CN104557439A - Spiro-benzofluorene derivative as well as preparation method and application thereof - Google Patents
Spiro-benzofluorene derivative as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a spiro-benzofluorene derivative as well as a preparation method and an application thereof, in particular provides a compound adopting the structure of formula I shown in the specification, wherein the definition of M is shown in the specification. The compound can be applied to preparation of luminescent materials or electroluminescent devices, has the characteristics of good stability, high performance and high efficiency, and is particularly applicable to preparation of blue-light luminescent devices.
Description
Technical field
The invention belongs to technical field of organic luminescence materials, be specifically related to a kind of spiral shell benzofluorene analog derivative and preparation method thereof, and relate to the application of these materials in field of organic electroluminescence.
Background technology
From Kodaks in 1987 with since nineteen ninety, univ cambridge uk reported organic electronic light emitting device (OLED) and polymer LED (PLED) respectively, organic flat pannel display becomes the another generation display product after liquid-crystal display.Organic electroluminescence device has plurality of advantages, comprises luminous, the reaction times is fast, visual angle is wide, cost is low, the feature such as low dc voltage driving.Therefore, the very big research interest that efficient luminous organic material causes scientists is developed.
At present, the green light material, the red light material that realize panchromatic realization have reached business-like requirement.And blue light material is a fort of failing to capture, emission wavelength is shorter, the driving voltage that high energy requirement is higher, causes material easily aging, has a strong impact on the performance of device.Therefore, the exploitation of blue light material is remained to the focus of international research.
People find in research process, and in numerous blue light material, fluorenes class material is the blue light material with high-efficiency fluorescence.But research shows, 9 easy oxidized formation Fluorenone structures of fluorenes, Fluorenone becomes energy trapping and its electron attraction derivative spectomstry red shift, the formation of Fluorenone defect, causes the green emission band strength of fluorenes class material to increase.Therefore, usually in 9 formation introduced other groups and suppress Fluorenone structure of fluorenes, to improve its stability.
9,9 '-spiral shell two fluorenes can suppress the formation of Fluorenone structure effectively, as far back as Salbeck in 1997 etc., spiral shell two fluorenes is used in electroluminescent organic material aspect, thus has caused spiral shell fluorenes extensively carrying out at organic photoelectric functional material area research.But thermostability and the luminescent properties of spiral shell two fluorenes are still not satisfactory.
Therefore, this area blue light material that still deficient in stability is high, efficiency is high and blue light organic electroluminescence device.
Summary of the invention
The object of the present invention is to provide a kind of stability is high, efficiency is high blue light material and blue light organic electroluminescence device.
A first aspect of the present invention, provides a kind of compound with formula I structure:
Wherein, M is selected from lower group: the aryl of substituted or unsubstituted C6-C30, the heteroaryl of substituted or unsubstituted C1-C30.
In another preference, described M is selected from lower group: the aryl of substituted or unsubstituted C12-C30, the heteroaryl of substituted or unsubstituted C6-C30.
In another preference, described M is-T
1-T
2structure, wherein, described T
1for phenyl or fused ring aryl, and described T
2for substituted or unsubstituted aryl, heteroaryl or nothing.
In another preference, described M is aryl or the heteroaryl with 2-6 aromatic ring, preferably for having aryl or the heteroaryl of 3-6 aromatic ring.
In another preference, described M is selected from lower group: anthryl, phenanthryl, pyrenyl, benzimidazolyl-.
A second aspect of the present invention, provides a kind of method for making of compound as described in the first aspect of the invention, comprises step:
In inert solvent, react with such as formula the compound shown in II and alkylating reagent, thus obtain formula I;
Wherein, described alkylating reagent is selected from lower group: M-B (OH)
2, M-B (OCCH
3cH
3)
2.
Above-mentioned various in, X is selected from lower group: F, Cl, Br, I;
M is selected from lower group: the aryl of substituted or unsubstituted C6-C30, the heteroaryl of substituted or unsubstituted C1-C30.
Preferably, described X is selected from lower group: Cl, Br.
In another preference, described reaction is carried out under catalyzer and/or alkali exist.
In another preference, described catalyzer is palladium catalyst, is preferably selected from lower group: tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, or its combination.
In another preference, described alkali comprises: sodium carbonate, salt of wormwood, cesium carbonate, Potassium ethanoate, potassiumphosphate, sodium hydroxide, potassium hydroxide, Potassium monofluoride, or its combination.
In another preference, the mol ratio of described formula II compound and formula III compound is 1:2 ~ 1:3.
In another preference, described inert solvent is selected from lower group: water, ethanol, glycol dimethyl ether, toluene, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane, or its combination.
In another preference, described formula II compound is prepared by the following method:
In inert solvent, with spiral shell [benzofluorene-7,9 '-fluorenes] and X
2reaction, obtains formula II compound.
Wherein, X is selected from lower group: F, Cl, Br, I; Be preferably Cl and/or Br.
In another preference, described inert solvent is selected from lower group: methylene dichloride, chloroform, tetracol phenixin, or its combination.
A third aspect of the present invention, provides a kind of compound as described in the first aspect of the invention for the preparation of luminescent material, or for the preparation of the purposes of electroluminescent device.
A fourth aspect of the present invention, provides a kind of luminescent material, and described luminescent material comprises formula I as described in the first aspect of the invention, or described luminescent material formula I is as described in the first aspect of the invention made.
In another preference, described material is luminescent material.
In another preference, described luminescent material is blue light emitting material.
In another preference, described luminescent material is electroluminescent material.
A fifth aspect of the present invention, provides a kind of device, and described device has the material as described in fourth aspect present invention, or described device makes with the material as described in fourth aspect present invention.
In another preference, described device is electroluminescent device.
In another preference, described electroluminescent device has:
(1) substrate;
(2) nesa coating on substrate is positioned at;
(5) luminescent layer; With
(8) negative electrode on luminescent layer is positioned at.
In another preference, described device also comprises:
(3) hole injection layer on nesa coating is positioned at;
(4) hole transmission layer on hole injection layer is positioned at;
(6) electron transfer layer on luminescent layer is positioned at;
(7) electron injecting layer on electron transfer layer is positioned at;
And
Described luminescent layer is between described hole transmission layer and described electron transfer layer;
Described negative electrode is positioned on described electron injecting layer.
In another preference, described electroluminescent device is blue light electroluminescent device.
Should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the present invention and can combining mutually between specifically described each technical characteristic in below (eg embodiment), thus form new or preferred technical scheme.As space is limited, tiredly no longer one by one to state at this.
Accompanying drawing explanation
Fig. 1 is compound PI-SBFF-PI DSC curve in a nitrogen atmosphere (heating rate 20 DEG C of min that embodiment 2 obtains
-1) and TGA curve (heating rate 20 DEG C of min
-1), wherein X-coordinate is temperature.
Fig. 2 is the absorption curve of compound PI-SBFF-PI in trichloromethane that obtain of embodiment 2 and the PL curve in methylene dichloride, and wherein X-coordinate is wavelength, and ordinate zou is intensity;
Fig. 3 is the cyclic voltammetry curve of compound PI-SBFF-PI in methylene dichloride that embodiment 2 obtains, and wherein X-coordinate is voltage, and ordinate zou is electric current.
Fig. 4 is the organic fluorescence EL device structure schematic diagram of embodiment 4, and wherein, the meaning of each legend is as follows:
1 is substrate, and 2 is nesa coating, and 3 is hole injection layer, and 4 is hole transmission layer, and 5 is electronic barrier layer, and 6 is luminescent layer, and 7 is electron transfer layer, and 8 is electron injecting layer, and 9 is negative electrode.
Embodiment
The present inventor is through long-term and deep research, be surprised to find that, having benzo spiral shell two fluorenes that 5,9-bis-replaces structure can be used for being built with organic electroluminescence devices as high-performance, high efficiency blue light material, and above-mentioned compound also has extraordinary stability.Based on above-mentioned discovery, contriver completes the present invention.
Term
As used herein, term " spiral shell benzofluorene analog derivative " or " the compounds of this invention " are used interchangeably, the disubstituted derivative that to refer to spiral shell [benzofluorene-7,9 '-fluorenes] be core.
Term " electroluminescent organic material " refers to polymer or the Small molecule organic materials that can send light 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, comprises monocycle, two rings, polyaromatic, such as phenyl, naphthyl, or similar group.
Term " C1 ~ C30 heteroaryl " refers to the heteroaryl with 1 ~ 30 carbon atom, comprises monocycle, two rings, polyaromatic, such as pyridyl, quinolyl, or similar group.
Term " replacement " refers to that the one or more hydrogen atoms on group are selected from the substituting group replacement of lower group: C1 ~ C4 alkyl, C3 ~ C6 cycloalkyl, halogen, phenyl; Wherein, described phenyl comprises unsubstituted phenyl or has 1-3 substituent substituted-phenyl, and described substituting group is selected from: halogen, C1-C4 alkyl.
Term " halogen " refers to F, Cl, Br and I.
Formula I
The invention provides a kind of compound with formula I structure:
Wherein, M is selected from lower group: the aryl of substituted or unsubstituted C6-C30, the heteroaryl of substituted or unsubstituted C1-C30.
In another preference, described M is selected from lower group: the aryl of substituted or unsubstituted C12-C30, the heteroaryl of substituted or unsubstituted C6-C30.
In another preference, described M is selected from lower group: anthryl, phenanthryl, pyrenyl, benzimidazolyl-.
Described compound may be used for preparing luminescent material, or for the preparation of electroluminescent device.
In another preference of the present invention, described compound can be prepared by the following method:
In inert solvent, react with such as formula the compound shown in II and formula III compound, thus obtain formula I.
Wherein, described formula III compound is selected from lower group: M-B (OH)
2, M-B (OCCH
3cH
3)
2.
Above-mentioned various in, X is selected from lower group: F, Cl, Br, I;
M is selected from lower group: the aryl of substituted or unsubstituted C6-C30, the heteroaryl of substituted or unsubstituted C1-C30.
Preferably, described X is selected from lower group: Cl, Br.
In another preference, described reaction is carried out under catalyzer and/or alkali exist.
In another preference, described catalyzer is palladium catalyst, is preferably selected from lower group: tetrakis triphenylphosphine palladium, two (triphenylphosphine) palladium chloride, or its combination.
In another preference, described alkali comprises: sodium carbonate, salt of wormwood, cesium carbonate, Potassium ethanoate, potassiumphosphate, sodium hydroxide, potassium hydroxide, Potassium monofluoride, or its combination.
In another preference, the mol ratio of described formula II compound and formula III compound is 1:2 ~ 1:3.
In another preference, described inert solvent is selected from lower group: water, ethanol, glycol dimethyl ether, toluene, tetrahydrofuran (THF), Isosorbide-5-Nitrae-dioxane, or its combination.
In another preference, described formula II compound is prepared by the following method:
In inert solvent, with spiral shell [benzofluorene-7,9 '-fluorenes] and X
2reaction, obtains formula II compound.
Wherein, X is selected from lower group: F, Cl, Br, I; Be preferably Cl and/or Br.
In another preference, described inert solvent is selected from lower group: methylene dichloride, chloroform, tetracol phenixin, or its combination.
Electroluminescent device
Spiral shell benzofluorene analog derivative of the present invention can use as luminescent layer in organic fluorescence electroluminescent device, to prepare electroluminescent device.
A kind of preferred electroluminescent device of the present invention, comprising:
(1) substrate;
(2) nesa coating on substrate is positioned at;
(3) hole injection layer on nesa coating is positioned at;
(4) hole transmission layer on hole injection layer is positioned at;
(5) electronic barrier layer on hole transmission layer is positioned at;
(6) luminescent layer on electronic barrier layer is positioned at;
(7) electron transfer layer on luminescent layer is positioned at;
(8) electron injecting layer on electron transfer layer is positioned at;
(9) negative electrode on electron injecting layer is positioned at;
And containing the compounds of this invention in described luminescent layer, or described luminescent layer prepares with compound as described in the first aspect of the invention.
The material of other layers such as described nesa coating, hole injection layer, hole transmission layer is not limit, and can be chosen according to actual needs, preferably, in described device by those skilled in the art:
Described hole injection layer can comprise MoO
3; And/or
Described hole transmission layer can comprise 4,4 '-two (9-carbazole) biphenyl; And/or
Described electronic barrier layer can comprise 4,4 ', 4 "-three (carbazole-9-base) triphenylamines; And/or
Described electron transfer layer can comprise 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene; And/or
Described electron injecting layer can comprise the material being selected from lower group: LiF, MoO
3, WO
3, or its combination.
Described each layer thickness is not particularly limited, and can be adjusted according to practical situation.In a preference of the present invention, in described device, the thickness of each layer is as follows:
The thickness of described hole injection layer (3) is 10-20nm; And/or
The thickness of described hole transmission layer (4) is 15-80nm; And/or
The thickness of described electronic barrier layer (5) is 0-10nm; And/or
Described luminescent layer (6) thickness is 10-30nm; And/or
Described electron transfer layer (7) thickness is 25-40nm; And/or
The thickness of described electron injecting layer (8) is 0.5-2nm.
A kind of preferred structure of described electroluminescent device is laminate structure, as shown in Figure 3, substrate (1), nesa coating (2), hole injection layer (3), hole transmission layer (4), electronic barrier layer (5), luminescent layer (6), electron transfer layer (7), electron injecting layer (8), negative electrode (9) is followed successively by negative electrode by substrate, wherein, luminescent layer (6) adopts undoped spiral shell benzofluorene analog derivative.
In above-mentioned organic fluorescence electroluminescent device:
Hole injection layer (3) material is preferably 4,4 ', 4 '-three (carbazole-9-base) triphenylamine, and its thickness is preferably 10-20nm;
Hole transmission layer (4) material is preferably 4,4 '-two (9-carbazole) biphenyl, and its thickness is preferably 15-80nm;
Electronic barrier layer (5) material is preferably 4,4 ', 4 "-three (carbazole-9-base) triphenylamine, its thickness is preferably 0-10nm;
Luminescent layer (6) thickness is preferably 10-30nm;
Electron transfer layer (7) material is preferably 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene, and its thickness is preferably 25-40nm;
Electron injecting layer (8) material is preferably LiF, MoO
3, WO
3deng, its thickness is preferably 0.5-2nm; Negative electrode (9) material is preferably aluminium, and silver, calcium, magnesium etc., its thickness is preferably 100-200nm.
Major advantage of the present invention comprises:
Provide a kind of spiral shell benzofluorene material, spiral shell benzofluorene is asymmetric structure, Heat stability is good, and has the comparatively more active site of spiral shell two fluorenes, easily realizes the adjustment to its structure, thus optimizes energy level and the electroluminescent properties of material.
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example, usually conveniently condition, or according to the condition that manufacturer advises.Unless otherwise indicated, otherwise per-cent and number calculate by weight.
The preparation of embodiment 1:5,9-bis-(anthracene-9-base) spiral shell [benzofluorene 7,9 '-fluorenes]
In the present embodiment, the structural formula of 5,9-bis-(anthracene-9-base) spiral shell [benzofluorene 7,9 '-fluorenes] compound is:
The preparation method of above-mentioned 5,9-bis-(anthracene-9-base) spiral shell [benzofluorene 7,9 '-fluorenes] compound comprises the steps:
Step 1: synthetic intermediate 1:1-(2-bromophenyl) naphthalene
Under nitrogen protection; 1-naphthalene boronic acids (5.33g is added successively at 500ml there-necked flask; 30mmol); tetrakis triphenylphosphine palladium (0.7g; 0.60mmol); adjacent bromo-iodobenzene (8.64g; 30mmol), toluene (300ml), the aqueous sodium carbonate (90ml) of 2M; dehydrated alcohol (90ml); back flow reaction 24hr, with dichloromethane extraction, anhydrous magnesium sulfate drying; remove solvent, cross post separation and obtain white solid product 1-(2-bromophenyl) naphthalene.Productive rate: 87%.
Step 2: synthetic intermediate 2: spiral shell [benzofluorene 7,9 '-fluorenes]
Under nitrogen protection, intermediate 1-(2-bromobenzene)-naphthalene (7.08g that step 1 is synthesized is added in 500ml bottle with two necks, 25mmol), anhydrous tetrahydro furan (50ml), be placed in-78 DEG C of cooling 10min, drip n-BuLi (21ml, 50mmol), stir 3h, add the 9-Fluorenone (9.0g being dissolved in 30ml THF, 50mmol), be placed in room temperature reaction 16h, react with saturated sodium bicarbonate aqueous solution (75ml) cancellation, with dichloromethane extraction, anhydrous magnesium sulfate drying, remove solvent, be placed in 500ml single port bottle, add acetic acid, add the hydrochloric acid soln (1.5ml of catalytic amount, 12N), back flow reaction 12h, with dichloromethane extraction, anhydrous magnesium sulfate drying, remove solvent, cross post separation and obtain white solid product spiral shell [benzofluorene 7, 9 '-fluorenes].Productive rate: 70%.
Step 3: synthetic intermediate 3:5,9-dibromo spiral shell [benzofluorene 7,9 '-fluorenes]
The intermediate spiral shell [benzofluorene 7,9 '-fluorenes] (3.29g, 9mmol) of the 2-in-1 one-tenth of step is added in 250ml there-necked flask, chloroform dissolves, and is dissolved in bromine (4.32g, the 27.0mmol of 25ml chloroform, 1.36ml) be added drop-wise in there-necked flask, stirring at room temperature 18h, aqueous sodium hydroxide solution removes unreacted bromine, with dichloromethane extraction, anhydrous magnesium sulfate drying, removes solvent, crosses post separation and obtains yellow solid product 5,9-dibromo spiral shell [benzofluorene 7,9 '-fluorenes].Productive rate: 93%.
Above-mentioned intermediate 3 is analyzed: ultimate analysis: C, 66.45; H, 3.09, calculated value: C, 66.44; H, 3.08; Br, 30.48.Proton nmr spectra (400MHz, d
6-Acetone): δ 9.01 (d, 1H, J=8.32Hz), 8.59 (d, 1H, J=8.32Hz), 8.35 (d, 1H, J=8.32Hz), 8.08 (d, 2H, J=7.39Hz), 7.91 (t, 1H, J=7.39Hz), 7.81 (t, 1H, J=7.86Hz), 7.72 (d, 1H, J=8.32Hz), 7.49 (t, 2H, J=7.39Hz), 7.20 (t, 2H, J=7.86Hz), 7.10 (s, 1H), 6.91 (s, 1H), 6.78 (d, 2H, J=7.39Hz).
Step 4: synthesis 5,9-bis-(anthracene-9-base) spiral shell [benzofluorene 7,9 '-fluorenes] AN-SBFF-AN
Under nitrogen protection; the intermediate 5 that step 3 is synthesized is added successively in 250ml there-necked flask; 9-dibromo spiral shell [benzofluorene 7; 9 '-fluorenes] (1.0g; 2.0mmol); 9-anthracene boric acid (1.0g; 4.6mmol), tetrakis triphenylphosphine palladium (0.30g), toluene (150ml), the wet chemical (30ml) of 2M; dehydrated alcohol (30ml); back flow reaction 3d, with dichloromethane extraction, anhydrous magnesium sulfate drying; remove solvent, cross post separation and obtain solid product AN-SBFF-AN.
Above-mentioned AN-SBFF-AN is analyzed: ultimate analysis: C, 95.22; H, 4.78, calculated value: C, 95.23; H, 4.77.Proton nmr spectra (400MHz, CDCl
3): δ 9.14 (d, 1H, J=8.56), 8.77 (d, 1H, J=8.03), 8.52 (s, 1H), 8.44 (s, 1H), 8.04 ~ 8.00 (m, 4H), 7.78 ~ 7.75 (m, 1H), 7.70 (d, 2H, J=9.10), 7.65 (d, 3H, J=6.96), 7.45 ~ 7.30 (m, 9H), 7.26 ~ 7.15 (m, 7H), 7.08 (d, 2H, J=7.49), 6.98 (s, 2H).
The preparation of embodiment 2:5,9-bis-(phenanthrene-9-base) spiral shell [benzofluorene 7,9 '-fluorenes]
In the present embodiment, the structural formula of 5,9-bis-(phenanthrene-9-base) spiral shell [benzofluorene 7,9 '-fluorenes] compound is:
The preparation method of above-mentioned 5,9-bis-(phenanthrene-9-base) spiral shell [benzofluorene 7,9 '-fluorenes] compound comprises the steps:
Step 1: synthesis 5,9-bis-(phenanthrene-9-base) spiral shell [benzofluorene 7,9 '-fluorenes] PI-SBFF-PI
Under nitrogen protection; embodiment 1 step 3 synthetic intermediate 5 is added successively in 500ml there-necked flask; 9-dibromo spiral shell [benzofluorene 7; 9 '-fluorenes] (0.68g; 1.3mmol); luxuriant and rich with fragrance boric acid (the 0.86g of 9-; 3.9mmol), two (triphenylphosphine) palladium chloride (0.16g), toluene (100ml), the wet chemical (30ml) of 2M; dehydrated alcohol (30ml); back flow reaction 3d, with dichloromethane extraction, anhydrous magnesium sulfate drying; remove solvent, cross post separation and obtain white solid product PI-SBFF-PI.Productive rate: 70%.
Above-mentioned PI-SBFF-PI is analyzed: ultimate analysis: C, 95.22; H, 4.78, calculated value: C, 95.23; H, 4.77.Proton nmr spectra (400MHz, CDCl
3): δ 9.06 (d, 1H, J=8.62), 8.75 ~ 8.70 (m, 3H), 8.67 (dd, 2H, J
1=8.13, J
2=2.96), 7.87 ~ 7.80 (m, 3H), 7.78 ~ 7.71 (m, 4H), 7.69 ~ 7.55 (m, 9H), 7.45 (td, 1H, J
1=8.13, J
2=0.98), 7.40 ~ 7.33 (m, 4H), 7.30 (td, 1H, J
1=7.51, J
2=0.99), 7.20 (td, 1H, J
1=7.63, J
2=0.99), 7.14 (td, 1H, J
1=7.63, J
2=0.99), 7.04 ~ 6.96 (m, 4H).
Fig. 1 is compound PI-SBFF-PI DSC curve in a nitrogen atmosphere (heating rate 20 DEG C of min that embodiment 2 obtains
-1) and TGA curve (heating rate 20 DEG C of min
-1), wherein X-coordinate is temperature, finds that its decomposition temperature is 468 DEG C, have high thermostability by TGA, and DSC fails to obtain its melt temperature, illustrates that PI-SBFF-PI has the structure of high distortion, can eliminate the interaction between solid-state molecular.
Fig. 2 is the absorption curve of compound PI-SBFF-PI in trichloromethane that obtain of embodiment 2 and the PL curve in methylene dichloride, and wherein X-coordinate is wavelength, and ordinate zou is intensity, absorbs threshold value λ
onsetfor 389nm, according to
obtain its optical energy band
Fig. 3 is that the compound PI-SBFF-PI that embodiment 2 obtains adopts 0.01cm
2platinum dish as working electrode, platinum filament as to electrode, silver/silver chloride as reference electrode, at 0.1molL
-1bu
4nPF
6methylene dichloride in cyclic voltammetry curve, the HOMO value calculating compound by oxidation peak is-5.60eV, and the LUMO value obtaining compound according to optical band gap is-2.4eV, and this material can be applied to blue light organic emissive field.
The preparation of embodiment 3:5,9-bis-(benzoglyoxaline-9-base) spiral shell [benzofluorene 7,9 '-fluorenes]
In the present embodiment, the structural formula of 5,9-bis-(benzoglyoxaline-9-base) spiral shell [benzofluorene 7,9 '-fluorenes] compound is:
The preparation method of above-mentioned 5,9-bis-(benzoglyoxaline-9-base) spiral shell [benzofluorene 7,9 '-fluorenes] compound comprises the steps:
Step 1: synthesis 5,9-bis-(benzoglyoxaline-9-base) spiral shell [benzofluorene 7,9 '-fluorenes] MI-SBFF-MI
Under nitrogen protection; embodiment 1 step 3 synthetic intermediate 5 is added successively in 250ml there-necked flask; 9-dibromo spiral shell [benzofluorene 7; 9 '-fluorenes] (1.0g; 2.0mmol); benzoglyoxaline tetramethyl ethylene ketone boric acid ester (1.75g; 4.4mmol), two (triphenylphosphine) palladium chloride (0.20g), toluene (100ml), the wet chemical (20ml) of 2M; dehydrated alcohol (30ml); back flow reaction 3d, with dichloromethane extraction, anhydrous magnesium sulfate drying; remove solvent, cross post separation and obtain white solid product MI-SBFF-MI.Productive rate: 45%.
Above-mentioned MI-SBFF-MI is analyzed: ultimate analysis: C, 89.12; H, 4.68, N, 6.20, calculated value: C, 89.11; H, 4.69; N, 6.20.Proton nmr spectra (400MHz, CDCl
3): δ 8.95 (d, 1H, J=8.51Hz), 8.53 (d, 1H, J=8.19Hz), 8.00-7.94 (m, 3H), 7.89 (d, 2H, J=7.53Hz), 7.79-7.73 (m, 2H), 7.66-7.23 (m, 27H), 7.13 (td, 2H, J
1=7.61Hz, J
2=0.74Hz), 7.00 (d, 1H, J=1.64Hz), 6.79 (d, 2H, J=7.53Hz), 6.75 (s, 1H).
The performance comparison of material of the present invention and 2,7-bis-(phenanthrene-9-base) of the prior art-9,9 '-spiral shell two fluorenes is as shown in table 1 below:
Table 1: the performance comparison of material of the present invention and current material
| Decomposition temperature (DEG C) | Optical energy band (eV) | HOMO value (eV) | LUMO value (eV) | |
| Embodiment 1 | - | - | - | - |
| Embodiment 2 | 468 | 3.20 | -5.70 | -2.50 |
| Embodiment 3 | 524 | 3.00 | -5.62 | -2.62 |
| Prior art | 503 | 3.50 | -5.80 | -2.30 |
* "-" indicates without corresponding parameter
Material of the present invention has high thermostability, and the spirobifluorene derivative of existing bibliographical information has close even higher stability.The electronic mobility of usual OLED material is less than hole mobility, and material of the present invention has relatively low lumo energy, can reduce electron injection potential barrier, and equilbrium carrier injects, and improves the composite efficiency of current carrier, improves luminescent properties.
The preparation of embodiment 4:MI-SBFF-MI organic electroluminescence device
By the materials application prepared in embodiment 3 in preparing organic electroluminescence device.This electroluminescent device is laminate structure, as shown in Figure 4, comprises substrate successively and is followed successively by substrate 1, nesa coating 2, hole injection layer 3, hole transmission layer 4, electronic barrier layer 5, luminescent layer 6 to negative electrode, electron transfer layer 7, electron injecting layer 8 and negative electrode 9.Wherein, substrate 1 selects glass or transparent plastics; Nesa coating 2 selects tin indium oxide (ITO) as anode; After being cleaned by substrate, glow discharge under high purity oxygen atmosphere (plasma) processes 10min, under a high vacuum (2 × 10
-6pa) under, the MoO that evaporation one deck 10nm is thick on nesa coating 2
3as hole injection layer 3, then continue on hole injection layer 3 evaporation one deck 80nm thick 4,4 '-two (9-carbazole) biphenyl is as hole transmission layer 4, then on hole transmission layer 4 evaporation one deck 5nm thick 4,4 ', 4 "-three (carbazole-9-base) triphenylamine is as electronic barrier layer 5; luminescent layer 6 that then evaporation one deck 20nm is thick on electronic barrier layer 5; luminescent layer 6 adopts prepare in the present embodiment 35; 9-bis-(benzoglyoxaline-9-base) spiral shell [benzofluorene 7,9 '-fluorenes]; Thick 1,3,5-tri-(1-phenyl-1H-benzimidazolyl-2 radicals-Ji) benzene of evaporation one deck 40nm is continued afterwards as electron transfer layer 7 on luminescent layer 6; Then on electron transfer layer 7, deposit electron injecting layer 8, electron injecting layer 8 selects LiF, and its thickness is 1nm; Finally deposition cathode 9 on electron injecting layer 8, negative electrode 9 selects Al, and its thickness is 100nm.
In the preparation process of above-mentioned organic fluorescence electroluminescent device, the thickness of film adopts miniature thickness tester to measure it, measures luminosity with luminance meter, and all organic materialss and LiF and metal A l adopt the mode of vacuum evaporation film forming.
When applying suitable external voltage to above-mentioned organic fluorescence electroluminescent device, the performance recording this electroluminescent fluorescent luminescent device is as shown in table 2.
Table 2: the performance table (PR655 test) of organic electroluminescence device in embodiment 3
As can be seen from above-mentioned table 1, the blue emission of electroluminescent spectrum peak value at 436nm can be realized with material of the present invention.
The all documents mentioned in the present invention are quoted as a reference all in this application, are just quoted separately as a reference as each section of document.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read above-mentioned teachings of the present invention, these equivalent form of values fall within the application's appended claims limited range equally.
Claims (10)
1. one kind has the compound of formula I structure:
Wherein, M is selected from lower group: the aryl of substituted or unsubstituted C6-C30, the heteroaryl of substituted or unsubstituted C1-C30.
2. the method for making of compound as claimed in claim 1, is characterized in that, comprise step:
In inert solvent, react with such as formula the compound shown in II and alkylating reagent, thus obtain formula I;
Wherein, described alkylating reagent is selected from lower group: M-B (OH)
2, M-B (OCCH
3cH
3)
2;
Above-mentioned various in, X is selected from lower group: F, Cl, Br, I;
M is selected from lower group: the aryl of substituted or unsubstituted C6-C30, the heteroaryl of substituted or unsubstituted C1-C30.
3. the purposes of compound as claimed in claim 1, is characterized in that, for the preparation of luminescent material, or for the preparation of electroluminescent device.
4. a luminescent material, is characterized in that, described luminescent material comprises formula I as claimed in claim 1, or described luminescent material formula I as claimed in claim 1 is made.
5. material as claimed in claim 4, it is characterized in that, described material is luminescent material.
6. material as claimed in claim 5, it is characterized in that, described luminescent material is blue light emitting material.
7. material as claimed in claim 5, it is characterized in that, described luminescent material is electroluminescent material.
8. a device, is characterized in that, described device has material as claimed in claim 4, or described device material as claimed in claim 4 is made.
9. device as claimed in claim 8, it is characterized in that, described device is electroluminescent device.
10. device as claimed in claim 9, it is characterized in that, described electroluminescent device is blue light electroluminescent device.
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Cited By (2)
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| CN105131939A (en) * | 2015-08-28 | 2015-12-09 | 中节能万润股份有限公司 | Organic electroluminescence material with spiral structure and application thereof |
| CN109704913A (en) * | 2018-12-27 | 2019-05-03 | 瑞声科技（南京）有限公司 | A kind of spiro fluorene compound and its application |
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Cited By (2)
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| CN105131939A (en) * | 2015-08-28 | 2015-12-09 | 中节能万润股份有限公司 | Organic electroluminescence material with spiral structure and application thereof |
| CN109704913A (en) * | 2018-12-27 | 2019-05-03 | 瑞声科技（南京）有限公司 | A kind of spiro fluorene compound and its application |
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