improper or low triplet (E of defect, such as HOMO/LUMOT) blue-light device of higher performance cannot be obtained.
The triplet of HONGGUANG and green glow guest materials is relatively low, and its material of main part such as PFO, PVK, PFB etc. are achieved very
Big progress, device has met business-like requirement.But, because blue light object such as FIrPic has high triplet,
Above material of main part cannot meet the demand of blue light electro phosphorescent device.
In sum, this area still lacks a kind of with good charge transport properties and high triplet (ET), fit
Share in the material of main part for preparing multiple color device, particularly blue light emitting device.
The content of the invention
It is an object of the invention to provide a kind of with good charge transport properties and high triplet (ET), it is adapted to use
In the material of main part for preparing red, green, blue, Huang Si kind color devices.
A kind of a first aspect of the present invention, there is provided compound as shown in following formula I：
Wherein, described R is selected from the group：The aryl of substituted or unsubstituted C6-C30, substituted or unsubstituted C1-C30
Heteroaryl.
In another preference, described R is selected from the group：The aryl of substituted or unsubstituted C12-C30, replaces or does not take
The heteroaryl of the C6-C30 in generation.
In another preference, described R is selected from the group：The aryl of substituted or unsubstituted C12-C30, replaces or does not take
The heteroaryl of the C6-C30 in generation；Wherein, there are at least 2 six-membered ring structures in the aryl or heteroaryl.
In another preference, described R is selected from the group：The aryl of substituted or unsubstituted C12-C30, replaces or does not take
The heteroaryl of the C6-C30 in generation；Wherein, there are at least 3 six-membered ring structures in the aryl or heteroaryl.
In another preference, described R is selected from the group：The aryl of substituted or unsubstituted C12-C30, replaces or does not take
The heteroaryl of the C6-C30 in generation；Wherein, there are at least 3 benzene ring structures in the aryl or heteroaryl.
In another preference, described R is selected from the group：Triphenylamine base, N- phenyl carbazole bases.
In another preference, the triplet >=2.8eV of the compound, preferably >=3eV.
A second aspect of the present invention, there is provided a kind of preparation method of compound as described in the first aspect of the invention, the side
Method includes step：
In atent solvent, reacted with Formula II compound and formula III compound, obtain compound of formula I.
Wherein, described formula III compound is selected from the group：R-B(OH)2、R-B(OCCH3CH3)2。
X is selected from the group：H、F、Cl、Br、I；
R is selected from the group：The aryl of substituted or unsubstituted C6-C30, the heteroaryl of substituted or unsubstituted C1-C30.
It is preferred that described X is selected from the group：Cl、Br.
In another preference, described reaction is carried out in the presence of catalyst and/or alkali.
In another preference, described catalyst is palladium catalyst, is preferably selected from the group：Tetrakis triphenylphosphine palladium,
Two (triphenylphosphine) palladium chlorides, or its combination.
In another preference, the alkali includes：Sodium carbonate, potassium carbonate, cesium carbonate, potassium acetate, potassium phosphate, hydroxide
Sodium, potassium hydroxide, potassium fluoride, or its combination.
In another preference, the Formula II compound is 1 with the mol ratio of formula III compound:2～1:3.
In another preference, described atent solvent is selected from the group：Water, ethanol, glycol dimethyl ether, toluene, tetrahydrochysene
Furan, Isosorbide-5-Nitrae-dioxane, or its combination.
In another preference, methods described also bag step：
In atent solvent, with Formula II ' a compounds, Formula II ' b compounds withReaction, obtains formula
II ' compounds；
It is above-mentioned it is various in, X ' is selected from the group：H、F、Cl、Br、I；And X ' and X may be the same or different.
In another preference, described atent solvent is selected from the group：Acetic acid, acetic anhydride, or its combination.
In another preference, described reaction is carried out in the presence of acetic acid and/or ammonium acetate.
In another preference, methods described also includes step：In atent solvent, with Formula II ' compound and X2Reaction,
Obtain Formula II compound.
A kind of a third aspect of the present invention, there is provided purposes of compound as described in the first aspect of the invention, it is described
Compound is used to prepare electroluminescent material, or described compound is used to prepare electroluminescent device.
In another preference, described electroluminescent device is Phosphorescent adulterated EL part.
A fourth aspect of the present invention, there is provided a kind of electroluminescent material, described electroluminescent material is included such as this
Compound described in bright first aspect, or described electroluminescent material is with compound system as described in the first aspect of the invention
Standby.
In another preference, described material also includes guest materials.
In another preference, described guest materials is Ir (PPy)3、FIrPic、Ir(f-ppy)2(acac)、Ir
(ppy)2pc、Ir(piq)3、Ir(mppy)3Or its combination.
In another preference, described compound of formula I and the mass ratio of guest materials is 50-99:1-10.
In another preference, described electroluminescent material is blue light material.
In another preference, described electroluminescent material is green light material.
In another preference, described electroluminescent material is yellow light material.
In another preference, described electroluminescent material is red light material.
A fifth aspect of the present invention, there is provided a kind of electroluminescent device, described device includes：
(1) substrate；
(2) nesa coating on substrate；
(5) luminescent layer；With
(8) negative electrode on electron injecting layer；
And described luminescent layer includes compound as described in the first aspect of the invention, or described luminescent layer is with such as this
Prepared by the compound described in invention first aspect.
In another preference, described electroluminescent device is blue-light device.
In another preference, described electroluminescent device is green device.
In another preference, described electroluminescent device is gold-tinted device.
In another preference, described electroluminescent device is red device.
In another preference, described luminescent layer includes the electroluminescent material described in fourth aspect present invention.
In another preference, described device also includes：
(3) hole injection layer on nesa coating；
(4) hole transmission layer on hole injection layer；
(6) electron transfer layer on luminescent layer；
(7) electron injecting layer on electron transfer layer；
And
Described luminescent layer is located between described hole transmission layer and described electron transfer layer；
Described negative electrode is located on described electron injecting layer.
In another preference, described device includes one or more features being selected from the group：
The material of described hole injection layer includes 4,4 ', 4 '-three (carbazole -9- bases) triphenylamines；And/or
The material of described hole transmission layer includes 4,4 '-two (9- carbazoles) biphenyl；And/or
The material of described electron transfer layer includes 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene；And/or
Described electron injecting layer includes the material being selected from the group：LiF、MoO3、WO3, or its combination.
In another preference, described substrate is glass and/or transparent plastic.
In another preference, the material of described nesa coating is tin indium oxide.
In another preference, the material of described negative electrode is Al.
In another preference, described device also includes one or more features being selected from the group：
The thickness of described hole injection layer (3) is 10-30nm；And/or
The thickness of described hole transmission layer (4) is 15-35nm；And/or
Described luminescent layer (5) thickness is 10-30nm；And/or
Described electron transfer layer (6) thickness is 25-40nm；And/or
The thickness of described electron injecting layer (5) is 0.5-2nm.
A kind of a sixth aspect of the present invention, there is provided preparation method of the device as described in fifth aspect present invention, it is described
Method includes step：
One substrate with nesa coating is provided, and there is successively hole injection layer and sky on described nesa coating
Cave transport layer；
Described emitting layer material is deposited on described hole transmission layer, form luminescent layer；
Make to sequentially form the electron transfer layer, electron injecting layer and negative electrode on described luminescent layer, obtain described device
Part.
In another preference, the luminescent layer is deposited by evaporation mode.
In another preference, described method includes step：
I () provides a substrate with nesa coating；
(ii) material for making the hole injection layer is deposited on described nesa coating, forms hole injection layer；
(iii) material for making the hole transmission layer is deposited on described hole injection layer, forms hole transmission layer；
(iv) material for making the luminescent layer is deposited on described hole transmission layer, forms luminescent layer；
V () makes the material of the electron transfer layer deposit on described luminescent layer, form electron transfer layer；
(vi) material for making the electron injecting layer is deposited on described electron transfer layer, forms electron injecting layer；
(vii) material for making the negative electrode is deposited on described electron injecting layer, forms negative electrode.
It should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and have in below (eg embodiment)
Can be combined with each other between each technical characteristic of body description, so as to constitute new or preferred technical scheme.As space is limited, exist
This no longer tires out one by one states.
Description of the drawings
Fig. 1 is the Phosphorescent doping type EL device structure schematic diagram of the present invention and imidazole derivative；
Fig. 2 is the low temperature of obtained compound in embodiment 1,2（77K）Phosphorescence spectrum；
Fig. 3 is Ir (PPy) in embodiment 3,43The electroluminescence spectrum of doped body material devices.
Specific embodiment
The present inventor is through long-term and in-depth study, it has unexpectedly been found that a class has the chemical combination of structure shown in formula I
Thing.Described compound triplet is high, can be used for preparing electroluminescent device, it is particularly possible to prepare luminescent spectrum wave band
For the material of blue light, have a good application prospect in monochromatic, total colouring and illumination white light parts.
Term
Term " electroluminescent organic material " refers to the macromolecule or Small molecule organic materials that light can be sent under electric field action.
Especially, in the present invention, described electroluminescent organic material is Small molecule organic materials.
Term " C6～C30 aryl " refers to the aryl with 6～30 carbon atoms, including monocyclic, bicyclo-, polyaromatic, example
Such as phenyl, naphthyl, or similar group.
Term " C1～C30 aryl " refers to the aryl with 1～30 carbon atom, including monocyclic, bicyclo-, polyaromatic, example
Such as pyridine radicals, quinolyl, or similar group.
Term " replacement " refers to that one or more hydrogen atoms on group are selected from the substituent group of the following group and replace：C1～C4 alkane
Base, C3～C6 cycloalkyl, halogen, phenyl；Wherein, described phenyl includes unsubstituted phenyl or with 1-3 substituent group
Substituted-phenyl, the substituent group is selected from：Halogen, C1-C4 alkyl.
Term " halogen " refers to F, Cl, Br and I.
Compound name is abridged：
Material of main part
In phosphorescent OLED device, in order to avoid or reduce concentration quenching and triplet state-triplet state annihilation effect, cause phosphorus
The reduction of photo-quantum efficiency, so usual phosphorescent devices adopt that luminous phosphor material is entrained in material of main part forms object
Structure.Additionally, material of main part also plays the effects such as electric charge transmission.
Luminescent device requires material of main part triplet higher than doping triplet, and blue light material then has four kinds
Highest triplet in color, thus can as the material of blue light main body can as HONGGUANG, green glow, gold-tinted main body
Material, Blue-light emitting host material typically requires that triplet, more than 2.8eV, is that doping can realize different face by different materials
Color lights, and blue-light-emitting, Ir (ppy) are realized in such as FirPic doping2Yellow luminous, Ir (piq) is realized in pc doping3Doping is realized red
Color is luminous etc..
Guest materials
In the phosphorescent OLED device of Subjective and Objective structure, luminous phosphor material is referred to as guest materials.Generally, guest materials
It is some transient metal complexes, such as Ir, the coordination compound of the metal such as Os, Pt, Cu.
Compound of formula I
The invention provides a kind of compound as shown in following formula I：
Wherein, described R is selected from the group：The aryl of substituted or unsubstituted C6-C30, substituted or unsubstituted C1-C30
Heteroaryl.
In another preference, described R is selected from the group：The aryl of substituted or unsubstituted C12-C30, replaces or does not take
The heteroaryl of the C6-C30 in generation.
In another preference, described R is selected from the group：Triphenylamine base, N- phenyl carbazole bases.
Described compound can be prepared by the following method：
In atent solvent, reacted with Formula II compound and formula III compound, obtain compound of formula I.
Wherein, described formula III compound is selected from the group：R-B(OH)2、R-B(OCCH3CH3)2。
X is selected from the group：H、F、Cl、Br、I；
R is selected from the group：The aryl of substituted or unsubstituted C6-C30, the heteroaryl of substituted or unsubstituted C1-C30.
It is preferred that described X is selected from the group：Cl、Br.
In another preference, described reaction is carried out in the presence of catalyst and/or alkali.
In another preference, described catalyst is palladium catalyst, is preferably selected from the group：Tetrakis triphenylphosphine palladium,
Two (triphenylphosphine) palladium chlorides, or its combination.
In another preference, the alkali includes：Sodium carbonate, potassium carbonate, cesium carbonate, potassium acetate, potassium phosphate, hydroxide
Sodium, potassium hydroxide, potassium fluoride, or its combination.
In another preference, the Formula II compound is 1 with the mol ratio of formula III compound:2～1:3.
In another preference, described atent solvent is selected from the group：Water, ethanol, glycol dimethyl ether, toluene, tetrahydrochysene
Furan, Isosorbide-5-Nitrae-dioxane, or its combination.
Wherein, raw material II can be prepared by the following method：
In atent solvent, with Formula II ' a compounds, Formula II ' b compounds withReaction, obtains formula
II ' compounds；
It is above-mentioned it is various in, X ' is selected from the group：H、F、Cl、Br、I；And X ' and X may be the same or different.
In another preference, described atent solvent is selected from the group：Acetic acid, acetic anhydride, or its combination.
In another preference, described reaction is carried out in the presence of acetic acid and/or ammonium acetate.
In another preference, methods described also includes step：In atent solvent, with Formula II ' compound and X2Reaction,
Obtain Formula II compound.
Described compound can be used for preparing electroluminescent material, or electroluminescent device.
Electroluminescent material
The invention provides a kind of have ambipolar phenanthro- imidazole derivative, can be applied to stratiform doping type
In the organic electrophosphorescenpolymer doping type luminescent device of structure, as the material of main part of luminescent layer.
In general, the design of material of main part should meet following condition:The singletstate and triplet excitons energy of material of main part
Amount can effectively be transferred to guest materials, while the quenching effect very little of the exciton energy of main object, i.e. main body send out
Penetrating the absorption spectrum of spectrum and object has larger overlap, namely energy match；Material of main part should have good carrier to move
Move property.
The present invention compound due to being doped from different phosphorescent guest materials, therefore can prepare red, yellow, and green,
Various light section transmittings such as indigo plant, purple.Further, since it has high triplet energy level (＞ 3.0eV), high triplet energy level is suitable as
Blue light guest materials material of main part, it is panchromatic and illumination white light parts in be respectively provided with good application prospect.
Electroluminescent material of the present invention includes compound as described in the first aspect of the invention, or described electroluminescent
Luminescent material is prepared with compound as described in the first aspect of the invention.
Described material can also optionally include guest materials, such as heavy metal phosphor material.In the present invention, preferably
Guest materials includes（But it is not limited to）：Ir(PPy)3、FIrPic、Ir(f-ppy)2(acac)、Ir(ppy)2pc、Ir(piq)3、
Ir(mppy)3, or its combination.
In another preference, described compound of formula I and the mass ratio of guest materials is 50-99:1-10.
Electroluminescent device
The phenanthro- imidazole derivative of the present invention can be used as the main body material of luminescent layer in organic phosphorescent electroluminescence device
Material is used, to prepare electroluminescent device.
Specifically, described device includes：
(1) substrate；
(2) nesa coating on substrate；
(5) containing compound as described in the first aspect of the invention, or with compound as described in the first aspect of the invention
The luminescent layer of preparation；With
(8) negative electrode on electron injecting layer；
Preferably, device of the invention can also include other assemblies or coating, and e.g., a kind of preferred present invention's is electroluminescent
Luminescent device includes：
(1) substrate；
(2) nesa coating on substrate；
(3) hole injection layer on nesa coating；
(4) hole transmission layer on hole injection layer；
(5) luminescent layer on hole transmission layer；
(6) electron transfer layer on luminescent layer；
(7) electron injecting layer on electron transfer layer；With
(8) negative electrode on electron injecting layer；
And described luminescent layer includes compound as described in the first aspect of the invention, or described luminescent layer is with such as this
Prepared by the compound described in invention first aspect.
In another preference, described luminescent layer can be the compound and object material described in first aspect present invention
Material, the such as electroluminescent material that such as heavy metallic salt is collectively forming, compound of formula I and Ir (PPy)3The electroluminescent being collectively forming
Material etc..
The material of other layers such as described nesa coating, hole injection layer, hole transmission layer is not limited, can be by this area skill
Art personnel choose according to actual needs, it is preferable that in described device：
Described hole injection layer may include 4,4 ', 4 '-three (carbazole -9- bases) triphenylamines；And/or
Described hole transmission layer may include 4,4 '-two (9- carbazoles) biphenyl；And/or
Described electron transfer layer may include 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene；And/or
Described electron injecting layer may include the material being selected from the group：LiF、MoO3、WO3, or its combination.
Described each thickness degree is not particularly limited, and can be adjusted according to practical situation.One in the present invention is excellent
In selecting example, the thickness of each layer is as follows in described device：
The thickness of described hole injection layer (3) is 10-30nm；And/or
The thickness of described hole transmission layer (4) is 15-35nm；And/or
Described luminescent layer (5) thickness is 10-30nm；And/or
Described electron transfer layer (6) thickness is 25-40nm；And/or
The thickness of described electron injecting layer (5) is 0.5-2nm.
A kind of preferred structure of described electroluminescent device is stratiform doping type structure, as shown in figure 1, by substrate to the moon
Pole is followed successively by substrate (1), nesa coating (2), hole injection layer (3), hole transmission layer (4), luminescent layer (5), hole barrier
Layer (6), electron transfer layer (7), electron injecting layer (8), negative electrode (9), it is characterised in that：Luminescent layer (5) is using phenanthro- imidazoles
The sub- Ir (PPy) of derivant bipolar host material doping phosphorescence3。
In above-mentioned Phosphorescent doping type electroluminescent device：
Hole injection layer (3) material is preferably 4,4 ', 4 '-three (carbazole -9- bases) triphenylamines, and its thickness is preferably 10-
30nm；
Hole transmission layer (4) material is preferably 4,4 '-two (9- carbazoles) biphenyl, and its thickness is preferably 15-35nm；
Luminescent layer (5) material of main part, guest materials mass ratio are preferably 1～10:90, light emitting layer thickness is preferably 10-
30nm；
Electron transfer layer (7) material is preferably 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene, and its thickness is preferred
For 25-40nm；
Electron injecting layer (8) material is preferably LiF, MoO3、WO3Deng its thickness is preferably 0.5-2nm；Negative electrode (9) material
Preferably aluminum, silver-colored, calcium, magnesium etc., and its thickness is preferably 100-200nm.
Main advantages of the present invention
The present invention has been obtained material of main part of the class with very high triplet (>=2.8eV), described main body material
Material can be doped with various guest materials, so as to prepare the luminescent device of different colours.Especially, material of the invention is also
Can be adulterated with blue light guest materials, prepare blue light emitting device.
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than restriction the scope of the present invention.The experimental technique of unreceipted actual conditions in the following example, generally according to conventional strip
Part, or according to the condition proposed by manufacturer.Unless otherwise indicated, otherwise percentage ratio and number are calculated by mol.
Embodiment 1：2- (4,4 "-two (oxazolyl)-(1,1 ':3 ', 1 "-terphenyl) (4- (trifluoromethyl) is luxuriant and rich with fragrance for -1-
And the synthesis of imidazoles (DCzBPI)
In the present embodiment, and 2- (4,4 "-two (oxazolyl)-(1,1 ':3 ', 1 "-terphenyl) -1- (4- (trifluoromethyl)
The structural formula of phenanthro- imidazoles is：
Above-mentioned 2- (4,4 "-two (oxazolyl)-(1,1 ':3 ', 1 "-terphenyl) -1- (4- (trifluoromethyl) phenanthro- miaows
The Preparation Method of azoles comprises the steps：
Step 1：Synthetic intermediate 1：2- (3,5- dibromo phenyls) -1- (4- (trifluoromethyl) phenanthro- imidazoles
(Br2BPI)：
In equipped with stirring, thermometer, the 500mL there-necked flasks of gas access equipment, argon 10min is passed through, is sequentially added
200 parts of acetic acid is dissolved in 85 parts of 100 parts of p-trifluoromethylaniline, 20 parts of phenanthrenequione, 20 parts of 3,5- dibromo benzaldehydes and ammonium acetate
In, high-temperature is risen to 125 DEG C of reaction 12h, cooling is filtered, and filtrate is evaporated and obtains crude product, and crude product adopts column chromatography silica gel mistake
Post separation, purification obtains the (Br of intermediate 12BPI)：2- (3,5- dibromo phenyls) -1- (4- (trifluoromethyl) phenanthro- imidazoles.
Above-mentioned intermediate 1 is analyzed：Nuclear-magnetism：1H NMR(400MHz,CDCl3):δ8.85(d,1H,J=8.08Hz),
8.81(d,1H,J=8.22Hz),8.73(d,1H,J=8.21Hz),7.97(d,2H,J=8.31Hz),7.79(t,1H,J=
8.14Hz),7.73-7.65(m,4H),7.60-7.56(m,3H),7.38-7.32(m,1H),7.18(d,1H,J=8.44Hz)；
Mass spectrum：(M+)：595.8,594.1；Elementary analysiss：C56.13, H2.92, N4.27, value of calculation：C56.40, H2.54, N4.70.
Step 2：Target compound 2- (4,4 "-two (oxazolyl)-(1,1 ':3 ', 1 "-terphenyl) -1- (4- (trifluoromethyls
Phenyl) phenanthro- imidazoles preparation (DCzBPI)
In the there-necked flask equipped with magnetic stirring apparatuss, the intermediate 1 that 3 parts of steps 1 are synthesized：2- (3,5- dibromobenzenes
Base) -1- (4- (trifluoromethyl) phenanthro- imidazoles, 7.5 parts of 4- (9- carbazyls) phenylboric acids, the 20% of 8 parts tetraethyl hydrogen-oxygens
Change amine and 0.2 part of four triphenyl phosphorus palladium is dissolved in the toluene of 100 deals, 24h is reacted at 105 DEG C under argon protection, remove molten
Agent, cross post separation, purification obtain target compound 2- (4,4 "-two (oxazolyl)-(1,1 ':3 ', 1 "-terphenyl) -1- (4- (three
Trifluoromethylphenyl) phenanthro- imidazoles.
Above-mentioned target compound is analyzed：
Nuclear-magnetism：1H NMR(400MHz,CDCl3):δ8.98(d,1H,J=8.21Hz),8.84(d,1H,J=8.20Hz),
8.76(d,1H,J=8.21Hz),8.18(d,4H,J=7.82Hz),8.05(d,2H,J=8.21Hz),7.97(s,H),7.79(t,
1H,J=8.14Hz),7.86-7.79(m,5H),7.73-7.67(m,4H),7.59(t,1H,J=7.78Hz),7.51-7.44(m,
8H),7.39-7.30(m,6H);13CNMR(100MHz,CDCl3):δ150.1,142.4,141.3,140.8,139.3,137.9,
137.6,132.4,132.1,131.2,130.1,129.6,128.6,128.5,128.0,127.6,127.5,127.4,
127.3,127.1,126.7,127.6,126.1,125.4,125.0,124.5,123.6,132.3,123.0,122.6,
122.3,120.8,120.4,120.2,109.8.Anal. theoretical value：C64H43F3N4:C,83.46;H,4.27;N, 6.08. are tested
Value：C,83.01;H,4.30;N,5.99.
It is electroluminescent that above-mentioned phenanthro- imidazole derivative bipolar host material DCzBPI can apply to Phosphorescent doping type
In luminescent device.Low temperature（77K）Phosphorescence spectrum assay method obtain target compound 2- (4,4 "-two (oxazolyl)-(1,1 ':3’,1”-
Terphenyl) (4- (trifluoromethyl) phenanthro- imidazoles triplet is 3.09eV (Fig. 2) to -1-.
Embodiment 2：2- (4,4 "-two (diphenylamines)-(1,1 ':3 ', 1 "-terphenyl) -1- (4- (trifluoromethyl)
The preparation of phenanthro- imidazoles (DTPABPI)
In the present embodiment, and 2- (4,4 "-two (diphenylamines)-(1,1 ':3 ', 1 "-terphenyl) -1- (4- (trifluoromethylbenzenes
Base) structural formula of phenanthro- imidazoles is：
Above-mentioned 2- (4,4 "-two (diphenylamines)-(1,1 ':3 ', 1 "-terphenyl) -1- (4- (trifluoromethyl) phenanthro-s
The Preparation Method of imidazoles comprises the steps：
Step 1：Target compound 2- (4,4 "-two (diphenylamines)-(1,1 ':3 ', 1 "-terphenyl) -1- (4- (fluoroforms
Base phenyl) phenanthro- imidazoles preparation (DTPABPI)
In the there-necked flask equipped with magnetic stirring apparatuss, the intermediate 1 that step 1 in 1 part of embodiment 1 is synthesized：2-(3,5-
Dibromo phenyl) -1- (4- (trifluoromethyl) phenanthro- imidazoles, 2.5 parts of 4- boric acid triphenylamines, the 20% of 4 parts tetraethyl hydrogen-oxygens
Change amine and 0.1 part of four triphenyl phosphorus palladium is dissolved in the toluene of 50 deals, 24h is reacted at 105 DEG C under argon protection, remove molten
Agent, cross post separation, purification obtain target compound 2- (4,4 "-two (diphenylamines)-(1,1 ':3 ', 1 "-terphenyl) -1- (4-
(trifluoromethyl) phenanthro- imidazoles.
Above-mentioned target compound 2b is analyzed：1H NMR(400MHz,CDCl3):δ8.91(d,1H,J=7.43Hz),
8.80(d,1H,J=8.17Hz),8.73(d,1H,J=7.43Hz),7.92(d,2H,J=7.40Hz),7.75-7.55(m,8H),
7.31-7.06(m,31H).13C NMR(100MHz,CDCl3):δ150.7,147.6,142.4,141.3,137.8134.2,
132.1,131.8,130.7,130.0,129.6,129.5,129.3,128.4,127.8,127,5,127.4,127.3,
127.1,126.5,126.2,125.9,125.7,125.2,124.9,124.5,124.4,123.8,123.1,123.0,
122.9,122.7,122.2,120.7.Anal. theoretical value：C64H43F3N4:C,83.10;H,4.69;N, 6.06. experiment value：C,
82.88;H,4.67;N,5.99。
It is electroluminescent that above-mentioned phenanthro- imidazole derivative bipolar host material DTPABPI can apply to Phosphorescent doping type
In luminescent device.Low temperature（77K）Phosphorescence spectrum assay method obtain target compound 2- (4,4 "-two (diphenylamines)-(1,1 ':3’,
1 "-terphenyl) (4- (trifluoromethyl) phenanthro- imidazoles (DTPABPI) triplet is 3.04eV (Fig. 2) to -1-.
Embodiment 3：The preparation of DCzBPI Phosphorescent doping type electroluminescent devices
It is electroluminescent that above-mentioned phenanthro- imidazole derivative bipolar host material DCzBPI can apply to Phosphorescent doping type
In luminescent device.The electroluminescent device is stratiform doping type structure, as shown in figure 1, being followed successively by negative electrode including substrate successively
Substrate 1, nesa coating 2, hole injection layer 3, hole transmission layer 4, luminescent layer 5, electron transfer layer 6, electron injecting layer 7 and the moon
Pole 8.Wherein, substrate 1 is from glass or transparent plastic；Nesa coating 2 is from the tin indium oxide (ITO) that face resistance is 20 Ω/sq
As anode；By substrate clean after under high pure oxygen atmosphere glow discharge (plasma) process 10min, under a high vacuum (3～
2×10-4Pa under), 4,4 ', 4 '-three thick (carbazole -9- bases) triphenylamines of one layer of 20nm are deposited with nesa coating 2 as sky
Cave implanted layer 3, then continues to be deposited with 4,4 '-two thick (9- carbazoles) biphenyl of one layer of 24nm as hole on hole injection layer 3
Transport layer 4, is then deposited with the thick luminescent layers 5 of one layer of 20nm on hole transmission layer 4, and luminescent layer 5 is prepared using in the present embodiment 1
Obtain phenanthro- imidazole derivative bipolar host material DCzBPI and complex of iridium Ir (PPy)3And FIrPic, its mass ratio
For 100：X, wherein X=6；Continue afterwards to be deposited with the thick (1- phenyl -1H- benzo miaows of 1,3,5- tri- of one layer of 30nm on luminescent layer 5
Azoles -2- bases) benzene is used as electron transfer layer 6；Electron injecting layer 7 is then deposited on luminescent layer 6, electron injecting layer 7 selects LiF,
Its thickness is 1nm；Last that negative electrode 8 is deposited on electron injecting layer 7, negative electrode 8 selects Al, and its thickness is 100nm.
In the preparation process of above-mentioned Phosphorescent doping type electroluminescent device, the thickness of thin film adopts miniature calibrator pair
It is measured, and with luminance meter luminosity is measured, and all organic materials and LiF and metal Al adopt the side of vacuum evaporation film forming
Formula.
When applying appropriate external voltage to above-mentioned Phosphorescent doping type electroluminescent device, measure the electroluminescent phosphorescence and light
The performance of device is as shown in table 1.
Embodiment 4：The preparation of DTPABPI Phosphorescent doping type electroluminescent devices
It is essentially identical with the step in embodiment 3, except that, with the phenanthro- imidazoles prepared in embodiment 2
Derivant bipolar host material DTPABPI replaces DCzBPI.
In above-described embodiment 3-4, the performance of Phosphorescent doping type electroluminescent device is as shown in table 1 below：
Table 1：The performance table of organic electroluminescence device in embodiment 3-4
As can be seen that fluorine-containing phenanthro- imidazole derivative DTPABPI and DCzBPI is suitable for as phosphorescence from above-mentioned table 1
The material of main part of the luminescent layer in OLED.When Ir (PPy) is respectively adopted3During with FIrPic as guest materials, electricity is realized
Photoluminescence spectrum peak is in the green emission of 512 ± 3nm and the blue emission of 476 ± 5nm（Emission spectrum passes through PR705 equipment
Test）.Therefore, phenanthro- imidazole derivative bipolar host material derivant of the present invention can be in monochromatic, total colouring and photograph
Understand in optical device and be applied.
The all documents referred in the present invention are all incorporated as in this application reference, independent just as each document
It is incorporated as with reference to such.In addition, it is to be understood that after the above-mentioned teachings for having read the present invention, those skilled in the art can
To make various changes or modifications to the present invention, these equivalent form of values equally fall within the model that the application appended claims are limited
Enclose.
Claims (6)
1. a kind of electroluminescent device, it is characterised in that described device includes：
(1) substrate；
(2) nesa coating on substrate；
(5) luminescent layer；With
(8) negative electrode on electron injecting layer；
And described luminescent layer includes the compound as described in following formula, or described luminescent layer is with the compound as described in following formula
Prepare：
And described luminescent layer also includes guest materials FIrPic.
2. electroluminescent device as claimed in claim 1, it is characterised in that described device also includes：
(3) hole injection layer on nesa coating；
(4) hole transmission layer on hole injection layer；
(6) electron transfer layer on luminescent layer；
(7) electron injecting layer on electron transfer layer；
And
Described luminescent layer is located between described hole transmission layer and described electron transfer layer；
Described negative electrode is located on described electron injecting layer.
3. electroluminescent device as claimed in claim 1, it is characterised in that described device include for being selected from the group or
Multiple features：
The material of described hole injection layer includes 4,4 ', 4 '-three (carbazole -9- bases) triphenylamines；And/or
The material of described hole transmission layer includes 4,4 '-two (9- carbazoles) biphenyl；And/or
The material of described electron transfer layer includes 1,3,5- tri- (1- phenyl -1H- benzimidazolyl-2 radicals-yl) benzene；And/or
Described electron injecting layer includes the material being selected from the group：LiF、MoO3、WO3, or its combination.
4. the preparation method of device as claimed in claim 1, it is characterised in that including step：
One substrate with nesa coating is provided, and there is successively hole injection layer and hole to pass on described nesa coating
Defeated layer；
Described emitting layer material is deposited on described hole transmission layer, form luminescent layer；
Make to sequentially form the electron transfer layer, electron injecting layer and negative electrode on described luminescent layer, obtain described device.
5. method as claimed in claim 4, it is characterised in that described method also includes step：
In atent solvent, reacted with Formula II compound and formula III compound, obtain the compound being shown below：
Wherein, described formula III compound is selected from the group：R-B(OH)2、R-B(OCCH3CH3)2；
X is selected from the group：H、F、Cl、Br、I；
R is
Described atent solvent is selected from the group：Water, ethanol, glycol dimethyl ether, toluene, tetrahydrofuran, Isosorbide-5-Nitrae-dioxane, or
Its combination.
6. method as claimed in claim 5, it is characterised in that methods described also bag step：
In atent solvent, with Formula II ' a compounds, Formula II ' b compounds withReaction, obtains Formula II ' chemical combination
Thing；
It is above-mentioned it is various in, X ' is selected from the group：H、F、Cl、Br、I；And X ' is identical with X；
And described atent solvent is selected from the group：Acetic acid, acetic anhydride, or its combination.
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| JP2001023777A (en) * | 1999-07-08 | 2001-01-26 | Toray Ind Inc | Luminescent element |
| CN102190627A (en) * | 2010-12-10 | 2011-09-21 | 吉林大学 | 9,10-phenanthroimidazole derivatives and use thereof as electroluminescent materials |
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| CN102190627A (en) * | 2010-12-10 | 2011-09-21 | 吉林大学 | 9,10-phenanthroimidazole derivatives and use thereof as electroluminescent materials |
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