CN1793281A - Organic electroluminescent material, preparation and application thereof - Google Patents

Organic electroluminescent material, preparation and application thereof Download PDF

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CN1793281A
CN1793281A CN 200510125590 CN200510125590A CN1793281A CN 1793281 A CN1793281 A CN 1793281A CN 200510125590 CN200510125590 CN 200510125590 CN 200510125590 A CN200510125590 A CN 200510125590A CN 1793281 A CN1793281 A CN 1793281A
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acetone
salicylaldehyde
whipping appts
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CN100371417C (en
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许并社
郝玉英
王�华
软莉敏
周禾丰
陆路
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Taiyuan University of Technology
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Abstract

The invention relates to organic electroluminescence material and its manufacturing and application in organic electroluminescence technique field. Its luminescent material is used salicyic aldehyde crinkle amines derivative as ligand to complex Zn<SUP>2+</SUP>. The material is adopted liquid phase composing manufacturing method. It includes the following two steps: the first is composing salicyic aldehyde crinkle amines derivative ligand; the second is composing goal ligand. The formed material can be used as luminescent material or doping dye to be used in electroluminescence device. It adopts spin coating method to form film while the material is used as the former. And it adopts vacuum heating coating by vaporization method while as the latter. It is proved by experiment that the material is organic metal complexes with high stability, film forming capability, and easy to form nanometer grade function film, and can realize blue light, green light, yellow light multi-range luminescence.

Description

Electroluminescent organic material, preparation and application
One, technical field
Electroluminescent organic material of the present invention, preparation and application belong to technical field of organic electroluminescence, particularly the technical scheme of a class organometallic complex electroluminescent material, preparation and application thereof.
Two, technical background
Electroluminescent organic material is a kind of novel luminescent material, owing to it is widely studied in application prospect wide aspect the electroluminescent device, a large amount of achievements in research occurred.
That the salicylaldehyde-derived Schiff's base has is photic, thermochromism and nonlinear optical property, thereby earns widespread respect in fields such as information storage, photoswitch and information demonstrations.But this compounds and metal complexes thereof are at the application report in organic electroluminescent field seldom.1993, the people such as Yuji Hamada of Japan have reported the electroluminescent character of the zinc metal complexes of five kinds of salicylaldehyde-derived Schiff's base, wherein salicylidene 1, and luminescent properties the best of the zinc metal complexes of 6-hexanediamine Schiff's base (Jpn.J.Appl.Phys.1993,32:L511).Calendar year 2001, Changchun Physics Inst., Chinese Academy of Sciences has reported electroluminescent character (Synthetic Metals, 2001, the 117:211 of salicylidene triethylene tetramine zinc.) above these zinc metal complexess all have the blue light electroluminescence emission.
Three, research contents
Electroluminescent organic material of the present invention, preparation and application aims are to expand the research of the Zn metal complexes of salicylaldehyde-derived Schiff's base, realize that blue light, green glow, gold-tinted multiband are luminous, thereby a kind of technical scheme that is used for the luminescent material with multiband luminescent properties, preparation and the application thereof of organic electroluminescence device is provided.
Content of the present invention:
Luminescent material of the present invention is to be part with the salicylaldehyde-derived derivative, complexing divalent zinc ion Zn 2+Form.The molecular formula that this luminescent material has is:
ZnL n
L represents the salicylaldehyde-derived derivative ligand, and n can get 1 or 2, obtains the following structural coordination compound of having of 1: 2 type when n gets 2:
When getting 1, n obtains the title complex with following structure of 1: 1 type:
In the structural formula of 1: 2 type, when R was phenyl ring, this luminescent material was a salicylidene aniline zinc, has following molecular structural formula, and both title complex 1:
In the structural formula of 1: 1 type, when R is-CH 2CH 2In-time, this luminescent material is the double salicylaldehyde quadrol zinc that contracts, and has following structure, and promptly title complex 2:
Figure A20051012559000051
In the structural formula of 1: 1 type, when R was following structural formula, this luminescent material was the double salicylaldehyde mphenylenediamine zinc that contracts,
Figure A20051012559000052
Its molecule has following structure, and promptly title complex 3:
In the structural formula of 1: 1 type, when R was following structural formula, this luminescent material was the double salicylaldehyde O-Phenylene Diamine zinc that contracts,
Figure A20051012559000054
Its molecule has following structure, and promptly title complex 4:
Figure A20051012559000055
Material of the present invention adopts liquid phase synthetic preparation method, and the step of taking was divided into for two steps: the first step is the synthetic of salicylaldehyde-derived derivative ligand.Second step was the synthetic of target title complex.
The first step is taked following experimental program: the salicylic aldehyde adding of 0.2mol～0.8mol is furnished with in the there-necked flask of whipping appts, adds the toluene of 80～100ml simultaneously, slowly splash into amino derivative 0.3～0.4mol, and stirring is warming up to backflow, about 90 ℃ of reflux temperatures, reacted underpressure distillation afterwards 4 hours, remove and desolvate, cooling has yellow product body to separate out then, washs with normal hexane, be drying to obtain the salicylaldehyde-derived derivative ligand under the room temperature, productive rate 98～99%.
Second step was taked following experimental program: the salicylaldehyde-derived derivative of 0.01～0.03mol is dissolved in the mixing solutions (3: 1) of 40～60ml acetone soln or ethanol and acetone, place the there-necked flask of being furnished with whipping appts, add the triethylamine or 2～5 * 10 of 3～5ml -3The aqueous solution 4～15ml of the NaOH of mol/L starts whipping appts, and after 5 minutes, slowly splashing into concentration is 2～5 * 10 -4Methanol solution 20～the 40ml of the zinc acetate of mol/L, 15 ℃～65 ℃ were reacted 3 hours down, left standstill 2 hours, produced precipitation, filter, use acetone, deionized water wash 3-4 time, 80 ℃ of oven dry down, use acetone recrystallization again, obtain the very high target title complex of purity, productive rate 35～85%.
The material of the present invention's preparation can be used as luminescent material or dopant dye uses in electroluminescent device, when the material doped method film forming that in polymkeric substance, adopts spin coating during as luminescent material of the present invention, when material of the present invention adopts the method film forming of vacuum thermal evaporation during separately as luminescent material.
The step of taking when utilizing material preparation electroluminescent device of the present invention is, on a conductive glass substrate that cleaned, the luminescent material of the present invention of method evaporation one deck tens nanometer thickness by vacuum thermal evaporation, or luminescent material of the present invention is entrained in spin-coating film in the chloroformic solution of polycarbonate (PC) or polyvinyl carbazole (PVK), and then evaporation layer of metal electrode.Galvanic positive pole is added on the conductive glass, negative pole is added on the metal electrode, can observe luminous from conductive glass one side.
Advantage of the present invention: in organic electroluminescence device, luminescent material is to realize its photoelectric functional with indefiniteness nano level film, and mostly the inefficacy of device is because its indefiniteness film destruction causes.At present, the significant parameter of evaluation electroluminescent organic material is the film-forming properties of luminous efficiency, material, the stability of material.Experimental results show that, material of the present invention is the higher organometallic complex of class stability, has good film-forming properties, be easy to form the nano level function film, perhaps be entrained in spin-coating film in the chloroformic solution of polycarbonate (PC) or polyvinyl carbazole (PVK), perhaps pass through vacuum thermal evaporation film-forming.This material is difficult for forming exciplex with the interface of carrier blocking layers.In solid film, all has very strong fluorescence, higher purity of color; Material among the present invention is in organic electroluminescence device or made the nano level luminescent layer separately, perhaps mixes as dopant dye and make the nano level luminescent layer in matrix.And such material preparation process is simple, purifies easily, and starting material obtain easily.
Four, description of drawings
Fig. 1 is the infrared spectra of title complex 1 and ligand 1.Wherein a is the infrared spectra of ligand 1, and b is the infrared spectra of title complex 1.
Fig. 2 is the ultra-violet absorption spectrum of title complex 1 film.
Fig. 3 is the photoluminescence spectrum of title complex 1 film.
Five, embodiment
The preparation of part:
The preparation of ligand 1: the salicylic aldehyde of 0.3mol is added in the there-necked flask, the toluene that adds 80ml simultaneously slowly splashes into aniline 0.4mol, and stirring is warming up to backflow, about 90 ℃ of reflux temperatures, reacted 4 hours, underpressure distillation afterwards removes and desolvates, cooling then, there is yellow crystals to separate out,, is drying to obtain ligand 1 under the room temperature with the normal hexane washing.Productive rate 99%.
The preparation of part 2: the salicylic aldehyde of 0.7mol is added in the there-necked flask, the toluene that adds 80ml simultaneously, slowly splash into quadrol 0.3mol, and stirring is warming up to backflow, about 90 ℃ of reflux temperatures, reacted 4 hours, underpressure distillation afterwards removes and desolvates, then cooling, with the normal hexane washing, be drying to obtain part 2 under the room temperature.Productive rate 98.5%.
The preparation of part 3: the salicylic aldehyde of 0.7mol is added in the there-necked flask, the toluene that adds 80ml simultaneously, slowly splash into mphenylenediamine 0.3mol, stir and be warming up to backflow, about 90 ℃ of reflux temperatures, reacted 4 hours, underpressure distillation afterwards removes and desolvates, then cooling, with the normal hexane washing, be drying to obtain part 3 under the room temperature.Productive rate 98.5%
The preparation of part 4: the salicylic aldehyde of 0.7mol is added in the there-necked flask, the toluene that adds 80ml simultaneously, slowly splash into O-Phenylene Diamine 0.3mol, and stirring is warming up to backflow, about 90 ℃ of reflux temperatures, reacted 4 hours, underpressure distillation afterwards removes and desolvates, then cooling, with the normal hexane washing, be drying to obtain part 4 under the room temperature.Productive rate 98.5%
The preparation of title complex:
The preparation of title complex 1:
Method 1: the ligand 1 of 0.024mol is dissolved in the 48ml ethanol, places the there-necked flask of being furnished with whipping appts, add the triethylamine of 3.5ml, start whipping appts, after 5 minutes, slowly splashing into concentration is 5 * 10 -4The aqueous solution 20ml of the zinc chloride of mol/L, reaction is 3 hours under the room temperature, leaves standstill 2 hours, produces the needle-like crystal of light yellow green, filters, and uses ethanol, deionized water wash 3-4 time, and acetone recrystallization is used in 80 ℃ of oven dry down again, obtains the very high title complex of purity 1.Productive rate 76%.
Method 2: the ligand 1 of 0.024mol is dissolved in the 48ml ethanol, places the there-necked flask of being furnished with whipping appts, add the triethylamine of 3.5ml, start whipping appts, after 5 minutes, slowly splashing into concentration is 5 * 10 -4The methanol solution 20ml of the zinc acetate of mol/L, reaction is 3 hours under the room temperature, leaves standstill 2 hours, produces the needle-like crystal of light yellow green, filters, and uses ethanol, methanol wash 3-4 time, and acetone recrystallization is used in 80 ℃ of oven dry down again, obtains the very high title complex of purity 1.Productive rate 85%.
This luminescent material is the needle-like crystal of light yellow green, has green fluorescence, and powder produces glow peak at the 514.nm place, and half-peak width 69.0nm, chromaticity coordinates are x=0.2882, y=0.5851, purity of color 0.6802.189 ℃ of the fusing points of this material, 371 ℃ of decomposition temperatures.
The preparation of title complex 2:
The part 2 of 0.01mol is dissolved in the 40ml acetone, places the there-necked flask of being furnished with whipping appts then, add the triethylamine of 3.0ml, start whipping appts, after 5 minutes, slowly splashing into concentration is 2.5 * 10 -4The methanol solution 40ml of the zinc acetate of mol/L, 18 ℃ were reacted 3 hours down, obtained milky precipitation, left standstill 2 hours, filtered, and used acetone, methanol wash 3-4 time, and acetone recrystallization is used in 80 ℃ of oven dry down again, obtains the very high title complex of purity 2 (1).Productive rate 84%.This product has blue emission, and powder produces glow peak at the 459nm place, half-peak width 70.6nm, and purity of color 0.5636, chromaticity coordinates is x=0.1866, y=0.2028.412 ℃ of its decomposition temperatures.
The part 2 of 0.01mol is dissolved in the 40ml acetone, places the there-necked flask of being furnished with whipping appts then, add the triethylamine of 3.0ml, start whipping appts, after 5 minutes, slowly splashing into concentration is 2.5 * 10 -4The methanol solution 40ml of the zinc acetate of mol/L, 28 ℃ were reacted 3 hours down, obtained the precipitation of milk yellow, left standstill 2 hours, filtered, and used acetone, methanol wash 3-4 time, and acetone recrystallization is used in 80 ℃ of oven dry down again, obtains the very high title complex of purity 2 (2).Productive rate 82%.This product has the blue green light emission, and powder produces glow peak at the 471nm place, half-peak width 84.7nm, and purity of color 0.3985, chromaticity coordinates is x=0.2133, y=0.2657.412 ℃ of its decomposition temperatures.
The part 2 of 0.01mol is dissolved in the 40ml acetone, places the there-necked flask of being furnished with whipping appts then, add the triethylamine of 3.0ml, start whipping appts, after 5 minutes, slowly splashing into concentration is 2.5 * 10 -4The methanol solution 40ml of the zinc acetate of mol/L, reflux was reacted 3 hours, obtained the xanchromatic precipitation, left standstill 2 hours, filtered, and used acetone, methanol wash 3-4 time, and acetone recrystallization is used in 80 ℃ of oven dry down again, obtains the very high title complex of purity 2 (3).Productive rate 84%.This product has the yellow green light emission, and powder produces glow peak at the 527nm place, half-peak width 153.4nm, and purity of color 0.4016, chromaticity coordinates is x=0.3252, y=0.4485.412 ℃ of its decomposition temperatures.
The part 2 of 0.01mol is dissolved in the 40ml acetone, places the there-necked flask of being furnished with whipping appts then, the NaOH of 0.8g is dissolved in 4～5ml water, and it is slowly splashed in the there-necked flask, start whipping appts, after 5 minutes, slowly splashing into concentration is 2.5 * 10 -4The methanol solution 40ml of the zinc acetate of mol/L, 18 ℃ were reacted 3 hours down, left standstill 2 hours, filter, obtain linen precipitation, with acetone, methyl alcohol, deionized water wash 3-4 time, acetone recrystallization is used in 80 ℃ of oven dry down again, obtains the very high title complex of purity 2 (4).Productive rate 37.8%.This product has blue emission, and powder produces glow peak at the 455nm place, half-peak width 60.6nm, and purity of color 0.7452, chromaticity coordinates is x=0.1565, y=0.1455.412 ℃ of its decomposition temperatures.
The part 2 of 0.01mol is dissolved in the mixing solutions of 30ml ethanol and 10ml acetone, places the there-necked flask of being furnished with whipping appts then, the NaOH of 0.8g is dissolved in the 10ml water, and slowly splash into it in there-necked flask, start whipping appts, after 5 minutes, slowly splashing into concentration is 3 * 10 -4The aqueous solution 35ml of the zinc sulfate of mol/L, 18 ℃ were reacted 3 hours down, left standstill filtration in 2 hours, obtained linen precipitation, used acetone, deionized water wash 3-4 time, and acetone recrystallization is used in 80 ℃ of oven dry down again, obtains the very high title complex of purity 2 (4).Productive rate 83%.This product has blue emission, and powder produces glow peak at the 455nm place, half-peak width 60.6nm, and purity of color 0.7452, chromaticity coordinates is x=0.1565, y=0.1455.412 ℃ of its decomposition temperatures.
The preparation of title complex 3:
The part 3 of 0.01mol is dissolved in the 40ml acetone, places the there-necked flask of being furnished with whipping appts then, add the triethylamine of 3.0ml, start whipping appts, after 5 minutes, slowly splashing into concentration is 2.5 * 10 -4The methanol solution 40ml of the zinc acetate of mol/L, 18 ℃ were reacted 3 hours down, obtained the xanchromatic precipitation, left standstill 2 hours, filtered, and used acetone, methanol wash 3-4 time, dried down for 80 ℃, used acetone recrystallization again, obtained the very high title complex of purity 3.Productive rate 78%.This product has the yellow green light emission, and powder produces glow peak at the 521nm place, half-peak width 84.4nm, and purity of color 0.7764, chromaticity coordinates is x=0.3181, y=0.5928,385 ℃ of its decomposition temperatures.
The preparation of title complex 4
The part 4 of 0.01mol is dissolved in the 40ml acetone, places the there-necked flask of being furnished with whipping appts then, add the triethylamine of 3.0ml, start whipping appts, after 5 minutes, slowly splashing into concentration is 2.5 * 10 -4The methanol solution 40ml of the zinc acetate of mol/L, 18 ℃ were reacted 3 hours down, obtained the xanchromatic precipitation, left standstill 2 hours, filtered, and used acetone, methanol wash 3-4 time, dried down for 80 ℃, used acetone recrystallization again, obtained the very high title complex of purity 4.Productive rate 79%.This product has yellow emission, and powder produces glow peak at the 570nm place, half-peak width 80.4nm, and purity of color 0.6764, chromaticity coordinates is x=0.4507, y=0.5233,360 ℃ of its decomposition temperatures.
The infrared spectra and the ultraviolet spectrum data of part and title complex thereof see Table 1.
Prepare organic electroluminescence device with above-mentioned title complex:
Device 1: on a glass substrate that covers by Indium sesquioxide-stannic oxide (ITO) that cleaned, be 2 * 10 in vacuum tightness -6Under the condition of Torr, utilize the method for vacuum thermal evaporation to prepare the film of the title complex 1 among the thick the present invention of one deck 60nm, and then the thick Mg:Ag alloy of evaporation one deck 200nm, the positive pole of direct supply is added on the ITO layer, negative pole is added on the Mg:Ag alloy layer, can observe green emission from the ITO side, emission peak wavelength 508nm.
Device 2: on a glass substrate that covers by Indium sesquioxide-stannic oxide (ITO) that cleaned, be 2 * 10 in vacuum tightness -6Under the condition of Torr, utilize the method for vacuum thermal evaporation to prepare the film of the title complex 2 (4) among the thick the present invention of one deck 60nm, and then the thick Mg:Ag alloy of evaporation one deck 200nm, the positive pole of direct supply is added on the ITO layer, negative pole is added on the Mg:Ag alloy layer, can observe blue green light emission, emission peak wavelength 475nm from the ITO side
Device 3: take by weighing the polyvinyl carbazole (PVK) of 10mg and the title complex 2 (4) among 10mg the present invention, they are dissolved in the chloroform of 2ml, utilize the ultrasonic wave dissolving fully, then it is dropped on the glass substrate that cleaned by Indium sesquioxide-stannic oxide (ITO) covering, utilize the method for spin coating, with the thick film of speed spin coating one deck 60nm of 1000r/min, be 2 * 10 in vacuum tightness then -6Under the condition of Torr, utilize the method Mg:Ag alloy that evaporation one deck 200nm is thick again of vacuum thermal evaporation, the positive pole of direct supply is added on the ITO layer, negative pole is added on the Mg:Ag alloy layer, can observe blue emission from the ITO side, emission peak wavelength 455nm.
Device 4: take by weighing the polyvinyl carbazole (PVK) of 10mg and the title complex 2 (4) among 10mg the present invention, they are dissolved in the chloroform of 2ml, utilize the ultrasonic wave dissolving fully, then it is dropped on the glass substrate that cleaned by Indium sesquioxide-stannic oxide (ITO) covering, utilize the method for spin coating, the thick film of speed spin coating one deck 60nm with 1000r/min, utilize the method Mg:Ag alloy that evaporation one deck 200nm is thick again of vacuum thermal evaporation, the positive pole of direct supply is added on the ITO layer, negative pole is added on the Mg:Ag alloy layer, can observe yellow green light emission, emission peak wavelength 528nm from the ITO side.
Device 5: on a glass substrate that covers by Indium sesquioxide-stannic oxide (ITO) that cleaned, be 2 * 10 in vacuum tightness -6Under the condition of Torr, utilize the method for vacuum thermal evaporation to prepare the film of the title complex 4 among the thick the present invention of one deck 60nm, and then the thick Mg:Ag alloy of evaporation one deck 200nm, the positive pole of direct supply is added on the ITO layer, negative pole is added on the Mg:Ag alloy layer, can observe yellow emission from the ITO side, emission peak wavelength 583nm.
Table 1
Compound Infrared spectra/cm -1 UV spectrum
v C＝N v ph-O v C＝N v M-O Film Powder or ethanolic soln
Ligand 1 1617 (by force) 1277 (by force) 1401 (weak) 1320 (weak) 240nm, 337nm, 399nm (powder)
Title complex 1 1607 (by force) 1253 (weak) 1389 (in) 1324 (m) 608 (weak) 252nm，324nm，429nm 240nm, 396nm, 453nm (powder)
Part 2 1636 (by force) 1284 ((by force) 1419 (in) 1372 (weak) 212nm, 253nm, 311nm (solution)
Title complex 2 1654 (by force) 1283 (weak) 1392 (weak) 1342 (weak) 609 (weak) 472 (weak) 249nm，282nm，400nm 224nm, 239nm, 259nm, 268nm, 347nm (solution)
Part 3 1620 (by force) 1282 (by force) 1410 (weak) 1360 (weak) 239nm, 256nm, 369nm (solution)
Title complex 3 1607 (by force) 1281 (weak) 1384 (weak) 1351 (weak) 540 (weak) 240nm, 259nm, 391nm (solution)
Part 4 1614 (by force) 1277 (by force) 1419 (weak) 1362 (weak) 239nm, 256nm, 349nm (solution)
Title complex 4 1597 (in) 1298 (weak) 1443 (weak) 1365 (weak) 545 (weak) 240nm, 263nm, 377nm (solution)

Claims (4)

  1. The preparation method of 1 one kinds of electroluminescent organic materials, it is characterized in that a kind of is part with the salicylaldehyde-derived derivative, complexing divalent zinc ion Zn 2+The molecular formula that forms is:
    ZnL nThe preparation method, n in the formula gets 1, L represents the salicylaldehyde-derived derivative ligand, this electroluminescent organic material is meant double salicylaldehyde mphenylenediamine zinc and the double salicylaldehyde O-Phenylene Diamine zinc that contracts that contracts, this preparation method is a kind of liquid phase synthetic preparation method, the step of taking was divided into for two steps: the first step is the synthetic of salicylaldehyde-derived derivative ligand, and second step was the synthetic of target title complex:
    The first step is furnished with the salicylic aldehyde adding of 0.2mol～0.8mol in the there-necked flask of whipping appts, adds the toluene of 80～100ml simultaneously, slowly splashes into amino derivative 0.3～0.4mol, and stirring is warming up to backflow, about 90 ℃ of reflux temperatures, reacted underpressure distillation afterwards 4 hours, remove and desolvate, cooling has yellow crystals to separate out then, washs with normal hexane, be drying to obtain the salicylaldehyde-derived derivative ligand under the room temperature, productive rate 98～99%;
    Second step was dissolved in the salicylaldehyde-derived derivative of 0.01～0.03mol in the mixing solutions (3: 1) of 40～60ml acetone soln or ethanol and acetone, placed the there-necked flask of being furnished with whipping appts, added the triethylamine or 2 * 10 of 3～5ml -3The aqueous solution 5～15ml of the NaOH of mol/L starts whipping appts, and after 5 minutes, slowly splashing into concentration is 5 * 10 -4Methanol solution 20～the 40ml of the zinc acetate of mol/L, reaction is 3 hours under the room temperature, leaves standstill 2 hours, produces precipitation, filter, use acetone deionized water wash 3-4 time, 80 ℃ of oven dry down, use acetone recrystallization again, obtain the very high target title complex of purity, productive rate 35～85%.
  2. 2 preparation methods according to the described a kind of electroluminescent organic material of claim 1 is characterized in that the described double salicylaldehyde mphenylenediamine zinc that contracts
    The preparation method, adopt liquid phase synthetic method, step was divided into for two steps: the first step is the synthetic of salicylidene mphenylenediamine, second step was the synthetic of target title complex:
    The first step is furnished with the salicylic aldehyde adding of 0.2mol～0.8mol in the there-necked flask of whipping appts, adds the toluene of 80～100ml simultaneously, slowly splashes into mphenylenediamine 0.3～0.4mol, and stirring is warming up to backflow, about 90 ℃ of reflux temperatures, reacted underpressure distillation afterwards 4 hours, remove and desolvate, cooling has yellow crystals to separate out then, washs with normal hexane, be drying to obtain salicylidene mphenylenediamine part under the room temperature, productive rate 98～99%.
    Second step was dissolved in the salicylidene mphenylenediamine of 0.01～0.03mol in the mixing solutions (3: 1) of 40～60ml acetone soln or ethanol and acetone, placed the there-necked flask of being furnished with whipping appts, added the triethylamine or 2 * 10 of 3～5ml -3The aqueous solution 5～15ml of the NaOH of mol/L starts whipping appts, and after 5 minutes, slowly splashing into concentration is 5 * 10 -4Methanol solution 20～the 40ml of the zinc acetate of mol/L, reaction is 3 hours under the room temperature, leaves standstill 2 hours, produce precipitation, filter, use acetone deionized water wash 3-4 time, acetone recrystallization is used in 80 ℃ of oven dry down again, obtains the very high target title complex productive rate 35～85% of purity.
  3. 3 preparation methods according to the described a kind of electroluminescent organic material of claim 1 is characterized in that the described double salicylaldehyde O-Phenylene Diamine zinc that contracts
    The preparation method, adopt liquid phase synthetic method, step was divided into for two steps: the first step is the synthetic of salicylidene O-Phenylene Diamine part, second step was the synthetic of target title complex,
    The first step is furnished with the salicylic aldehyde adding of 0.2mol～0.8mol in the there-necked flask of whipping appts, adds the toluene of 80～100ml simultaneously, slowly splashes into O-Phenylene Diamine 0.3～0.4mol, and stirring is warming up to backflow, about 90 ℃ of reflux temperatures, reacted underpressure distillation afterwards 4 hours, remove and desolvate, cooling has yellow crystals to separate out then, washs with normal hexane, be drying to obtain salicylidene amine O-Phenylene Diamine part under the room temperature, productive rate 98～99%.
    Second step was dissolved in the salicylidene O-Phenylene Diamine of 0.01～0.03mol in the mixing solutions (3: 1) of 40～60ml acetone soln or ethanol and acetone, placed the there-necked flask of being furnished with whipping appts, added the triethylamine or 2 * 10 of 3～5ml -3The aqueous solution 5～15ml of the NaOH of mol/L starts whipping appts, and after 5 minutes, slowly splashing into concentration is 5 * 10 -4Methanol solution 20～the 40ml of the zinc acetate of mol/L, reaction is 3 hours under the room temperature, leaves standstill 2 hours, produces precipitation, filter, use acetone deionized water wash 3-4 time, 80 ℃ of oven dry down, use acetone recrystallization again, obtain the very high target title complex of purity, productive rate 35～85%.
  4. The application method of the 4 a kind of electroluminescent organic materials that obtain by the preparation method of claim 1, it is characterized in that, the double salicylaldehyde O-Phenylene Diamine zinc that contracts, use in electroluminescent device as luminescent material or dopant dye, the double salicylaldehyde mphenylenediamine zinc that contracts, use in electroluminescent device as dopant dye, in being entrained in polymkeric substance, adopt the method film forming of spin coating during as luminescent material, when separately as luminescent material, adopt the method film forming of vacuum thermal evaporation, step is, on a conductive glass substrate that cleaned, the luminescent material of the present invention of method evaporation one deck tens nanometer thickness by vacuum thermal evaporation, or luminescent material of the present invention is entrained in spin-coating film in the chloroformic solution of polycarbonate PC or polyvinyl carbazole PVK, and then evaporation layer of metal electrode, galvanic positive pole is added on the conductive glass, negative pole is added on the metal electrode, can observe luminous from conductive glass one side.
CNB2005101255901A 2004-06-09 2004-06-09 Organic electroluminescent material, preparation and application thereof Expired - Fee Related CN100371417C (en)

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WO2009062578A1 (en) * 2007-11-12 2009-05-22 Merck Patent Gmbh Organic electroluminescent devices comprising azomethine-metal complexes

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CN1164568C (en) * 2001-05-23 2004-09-01 中国科学院化学研究所 Process for condensating salicyladehyde with arylamine

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009062578A1 (en) * 2007-11-12 2009-05-22 Merck Patent Gmbh Organic electroluminescent devices comprising azomethine-metal complexes
JP2011503886A (en) * 2007-11-12 2011-01-27 メルク パテント ゲーエムベーハー Organic electroluminescent device
US8487300B2 (en) 2007-11-12 2013-07-16 Merck Patent Gmbh Organic electroluminescent devices comprising azomethine-metal complexes
CN101878279B (en) * 2007-11-12 2016-05-11 默克专利有限公司 Containing the organic electroluminescence device of azomethine-metal complexes

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