CN1240808C - Organic electroluminescent material of dendritic macromolecular naphthalene imide - Google Patents

Organic electroluminescent material of dendritic macromolecular naphthalene imide Download PDF

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CN1240808C
CN1240808C CN 03151150 CN03151150A CN1240808C CN 1240808 C CN1240808 C CN 1240808C CN 03151150 CN03151150 CN 03151150 CN 03151150 A CN03151150 A CN 03151150A CN 1240808 C CN1240808 C CN 1240808C
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naphthalimide
dendritic
naphthene
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CN1526789A (en
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朱为宏
杜葩
赵非
田禾
潘建峰
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East China University of Science and Technology
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Abstract

The present invention relates to organic electroluminescent material of naphthalimide dendritic macromolecules. Dendritic reaction is utilized to lead specific functional units onto dendron, a plurality of specific functional groups are connected to form functional molecular group clusters with dendritic peripheries, and then, the clusters are respectively connected with naphthalimide used as the core pigment to synthesize the novel functional organic luminescent material with dendritic peripheries. The material comprises 1, 8-naphthalimide and current carrier (carbazole or diazole) functional groups. The compound can ensure that the injection and the composition of current carriers and the produce of excitons all generate in molecules, and can also simplify the manufacturing technology of devices. In addition, the organic electroluminescent material of the present invention has better luminous efficiency and crystallization resisting performance than the existing luminescent material of organic small molecules and polymers.

Description

Naphthalimide dendritic macromole electroluminescent organic material
Technical field
The present invention relates to a kind of electroluminescent organic material, particularly naphthalimide dendritic macromole electroluminescent organic material.
Background technology
ORGANIC ELECTROLUMINESCENCE DISPLAYS is emerging in recent years a kind of technique of display, and wherein, the organic film El element has from main light emission, low voltage drive and luminous advantages such as adjustability, and therefore, the ORGANIC ELECTROLUMINESCENCE DISPLAYS technology has broad application prospects.
Adopting well behaved electroluminescent organic material is the important foundation that realizes ORGANIC ELECTROLUMINESCENCE DISPLAYS.At present, existing electroluminescent organic material mainly is divided into two kinds of organic molecule type and polymer-types, and the luminous efficiency of these two kinds of electroluminescent organic materials is all lower, as the early stage anthracene single crystal body of using, has reached 5% luminous efficiency (photon to iunjected charge than) in the research of EL.The double-deck luminescent device of the PPV that the PPV-itrile group of Friend manufacturing replaces, its luminous efficiency only is 4%.The active luminescent layer of the poly-bi-methoxy vinylbenzene individual layer of their manufacturing also obtains identical luminous efficiency.In addition, after the film of these the two kinds of electroluminescent organic materials process long " wearing out ", the phenomenon of recrystallize often occurs, and this phenomenon is considered to restrict the major cause that organic photoelectrical material is used.Seek a kind of electroluminescent organic material and become purpose of the present invention with higher photoluminescence efficiency and good anti-crystallization.
Summary of the invention
The object of the invention is, a kind of electroluminescent organic material with higher photoluminescence efficiency and good anti-crystallization is provided.
Design of the present invention is such:
Branch (Dendron) molecule is made up of conjugate light-emitting nuclear, conjugation branch and surface group.The radiative color of conjugate light-emitting nuclear control, peripheral group decision physical property, and branch allows electric transmission to nuclear.It is better than electroluminescent organic material main because be of organic molecule and polymkeric substance: (1) dendritic structure provides a kind of interactional method of controlling between the molecule: only be that surface group or outside branch are in contact with one another in the branch molecule in a high generation, this can be avoided some small molecules and the incident coacervation of polymkeric substance.(2) in the branch macromole, chromophoric group is unconjugated be connected with the peripheral chromophoric group that the mechanism that is independent of dendritic structure transfers energy to centronucleus chromophoric group branch molecule with the centronucleus chromophoric group with higher efficient on every side, the absorption spectrum of whole molecule is their spectrographic stacks separately, form the absorption spectrum of non-constant width, when having effective intramolecular energy transfer in the system, so wide spectral absorption only causes the very narrow fluorescent emission of centronucleus chromophoric group, and this light collection, the degree that light amplification is good are well imagined.Simultaneously, from space availability ratio, branch molecular energy accumulative cross-sectional area is far longer than the molecule of other type, because be that the photon energy that the multidimensional multiple spot is absorbed is focused on the single point by the branch molecule.Thereby raising luminous quantum efficiency.
The contriver is on the basis of big quantity research, based on 1, the 8-naphthalimide is that (its electron affinity is about 3.1eV for a kind of luminescent material of high performance electronic mode transmission, K.Utsugi, S.Takano, J.Electrochem.Soc., 1992,139 (12), 3610), utilize to innovation the branch reaction, go up at branch (Dendron) and introduce specific functional unit, synthesizing new Stability Analysis of Structures, electroluminescent organic material with better solubleness dendroid functionalization, have specific function group and couple together a plurality of, form functionalization dendroid periphery molecular cluster, then they are connected the electroluminescent organic material of the three-dimensional peripheral dendroid functionalization of synthesizing new respectively with core pigment naphthalimide.Such material contains 1,8-naphthalimide and current carrier (carbazole Huo oxadiazole) functional group.This compounds can guarantee that the injection of current carrier, the generation that is compound to exciton all occur in intramolecularly, simplify the manufacture craft of device, and studied the fluorescent characteristic of this compounds, be that the energy that peripheral functional group absorbs can pass to core pigment naphthalimide with higher efficient, have special light collection, light amplification.
Technical scheme
The said electroluminescent organic material of the present invention is the dendritic macromole compound that contains the carrier transport functional group, and its structure is as shown in the formula shown in (1):
Figure C0315115000051
In the formula:
R 1For amino, alkane for amino or alkoxyl group, preferred R 1Be dimethylamino, diethylin, piperidyl, piperazinyl, morphine quinoline base, methoxy or ethoxy;
R 2Be Qu Dai oxadiazole base or 9-alkyl carbazole base; Wherein: the structure of said Qu Dai oxadiazole base is suc as formula (2)
Figure C0315115000061
In the formula: X is H, C 1～C 12Alkyl or aryl, preferred tertiary butyl or phenyl.
The structure of said 9-alkyl carbazole base is suc as formula (3)
In the formula: n=1～6, preferred n=4.
The method for preparing the said electroluminescent organic material of the present invention comprises the steps:
(1) 4-R 1-1,8-naphthalimide synthetic
4-R 1-1, the 8-naphthalimide is the compound with following general structure:
With 4-bromo-1,8-naphthalene acid anhydride is raw material (its synthetic prior art that adopts does not repeat them here), works as R 1Synthetic method for amino, alkane during: 4-bromo-1 for amino, 8-naphthalene acid anhydride is catalyzer through reacting at organic solvent (as ethylene glycol monomethyl ether or DMF) with ammonia secondary amine with Salzburg vitriol or cuprous chloride, back flow reaction 2-8 hour, pour into and separate out solid in the frozen water, filter and collect 4-R 1-1,8-naphthalene acid anhydride;
Work as R 1Synthetic method during for alkoxyl group: 4-bromo-1,8-naphthalene acid anhydride, potassium hydroxide and a small amount of dioxane react in alcoholic solution, and backflow 2-8 hour, cooling had solid to separate out, and filtered and collected 4-R 1-1,8-naphthalene acid anhydride;
With 4-R 1-1,8-naphthalene acid anhydride, 5-amino-1,3-phthalic acid are raw material, are solvent with exsiccant DMF, under nitrogen protection, are heated to 100 ℃, stir after 2-24 hour, pour into and separate out solid in the frozen water, filter and collect 4-R 1-1, the 8-naphthalimide.
(2) replacement De oxadiazole branch is unitary synthetic
Said replacement De oxadiazole branch unit (2-(4 '-X) phenyl, 5-(4 '-brooethyl) phenyl-[1,3,4]-oxadiazoles) is for having the compound of following general structure:
Figure C0315115000071
Wherein, X is H, C 1～C 12Alkyl or aryl
With 2-(4 '-X) phenyl, 5-(4 '-methyl) phenyl-[1,3,4]-oxadiazoles (this compound is a known substance, its preparation can referring to existing document) were raw material, through NBS bromination promptly in benzoyl peroxide amine and tetracol phenixin backflow 4-10 hour, get 2-(4 '-X) phenyl behind the cold filtration, 5-(4 '-brooethyl) phenyl-[1,3,4]-oxadiazoles.
(3) the carbazole branch of Qu Daiing is unitary synthetic
Said substituted carbazole branch unit is a 9-bromo alkyl carbazole, and its structural formula is as follows
N=1 in the formula～6 are added to carbazole, potassium hydroxide and organic solvent DMF in two bromoalkanes after 1 hour in stirring at normal temperature and go, and at stirring at normal temperature 10-12 hour, pour in the water, have solid to separate out, and filter, and collect 9-bromo alkyl carbazole.
(4) the branch reaction of replacement De oxadiazole
(5-dihydroxy-benzyl alcohol, salt of wormwood and anhydrous propanone are raw material for 4 '-X) phenyl, 5-(4 '-brooethyl) phenyl-[1,3,4]-oxadiazoles, 3, and 18-hat-6 is a catalyzer, under argon shield, refluxes 24～56 hours with 2-.Be cooled to room temperature, revolve most of acetone, pour in the water, dichloromethane extraction discards water layer, the anhydrous MgSO of organic phase 4Drying is spin-dried for, and obtains compound (a);
With compound (a), methylsulfonyl chloride, triethylamine and anhydrous methylene chloride is raw material, stirring at normal temperature 10-24 hour.Pour in the water, dichloromethane extraction discards water layer.The anhydrous MgSO of organic phase 4Drying is spin-dried for, and obtains the methanesulfonates compound (b) of compound (a).
(5) the branch reaction of substituted carbazole
With 9-bromo alkyl carbazole, 3,5-dihydroxy-benzyl alcohol, salt of wormwood and anhydrous propanone are raw material, and 18-hat-6 is a catalyzer, under argon shield, refluxes 4～56 hours.Be cooled to room temperature, revolve most of acetone, pour in the water, dichloromethane extraction discards water layer.The anhydrous MgSO of organic phase 4Drying is spin-dried for, and obtains compound (c).
With compound (c), methylsulfonyl chloride, triethylamine and anhydrous methylene chloride is raw material, stirring at normal temperature 2-24 hour, pours in the water.Dichloromethane extraction discards water layer.The anhydrous MgSO of organic phase 4Drying is spin-dried for, and obtains the methanesulfonates compound (d) of compound (c).
Figure C0315115000091
N=1 in the formula～6
(6) contain dendritic macromole synthetic of carrier transport functional group
With 4-R 1-1,8-naphthalimide (compound N P), compound (b) or compound (d), salt of wormwood and exsiccant DMF are raw material, are heated to 100 ℃, stir after 10～24 hours, reaction solution is poured in the water, have light yellow solid to separate out, filter, wash with water, after the drying target product.
The dendritic macromole compound that electroluminescent organic material of the present invention promptly contains the carrier transport functional group can be used to prepare electroluminescent device.The luminescent layer of electroluminescent device adopts the dendritic macromole film forming of conventional film (as the method with spin coating lacquering technique or vacuum evaporation) with the carrier transport functional group of the present invention's proposition.When luminescent material of the present invention was applied to electroluminescent device, maximum emission wavelength was 518nm, is yellow green light, was 1, and the feature of 8-naphthalimide functional group is luminous, and maximum luminance is 1800cd/m under driving voltage 15V 2Its luminous efficiency of electroluminescent organic material of the present invention and anti-crystallization all are better than the luminescent material of existing organic molecule and polymkeric substance.
Description of drawings
Fig. 1 is fluorescence spectrum (excitation wavelength is 330nm)
Wherein: the mixture of the methyl esters of a-compound 3 and compound N P3;
B-compound N PCZ3.
Compound 3 is 2: 1 with the mol ratio of the methyl esters of compound N P3, and concentration is identical with compound N PCZ3.
Fig. 2 is fluorescence spectrum (excitation wavelength is 345nm)
Wherein: the mixture of the methyl esters of a-compound 3 and compound N P3;
B-compound N PCZ3.
Compound 3 is 2: 1 with the mol ratio of the methyl esters of compound N P3, and concentration is identical with compound N PCZ3.
Specific implementation method
Below by example the present invention is further illustrated, its objective is to better understanding content of the present invention.Therefore, the cited case does not limit protection scope of the present invention.
Embodiment 1
Synthesizing of the dendritic macromole of carrier transport functional group (compound N POXZ1)
Figure C0315115000101
(1) replace 1,8-naphthalimide (compound N P1) synthetic:
In 50ml single port bottle, add 4-N, N '-dimethyl-1, (1.0g, 4.15mmol) (nitrogen protection is heated to 100 ℃ to 8-naphthalene acid anhydride for 1.5g, 8.2mmol) exsiccant DMF (20ml), stirs after 24 hours, stops heating, is cooled to normal temperature with 5-amino-different metatitanic acid.Reaction solution is poured in the 100ml water, had a large amount of orange/yellow solid to separate out, filter, use massive laundering, drying gets the orange red solid of 0.9g (compound N P1) with the methylene dichloride recrystallization then, and productive rate is 54%, m.p.＞250 ℃.
1H-NMR(500MHz，DMSO-d 6，ppm)δ＝3.1(s，6H，N(CH 3) 2)，7.25(d，1H，naphthene-H，J＝8.3Hz)，7.8(t，1H，naphthene-H，J＝7.9Hz)，8.2(s，Ph-H，2H)，8.37(d，1H，naphthene-H，J＝8.2Hz)，8.45(d，lH，naphthene-H，J＝7.2Hz)，8.52(s，1H，Ph-H)，8.57(d，1H，naphthene-H，J＝8.5Hz)。
(2) the branch reaction of 2-(4 '-tert-butyl-phenyl)-5-(4 '-2-bromomethylphenyl)-[1,3,4]-oxadiazoles (compound 1):
In the 100ml there-necked flask; add 2-(4 '-tert-butyl-phenyl)-5-(4 '-2-bromomethylphenyl)-[1; 3; 4] oxadiazoles (5.6g, 15.62mmol), 3,5-dihydroxy-benzyl alcohol (1.0g; 7.1mmol), salt of wormwood (3.4g; 60.0mmol), (0.38g, 1.42mmol) and anhydrous propanone (50ml), backflow is 56 hours under argon shield for 18-hat-6.Be cooled to room temperature, revolve most of acetone, pour in the water, dichloromethane extraction discards water layer.The anhydrous MgSO of organic phase 4Drying is spin-dried for.With the methylene dichloride is that developping agent carries out the column chromatography purification, obtains 4.2g compound 1 (productive rate is 82.4%), m.p.199-200 ℃.
1H-NMR(500MHz，CDCl 3，ppm)：δ＝1.3(s，18H，-CH 3)，4.7(s，2H，-CH 2OH)，5.2(s，4H，-CH 2-)，6.5(s，1H，Ph-H)，6.7(s，2H，Ph-H)，7.5(d，4H，J＝8.1Hz)，7.55(d，4H，J＝7.8Hz)，8.05(d，4H，J＝8.0Hz)，8.15(d，4H，J＝7.8Hz)。
(3) the methylsulfonyl reaction of compound 1:
In 50ml single port bottle, with compound 1 (1.0g 1.39mmol) is dissolved in the anhydrous methylene chloride (20ml), drip methylsulfonyl chloride (0.158g, 1.39mmol) and 0.14g (1.39mmol) triethylamine, stirring at normal temperature 24 hours.Pour in the water, dichloromethane extraction discards water layer, the anhydrous MgSO of organic phase 4Drying is spin-dried for, and obtains 1.06g white solid (compound 2), and productive rate is 95.5%, m.p.＞250 ℃.
1H-NMR(500MHz，CDCl 3，ppm)：δ＝1.3(s，18H，-CH 3)，4.7(s，2H，-CH 2OH)，5.2(s，4H，-CH 2-)，6.5(s，1H，Ph-H)，6.7(s，2H，Ph-H)，7.5(d，4H，J＝8.4Hz)，7.55(d，4H，J＝7.6Hz)，8.05(d，4H，J＝8.0Hz)，8.15(d，4H，J＝8.3Hz)。
(4) preparation of compound N POXZ1:
In 50ml single port bottle, add compound N P1 (0.1g, 0.248mmol), compound 2 (0.41g, 0.52mmol), (0.1g 0.72mmol) and exsiccant DMF (10ml), is heated to 100 ℃ to salt of wormwood, stirs after 24 hours, stops to heat, and is cooled to normal temperature.Reaction solution is poured in the 40ml water, had light yellow solid to separate out, filter, use massive laundering, drying gets the light yellow target product of 0.073g (compound N POXZ1) with acetone recrystallization then, and productive rate is 16.3%, m.p.＞250 ℃.
1H-NMR(500MHz，CDCl 3，ppm)δ＝3.1(s，6H，N(CH 3) 2)，5.1(s，8H，PhO-CH 2-Ph)，5.4(s，4H，PhO-CH 2-Ph)，6.5(s，2H，PhO-CH 2-Ph)，6.7(s，4H，PhO-CH 2-Ph)，7.15(d，1H，naphthene-H，J＝8.3Hz)，7.5(d，8H，Ph-H(oxz)，J＝8.3Hz)，7.6(d，8H，Ph-H(oxz)，J＝8.0Hz)，7.7(t，1H，naphthene-H，J＝7.9Hz)，8.05(d，8H，Ph-H(oxz)，J＝8.2Hz)，8.13(d，8H，Ph-H(oxz)，J＝8.1Hz)，8.25(s，2H，Ph-H)，8.44(d，1H，naphthene-H，J＝8.2Hz)，8.48(d，1H，naphthene-H，J＝8.2Hz)，8.6(d，1H，naphthene-H，J＝7.1Hz)，8.9(s，1H，Ph-H)。
Embodiment 2
Synthesizing of the dendritic macromole of carrier transport functional group (compound N POXZ2).
Figure C0315115000121
(1) replace 1,8-naphthalimide (compound N P2) synthetic
Figure C0315115000122
In 50ml single port bottle, add 4-piperidyl-1,8-naphthalene (1.0g, 3.56mmol), 5-amino-different metatitanic acid (1.29g, 7.12mmol) and exsiccant DMF (20ml), reaction and treatment process are with compound NP1, obtain 0.88g yellow solid (compound N P2), productive rate is 56.1%, m.p.＞250 ℃.
1H-NMR(500MHz，DMSO-d 6，ppm)δ＝1.65(m，2H，-CH 2-)，1.85(m，4H，-CH 2-)，3.2(t，4H，N-CH 2)，7.25(d，1H，naphthene-H，J＝8.2Hz)，7.8(t，l?H，naphthene-H，J＝7.9Hz)，8.2(s，Ph-H，2H)，8.37(d，1H，naphthene-H，J＝8.2Hz)，8.45(d，1H，naphthene-H，J＝7.1Hz)，8.47(s，1H，Ph-H)，8.53(d，1H，naphthene-H，J＝8.1Hz)。
(2) dendritic macromole of carrier transport functional group (compound N POXZ2) is synthetic:
In 50ml single port bottle, add compound N P2 (0.1g, 0.225mmol), compound 2 (0.38g by step (3) gained in the example 1,0.473mmol), (0.1g is 0.72mmol) with exsiccant DMF (10ml) for salt of wormwood, be heated to 100 ℃, stir after 24 hours, stop heating, be cooled to normal temperature.Reaction solution is poured in 40 ml waters, had light yellow solid to separate out, filter, use massive laundering, drying gets 0.103g light yellow solid (compound N POXZ2) with acetone recrystallization then, and productive rate is 24.8%.m.p.＞250℃。
1H-NMR(500MHz，CDCl 3)δ＝1.4(s，36H，-CH 3)，1.65(m，2H，-CH 2-)，1.85(m，4H，-CH 2-)，3.2(t，4H，N-CH 2)，5.1(s，8H，PhO-CH 2-Ph)，5.4(s，4H，PhO-CH 2-Ph)，6.5(s，2H，PhO-CH 2-Ph)，6.7(s，4H，PhO-CH 2-Ph)，7.25(d，1H，naphthene-H，J＝8.2Hz)，7.55(d，8H，Ph-H(oxz)，J＝8.0Hz)，7.6(d，8H，Ph-H(oxz)，J＝7.8Hz)，7.7(t，1H，naphthene-H，J＝7.9Hz)，8.05(d，8H，Ph-H(oxz)，J＝8.0Hz)，8.13(d，8H，Ph-H(oxz)，J＝7.8Hz)8.25(s，2H，Ph-H)，8.44(d，1H，naphthene-H，J＝8.5Hz)，8.48(d，1H，naphthene-H，J＝8.0Hz)，8.6(d，1H，naphthene-H，J＝7.2Hz)，8.9(s，1H，Ph-H)。
Embodiment 3
Synthesizing of the dendritic macromole compound (NPOXZ3) of carrier transport functional group:
Figure C0315115000131
(1) replace 1,8-naphthalimide (NP3) synthetic:
Figure C0315115000132
In 50ml single port bottle, add 4-morphine quinoline base-1,8-naphthalene acid anhydride (1.0g, 3.53mmol) and 5-amino-different metatitanic acid (1.27g, 7.06mmol) and exsiccant DMF (20ml), reaction and treatment process are with the preparation of compound NP1, obtain 0.83g yellow solid (compound N P3), productive rate is 52.7%.m.p.＞250℃。
1H-NMR(500MHz，DMSO-d 6，ppm)δ＝3.2(t，4H，N-CH 2)，4.0(t，4H，O-CH 2-)，7.4(d，1H，naphthene-H，J＝8.2Hz)，7.85(t，1H，naphthene-H，J＝7.9Hz)，8.2(s，Ph-H，2H)，8.42(d，1H，naphthene-H，J＝8.1Hz)，8.47(d，1H，naphthene-H，J＝7.2Hz)，8.52(s，1H，Ph-H)，8.55(d，1H，naphthene-H，J＝8.4Hz)。
(2) compound N POXZ3's is synthetic:
In 50ml single port bottle, add compound N P3 (0.1g, 0.224mmol), compound 2 (0.38g by step (3) gained in the example 1,0.473mmol), (0.1g is 0.72mmol) with exsiccant DMF (10ml) for salt of wormwood, be heated to 100 ℃, stir after 24 hours, stop heating, be cooled to normal temperature.Reaction solution is poured in 40 ml waters, had light yellow solid to separate out, filter, use massive laundering, drying gets the 0.086g light yellow solid with acetone recrystallization then, and compound (NPOXZ3), productive rate are 20.7%.m.p.＞250℃。
1H-NMR(500MHz，CDCl 3)δ＝1.4(s，36H，-CH 3)，3.3(t，4H，N-CH 2-)，4.0(t，4H，O-CH 2-)，5.1(s，8H，PhO-CH 2-Ph)，5.4(s，4H，PhO-CH 2-Ph)，6.5(s，2H，PhO-CH 2-Ph)，6.7(s，4H，PhO-CH 2-Ph)，7.25(d，1H，naphthene-H，J＝8.1Hz)，7.55(d，8H，Ph-H(oxz)，J＝8.0Hz)，7.6(d，8H，Ph-H(oxz)，J＝7.8Hz)，7.7(t，1H，naphthene-H，J＝7.6Hz)，8.05(d，8H，Ph-H(oxz)，J＝7.9Hz)，8.13(d，8H，Ph-H(oxz)，J＝7.7Hz)8.25(s，2H，Ph-H)，8.44(d，1H，naphthene-H，J＝8.3Hz)，8.48(d，1H，naphthene-H，J＝7.8Hz)，8.6(d，1H，naphthene-H，J＝6.9Hz)，8.9(s，1H，Ph-H)。
Embodiment 4
Synthesizing of the dendritic macromole of carrier transport functional group (compound N PCZ1)
(1) the branch reaction of carbazole:
In the 100ml there-necked flask, add 9-(4 '-brombutyl) carbazole (5.0g, 15.62mmol), 3,5-dihydroxy-benzyl alcohol (1.0g; 7.1mmol), salt of wormwood (3.4g; 60mmol), (0.38g, 1.42mmol) and anhydrous propanone (50ml), backflow is 56 hours under argon shield for 18-hat-6.Be cooled to room temperature, revolve most of acetone, pour in the water, dichloromethane extraction discards water layer.The anhydrous MgSO of organic phase 4Drying is spin-dried for.With the methylene dichloride is that developping agent carries out column chromatography purification compound 3, and productive rate is 82.8%, m.p.＞250 ℃.
1H-NMR(500MHz，CDCl 3，ppm)：δ＝1.8(m，4H，-CH 2)，2.1(m，4H，-CH 2)，3.85(t，4H，N-CH 2-，J＝6.1Hz)，4.37(t，4H，O-CH 2-，J＝7.1Hz)，4.7(s，2H，-CH 2-OH)，6.25(s，1H，Ph-H)，6.5(s，1H，Ph-H)，7.2(t×d，4H，Ph-H(cz)，J＝6.8Hz，J＝1Hz)，7.4(d，4H，Ph-H(cz)，J＝8.0Hz)，7.48(t×d，4H，Ph-H(cz)，J＝7.9Hz，J＝1Hz)，8.2(d，4H，Ph-H(cz)，J＝7.8Hz)。
(2) the methylsulfonyl reaction of compound 3:
In 50ml single port bottle, with compound 3 (1.0g 1.63mmol) is dissolved in the anhydrous methylene chloride (20ml), drip methylsulfonyl chloride (0.185g, 1.63mmol) and triethylamine (0.164g, 1.63mmol), stirring at normal temperature 24 hours.Pour in the water, dichloromethane extraction discards water layer.Organic phase MgSO 4Drying is spin-dried for, and obtains 1.01g white solid compound 4, and productive rate is 96.2%, m.p.＞250 ℃.
1H-NMR(500MHz，CDCl 3，ppm)δ＝1.8(m，4H，-CH 2)，2.1(m，4H，-CH 2)，3.85(t，4H，N-CH 2-，J＝12Hz)，4.37(t，4H，O-CH 2-，J＝7.1Hz)，4.7(s，2H，-CH 2-OH)，6.30(s，1H，Ph-H)，6.45(s，1H，Ph-H)，7.2(t，4H，Ph-H(cz)，J＝7.3Hz)，7.4(d，4H，Ph-H(cz)，J＝8.0Hz)，7.48(t×d，4H，Ph-H(cz)，J＝7.8Hz，J＝1Hz)，8.2(d，4H，Ph-H(cz)，J＝8Hz)。
(3) compound N PCZ1's is synthetic:
In 50ml single port bottle, add compound N P1 (0.1g, 0.248mmol) (step among the embodiment 1 (1) is seen in its preparation), compound 4 (0.33g, 0.52mmol), (0.1g is 0.72mmol) with exsiccant DMF (10ml) for salt of wormwood, be heated to 100 ℃, stir after 24 hours, stop heating, be cooled to normal temperature.Reaction solution is poured in 40 ml waters, had light yellow solid to separate out, filter, use massive laundering, drying is crossed post with methylene dichloride then and is got 0.063g light yellow solid (compound N PCZ1), and productive rate is 16.6%.m.p.＞250℃。
1H-NMR(500MHz，CDCl 3)δ＝1.8(m，8H，-CH 2-)，2.1(m，8H，-CH 2)，3.05(s，6H，N(CH 3) 2)，3.85(t，8H，N-CH 2-，J＝6.1Hz)，4.37(t，8H，-CH 2-O，J＝6.5Hz)，5.25(s，4H，-CH 2-O)，6.3(s，2H，Ph-H)，6.5(s，4H，Ph-H)，7.05(d，1H，naphthalene-H，J＝8.3Hz)，7.2(t，8H，Ph-H(cz)，J＝7.1Hz)，7.38(d，8H，Ph-H(cz)，J＝7.9Hz)，7.42(t，8H，Ph-H(cz)，J＝7.4Hz)，7.6(t，1H，naphthalene-H，J＝7.9Hz)，8.05(d，8H，Ph-H(cz)，J＝7.6Hz)，8.2(s，2H，Ph-H)，8.37(d，1H，naphthalene-H，J＝8.3Hz)，8.42(d，1nmH，naphthalene-H，J＝8.4Hz)，8.5(d，1H，naphthalene-H，J＝7.1Hz)，8.82(s，1H，Ph-H)。
Embodiment 5
Synthesizing of the dendritic macromole of carrier transport functional group (compound N PCZ2)
Figure C0315115000161
(0.1g, 0.225mmol), (0.304g, 0.473mmol), (0.1g 0.72mmol) with exsiccant DMF (10ml), is heated to 100 ℃ to salt of wormwood to compound 4, stirs after 24 hours, stops heating, is cooled to normal temperature to add compound N P2 in 50ml single port bottle.Reaction solution is poured in 40 ml waters, had light yellow solid to separate out, filter, use massive laundering, drying is crossed post with methylene dichloride then and is got 0.072g light yellow solid (compound N PCZ2), and productive rate is 20.2%.m.p-＞250℃。
1H-NMR(500MHz，CDCl 3)δ＝1.65(m，2H，-CH 2-)，1.75(m，8H，-CH 2)，1.8(m，4H，-CH 2)，2.1(m，8H，-CH 2)，3.2(t，4H，N-CH 2)，3.85(t，8H，N-CH 2-，J＝6.1Hz)，4.37(t，8H，-CH 2-O，J＝7.1Hz,)，5.2(s，4H，-CH 2-O)，6.3(s，2H，Ph-H)，6.5(s，4H，Ph-H)，7.07(d，1H，naphthalene-H，J＝8.2Hz)，7.17(t，8H，Ph-H(cz)，J＝7.3Hz)，7.38(d，8H，Ph-H(cz)，J＝8.0Hz)，7.42(t，8H，Ph-H(cz)，J＝7.6Hz)，7.6(t，1H，naphthalene-H，J＝7.9Hz)，8.1(d，8H，Ph-H(cz)，J＝7.6Hz)，8.2(s，2H，Ph-H)，8.37(d，lH，naphthalene-H，J＝8.0Hz)，8.42(d，1H，naphthalene-H，J＝8.2Hz)，8.5(d，1H，naphthalene-H，J＝7.1Hz)，8.82(s，1H，Ph-H)。
Embodiment 6
Synthesizing of the dendritic macromole of carrier transport functional group (compound N PCZ3)
Figure C0315115000171
(0.1g, 0.224mmol), (0.31g, 0.473mmol), (0.1g 0.72mmol) with exsiccant DMF (10ml), is heated to 100 ℃ to salt of wormwood to compound 4, stirs after 24 hours, stops heating, is cooled to normal temperature to add compound N P3 in 50ml single port bottle.Reaction solution is poured in 40 ml waters, had light yellow solid to separate out, filter, use massive laundering, drying is crossed post with methylene dichloride then and is got 0.079g light yellow solid (compound N PCZ3), and productive rate is 22.3%.m.p.＞250℃。
1H-NMR(500MHz，CDCl 3)δ＝1.65(m，4H，-CH 2-)，1.7(m，8H，-CH 2)，1.95(m，8H，-CH 2)，3.2(t，4H，N-CH 2，J＝4.0Hz)，3.8(t，8H，N-CH 2，J＝6.0Hz)，3.94(t，4H，-CH 2-O，J＝4.2Hz)，4.25(t，8H，-CH 2-O，J＝2.1Hz)，6.3(s，2H，Ph-H)，6.4(s，4H，Ph-H)，7.05(d，1H，naphthalene-H，J＝8.1Hz)，7.2(t，8H，Ph-H(cz)，J＝7.3Hz)，7.3(d，8H，Ph-H(cz)，J＝8.0Hz)，7.38(t，8H，Ph-H(cz)，J＝7.5Hz)，7.55(t，1H，naphthalene-H，J＝7.9Hz)，7.98(d，8H，Ph-H(cz)，J＝7.7Hz)，8.12(s，2H，Ph-H)，8.33(d，1H，naphthalene-H，J＝8.0Hz)，8.37(d，1H，naphthalene-H，J＝8.2Hz)，8.45(d，1H，naphthalene-H?J＝7.1Hz，)，8.82(s，1H，Ph-H)。
Embodiment 7
The light amplification of institute's synthetic materials and light collection function:
No matter can be seen as compound N PCZ3 by Fig. 1 and Fig. 2 exciting with the absorption peak of carbazole, be with which absorption peak of carbazole to excite, and the fluorescence of carbazole almost by complete quencher, has only a very little peak because transmission ofenergy has been given the fluorescent core naphthalimide.And the fluorescent core naphthalimide has very strong fluorescence peak at the 513nm place.Excite the methyl esters of compound 3+NP3 with the absorption peak of carbazole, then when exciting, two very strong carbazole fluorescence peaks are arranged at 351nm and 366nm place with 330nm.This has illustrated that 95.9% transfer has taken place energy, and same when exciting with 345nm, the methyl esters of compound 3+NP3 has a very strong carbazole fluorescence peak at the 366nm place.95.9% transfer has also taken place in energy.This energy transfer efficiency is relatively to get by the integral area of compound N PCZ3 carbazole fluorescence peak and the integral area of compound 3 carbazole fluorescence peaks under the same excitation wavelength of same concentrations.The maximum absorption 301nm that can calculate the Yi oxadiazole with method of the same race excites, and the energy transfer efficiency of compound N POXZ1 is 64.8%, and the energy transfer efficiency of compound N POXZ2 is 65.5%, and the energy transfer efficiency of compound N POXZ3 is 76.7%.Compound N PCZ1 excites with 330nm, and energy transfer efficiency is 94%, excites with 345nm, and energy transfer efficiency is 94.5%, and compound N PCZ2 excites with 330nm, and energy transfer efficiency is 95.5%, excites with 345nm, and energy transfer efficiency is 95.6%.Can see simultaneously when absorption peak 330nm with carbazole excites, compound N PCZ3 has increased by 4.35 times at the fluorescence at 513nm place than the fluorescence of methyl esters at the 513nm place of compound N P3, when exciting with the absorption peak 345nm of carbazole, compound N PCZ3 has increased by 4.2 times at the fluorescence at 513nm place than the fluorescence of methyl esters at the 513nm place of compound N P3.This is relatively to get by the integral area to the fluorescence peak of the methyl esters of integral area by compound 13 fluorescent core fluorescence peaks and compound N P3 under the same excitation wavelength of same concentrations.The maximum absorption 298nm of same ， Yi oxadiazole excites, and compound N POXZ1 strengthens 12.5 times at 514nm place fluorescence, and compound N POXZ2 strengthens 17.9 times at 521nm place fluorescence, and compound N POXZ3 strengthens 20.6 times at 513nm place fluorescence.Compound N PCZ1 excites with 330nm, strengthens 4.7 times at 514nm place fluorescence, excites with 345nm, strengthens 4.8 times at 514nm place fluorescence.Compound N PCZ2 excites with 330nm, strengthens 4.3 times at 521nm place fluorescence, excites with 345nm, strengthens 4.8 times at 521nm place fluorescence.
Embodiment 8
With the dendritic macromole compound N PCZ1 that contains the carrier transport functional group as electroluminescent material, studied the performance of electroluminescent device, its structure is as follows: glass substrate/ITO//PEDOT/NPCZ1 (35nm)/NPCZ1: PBD (1: 0.3) (40nm) //LiF (7nm)/A1Li.The element manufacturing program is as follows: matrix adopts the ito glass of ultrasonic cleansing, and its resistance is 20 Ω/, the negative electrode (0.28cm of device 2) be that (vacuum tightness is 1 * 10 to employing vacuum vapour deposition coating -7Torr), luminescent layer NPCZ1 pure with doped layer be that to adopt methylene dichloride be solvent, concentration is that 10mg/ml selects and is coated with the whirl coating film forming.Wherein PBD is 2-(4-xenyl)-5-(4-tert-butyl-phenyl)-[1,3,4] oxadiazoles.The thickness of device is measured with step instrument (Tenco Alpha-step500), and the electroluminescent spectrogram is to measure with PTI QM1 luminoscope.Maximum emission wavelength is 518nm, is yellow green light, is 1, and the feature of 8-naphthalimide functional group is luminous, and maximum luminance is 1800cd/m under driving voltage 15V 2Device is after through 48 hours, and luminosity still can maintain more than the 100cd/m2.
Embodiment 9
As the individual layer electroluminescent material, studied the performance of typical sandwich individual layer electroluminescent device with NPCZ1, its structure is as follows: glass substrate //ITO//NPCZ1 (90nm) //LiF (7nm)/AlLi.Element manufacturing program and test are with embodiment 8.When driving voltage was 20V, the maximum emission wavelength in its electroluminescent peak was 522nm, and being yellow green light is 1 of NPCZ1, and the feature of 8-naphthalimide functional group is luminous, and luminosity is for reaching 635cd/m 2, current density is 250mA/cm 2Device is after through 48 hours, and luminosity still can maintain 100cd/m 2More than.
Embodiment 10
As the individual layer electroluminescent material, studied the performance of typical sandwich individual layer electroluminescent device with NPCZ3, its structure is as follows: glass substrate //ITO//NPCZ3 (110nm) //LiF (7nm)/AlLi.Element manufacturing program and test similar embodiment 8.When driving voltage was 20V, the maximum emission wavelength in its electroluminescent peak was 52nm, and being yellow green light is 1 of NPCZ1, and the feature of 8-naphthalimide functional group is luminous, and luminosity is very high, reaches 270cd/m 2, current density is 250mA/cm 2Device is after through 48 hours, and luminosity still can maintain 100cd/m 2More than.
Embodiment 11
As the individual layer electroluminescent material, studied the performance of typical sandwich individual layer electroluminescent device with NPOXZ1, its structure is as follows: glass substrate //ITO//NPOXZ1 (100nm) //LiF (7nm)/AlLi.Element manufacturing program and test similar embodiment 8.When driving voltage was 20V, the maximum emission wavelength in its electroluminescent peak was 520nm, and being yellow green light is 1 of NPOXZ1, and the feature of 8-naphthalimide functional group is luminous, reaches 780cd/m 2, current density is 380mA/cm 2Device is after through 48 hours, and luminosity still can maintain 100cd/m 2More than.
Embodiment 12
As the individual layer electroluminescent material, studied the performance of typical sandwich individual layer electroluminescent device with NPOXZ2, its structure is as follows: glass substrate //ITO//NPOXZ2 (100nm) //LiF (7nm)/AlLi.Element manufacturing program and test similar embodiment 8.When driving voltage was 15V, the maximum emission wavelength in its electroluminescent peak was 521nm, and being yellow green light is 1 of NPOXZ2, and the feature of 8-naphthalimide functional group is luminous, reaches 620cd/m 2, current density is 360mA/cm 2Device is after through 48 hours, and luminosity still can maintain 100cd/m 2More than.

Claims (4)

1, a kind of naphthalimide dendritic macromole electroluminescent organic material is characterized in that, said luminescent material is the dendritic macromole compound that contains the carrier transport functional group, and its structure is as shown in the formula shown in (1):
Figure C031511500002C1
(1) in the formula:
R 1For amino, alkane for amino or alkoxyl group; R 2Be Qu Dai oxadiazole base or 9-alkyl carbazole base;
Wherein: the structure of said Qu Dai oxadiazole base is suc as formula (2)
Figure C031511500002C2
(2) in the formula: X is H, C 1～C 12Alkyl or aryl,
The structure of said 9-alkyl carbazole base is suc as formula (3)
(3) in the formula: n=1～6.
2, electroluminescent organic material as claimed in claim 1 is characterized in that, wherein R1 is dimethylamino, diethylin, piperidyl, piperazinyl, morphine quinoline base, methoxy or ethoxy.
3, electroluminescent organic material as claimed in claim 2 is characterized in that, wherein X is the tertiary butyl or phenyl.
4, electroluminescent organic material as claimed in claim 2 is characterized in that, wherein n=4.
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