CN100348647C - Hyperbranched electrophosphorescent conjugated polymer with metal complex as core and its use - Google Patents
Hyperbranched electrophosphorescent conjugated polymer with metal complex as core and its use Download PDFInfo
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- CN100348647C CN100348647C CNB200510033101XA CN200510033101A CN100348647C CN 100348647 C CN100348647 C CN 100348647C CN B200510033101X A CNB200510033101X A CN B200510033101XA CN 200510033101 A CN200510033101 A CN 200510033101A CN 100348647 C CN100348647 C CN 100348647C
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Abstract
The present invention discloses a super-branch electrical phosphorescence conjugated polymer using a metal complex as a core and the application of the conjugated polymer in light emitting diodes, the luminescent layers of the panel displays and the reactive layers of solar batteries. The synthetic method of the present invention has the advantages of simplicity and easy operation, and has higher application value.
Description
Technical field
The present invention relates to a kind of polymkeric substance of metal-containing complex, specifically be a kind of with the metal complexes be nuclear over-branched phosphorescent conjugated polymer.
The invention still further relates to the metal complexes is the application of over-branched phosphorescent conjugated polymer in the active coating of the luminescent layer of photodiode, flat-panel monitor and solar-energy photo-voltaic cell of nuclear.
Background technology
Since Japanese scientist Bai Chuanying tree in 1977 was found the polyacetylene conduction, the conductive polymers of this being called as " the 4th generation macromolecular material " had attracted numerous scientists to study with its outstanding photoelectric properties.Compare with the inorganic materials with identical or close purposes, conducting polymer has advantages such as density is low, easy processing.Since the conjugate property of this class material structure, thus its energy transmission charge, stimulated luminescence can or may be applied on many electronics or opto-electronic device, as polymer LED, photovoltaic cell, field effect transistor etc.Potential application prospect and wide application field impel scientist competitively to study the conjugation material that this class has photoelectric activity, as polyacetylene, polypyrrole, Polythiophene, polyaniline, poly-fluorenes etc.
As electronics (π-π when bonding orbital transits to antibonding(molecular)orbital
*Transition), has the light of the common absorbing wavelength 300-500 nanometer of polymer of aromatic ring or heterocycle structure,, send the photon of respective wavelength in the visible region usually, Here it is luminous high polymer material when when antibonding(molecular)orbital transits to bonding orbital, giving off energy.In nearly ten years, people have developed the luminescence polymer of One's name is legion.Making can commercial luminescent device, and the life-time service stability of the luminous quantum efficiency of material, operating voltage (power consumption), device etc. must be optimized.Method, exploitation that people are making great efforts to seek to improve the photodiode performance always have high-quantum efficiency, high color purity, the luminescence polymer that permanent stability are good.
The luminous efficiency of organic/polymer electroluminescent device (O/PLED) is far below theoretical value, and wherein to be not used be major cause [Baldo, M.A. to the energy of triplet excitons; O ' Brien, D.F.; You Y.; Shoustikov, A.; Sibley, S.; Thompson, M.E.; Forrest, S.R.Nature 1998,395, and 151.].The organic/polymer electro phosphorescent device, the energy by the electrophosphorescent subject and object shifts, and can utilize the energy of triplet excitons and luminous, thereby improves the luminous efficiency of device.Because make simple, as to be easy to realize less energy-consumption big area demonstration, polymer electrophosphorescent material receives much attention.The luminescent material that is entrained in polymer body with the electrophosphorescent object is compared, by grafting, copolymerization the electrophosphorescent object is connected on the macromolecular chain, can realize intramolecularly and intermolecular energy transfer, effectively suppress triplet excitons self-quenching, improve the stability of material.Therefore, to the design of novel electrophosphorescent polymkeric substance and synthetic having important practical significance.
(J.Am.Chem.Soc.2003,125 (3): 636-637) utilize 2, position diketone structure coordination forms the dicyclo title complex of iridium to Chen Shouan etc. between the side chain of 7-dibromo alkyl fluorenes, with other monomer copolymerizations, the electrophosphorescent object is hung on the macromolecular chain then.Synthetic the reaching of polymer electrophosphorescent polymkeric substance studied, and mostly is at present the electrophosphorescent object is connected on the macromolecule side chain.The physical and chemical performance of this system and electrophosphorescent object doping system are very similar, are equivalent to link to each other with an alkyl chain between doping object and main body.NHK (WO 03018653) has also done similar work.They hang over three kinds of electrophosphorescent objects of red, green, blue on the side chain of non-conjugated polymeric thing PVK and have obtained red, green, blue three look electrophosphorescent polymkeric substance.Homles etc. (WO 03/091355 A2) utilize the monomeric Suzuki polycondensation of A-B type to obtain having the title complex of two long-chains.Though molecular weight has reached the standard of polymkeric substance, on stricti jurise, be the title complex of polymerization materialization, not multipolymer, so its electroluminescent efficiency is lower with structure diversity.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, providing a kind of is the over-branched phosphorescent conjugated polymer of nuclear with the metal complexes.
Another object of the present invention be with described be that the over-branched phosphorescent conjugated polymer of nuclear is as photodiode, the luminescent layer of flat-panel monitor and the active coating of solar-energy photo-voltaic cell with the metal complexes.
To achieve the above object of the invention, the present invention has taked following technical scheme:
The branches that with the metal complexes is the over-branched phosphorescent conjugated polymer of nuclear is 3 or 4, and metal complexes shared molecular fraction in over-branched phosphorescent conjugated polymer is 0.1～20%.
Described over-branched phosphorescent conjugated polymer has following chemical structural formula:
Wherein, A is the conjugated structure unit; M is an iridium metal complex; n
1, n
2, n
3, n
4, n
5, n
6, n
7And n
8Be all natural number.
Described M is the iridium metal complex with following chemical structural formula:
Or
Wherein, R is the side chain of alkyl or alkoxyl group.
Described A has following one or more chemical structure:
Wherein, Ar is fragrant heterocyclic units; R
1, R
2Be C
1～C
10Alkyl or the side chain of alkoxyl group; M is an integer.Described over-branched phosphorescent conjugated polymer also can be the material with following chemical structural formula:
Wherein, A is the conjugated structure unit; M is the metalloporphyrin title complex; n
1, n
2, n
3, n
4And n
13Be all natural number.
Described M is the metalloporphyrin title complex with following chemical structural formula:
Described M ' is Pt, Zn or Cu.
Described A has following one or more chemical structures:
Wherein, Ar is fragrant heterocyclic units; R
1, R
2Be C
1～C
10Alkyl or the side chain of alkoxyl group; M is an integer.
Above technical scheme is described to be that the over-branched phosphorescent conjugated polymer of examining can be used as the luminescent layer of photodiode, flat-panel monitor and the active coating of solar-energy photo-voltaic cell with the metal complexes.The light emitting region of over-branched phosphorescent conjugated polymer that with the metal complexes is nuclear is in 400～800 nanometers, and dissolves in common organic solvents.
Compared with the prior art, the present invention has following beneficial effect: of the present invention is that the synthetic method of over-branched phosphorescent conjugated polymer of nuclear is simple with the metal complexes.The photoluminescence efficiency of over-branched phosphorescent conjugated polymer that wherein with the complex of iridium is nuclear is 80%, the electroluminescent external quantum efficiency is 14%, has very high using value.
Description of drawings
Fig. 1 is the chemical structural drawing of the over-branched phosphorescent conjugated polymer of nuclear with the complex of iridium for the present invention;
Fig. 2 is the chemical structural drawing of the over-branched phosphorescent conjugated polymer of nuclear with the metalloporphyrin title complex for the present invention.
Embodiment
One) by the following examples to synthetic being further described of tricyclic ligand and Fourth Ring porphyrin part, but following example is the synthetic explanation to part proposed by the invention, and the present invention will be not limited to listed example.
Embodiment 1
The synthesized reference patent of 2-(3 '-bromo-phenyl)-pyridine [Paul F.Ranken, Baton La.Rouge,, U.S.Patent 4,554, and 352].
In the there-necked flask of the 500ml that has constant pressure funnel, thermometer, add 2-phenylpyridine (1 mole), aluminum trichloride (anhydrous) (1.2 moles), oil of mirbane (4.9 moles), under nitrogen protection, be heated to 85-95 ℃.Liquid bromine (1.2 moles) slowly splashed in the mixing solutions, 85-95 ℃ of reaction 12 hours.Reaction mixture is poured in the trash ice, and behind the bromine flush away, product is purified with column chromatography, obtains the white needles solid.
Embodiment 2
Synthetic reference [Lamansky, the S. of 5-bromo-2-phenylpyridine; Djurovich, P.; Murphy, D.; Abdel-Razzaq, F.; Kwong, R.; Tsyba, I.; Bortz, M.; Mui, B.; Bau, R.; Thompson, M.E.; Inorganic Chemistry.2001,40,1704-1711] reported method
Weighing Zinc Chloride Anhydrous 6.48 gram, four (triphenyl phosphorus) close palladium 0.49 gram, 2 in glove box, 5-dibromo pyridine 5.5 grams, and inject 25,25 respectively, the THF wiring solution-forming of 35ml.
Have in the there-necked flask of 500ml of constant pressure funnel, thermometer and add BuLi 31.3ml, THF 20ml.Cooled with liquid nitrogen begins to drip and contains bromobenzene 5ml/THF (25ml) solution after-78 ℃, and continues reaction 40min down at-70 ℃.Under-70 ℃, from constant pressure funnel, drip zinc chloride/THF solution then.After progressively being warmed up to room temperature, reaction 30min.Add four (triphenyl phosphorus) successively in room temperature and close palladium 0.49 gram/THF solution and 2,5-dibromo pyridine 5.5 gram/THF solution.After dropwising, at room temperature reacted 20 hours.After reaction finishes with the solvent evaporate to dryness, product water/ethyl acetate extraction.Organic layer water, saturated common salt successively is washed to neutrality, anhydrous magnesium sulfate drying, filtration.The distillation ethyl acetate, solid product normal hexane recrystallization obtains light yellow crystal 3.49 grams, and productive rate is 64%.
1HNMR and GC-MASS test shows are target product.
Embodiment 3
The building-up reactions step of 5-bromo-2-(4 '-aminomethyl phenyl)-pyridine such as embodiment 2
Bromobenzene in the raw material changes para-bromo toluene into, gets pale yellow powder 3.58 grams at last,
Productive rate is 60.8%.
1HNMR and GC-MASS test shows are target product.
Embodiment 4
2-[4-(4-bromo-phenoxymethyl)-phenyl] pyridine synthetic
(1) 2-(to 2-bromomethylphenyl)-pyridine is synthetic
In the there-necked flask of the 250ml that thermometer, reflux condensing tube are housed, add 2-(p-methylphenyl)-pyridine 3.4 grams (20mmol), bromo-succinimide (NBS) 4.3 gram (24mmol), 40 milligrams of BPO and tetracol phenixin 100ml.Be heated to backflow, reacted 2 hours.Cooling, filtration.Solution after partly collecting steams solvent.Product is crossed post with 300-400 order silica gel, and eluent is a sherwood oil: the mixed solvent of ethyl acetate=4: 1.With the solvent evaporate to dryness, obtain white crystal 3 grams, productive rate is 60%.
(2) target product is synthetic
In the four-hole boiling flask of the 250ml that thermometer, reflux condensing tube, constant pressure funnel are housed, add p bromophenol 2.3 grams (13.4mmol), sodium methylate 0.8 gram (14.8mmol) and dehydrated alcohol 50ml.After the reflux one hour, slowly drip 2-(to brooethyl)-phenyl-pyridine 4 gram (16mmol)/chloroform (30ml) solution.After dripping, temperature descends but still refluxes.Under the reflux temperature after the decline, continue reaction 8 hours.After reaction finished, with the solvent evaporate to dryness, product extracted with methylene dichloride/water.Organic layer is washed till neutrality with aqueous sodium hydroxide solution, distilled water successively, anhydrous magnesium sulfate drying.Distillation after product ethyl alcohol recrystallization gets white flocculus shape crystal 3 .5 gram, and productive rate is 76%.
1H NMR and GC-MASS test shows are target product.
Embodiment 5
2,7,12,17-tetrabromo-5,10,15, the synthetic reference of 20-tetraphenylporphyrin [Callor, par H.J.Bul.Soc.Chim.France1974,7-8,1492-1496] method.
In the 500ml there-necked flask, add 5,10,15,20-tetraphenylporphyrin (TPP) 1 gram, chloroform 300ml and NBS 1.8 grams.Reflux and be chilled to room temperature after 1 hour.Add a spot of pyridine, pour precipitation in the methyl alcohol after the solution concentration into, filter.The solid that obtains methylene chloride recrystallization is used 300-400 purpose silica gel/benzene: hexanaphthene (volume ratio 1: 1) column chromatography then.Productive rate: 80%.
Embodiment 6
5,10,15, and the synthetic reference of 20-four (p-bromine (iodine, chlorine)-phenyl)-porphyrin [Z.P.Fei, B.S.Li, Z.S.Bo, R.Lu, OrganicLetter 2004,6 (25), 4703-4706] method.
With 5,10,15,20-four (p-iodo-phenyl)-porphyrin synthesize example illustrated
In the 250ml there-necked flask, add 4-benzaldehyde iodine 0.3 gram (1.29 mmole), pyrroles's 0.091 gram (1.36 mmole), with 130 milliliters of dissolvings of chloroform.After the careful degassing, add 0.15 milliliter of trifluoroacetic acid (1.94 mmole).After at room temperature stirring 16 hours, add 0.323 milligram of DDQ (1.42 mmole), continue reaction after 7 hours, add 0.27 milliliter of triethylamine (1.94 mmole) again.Reaction mixture separates through post, gets crude product.Further cross silicagel column (CH
2Cl
2/ Hexane=1: 4v/v), get elaboration.Productive rate: 38%.
Two) by following example three ring complex of iridium and monomeric synthesizing of Fourth Ring metalloporphyrin complex are described further.Following example is the explanation to coordination compound monomer proposed by the invention, but the present invention will be not limited to listed example.
1) tricyclic ligand of above related structure obtains having the title complex of three polymerizable active groups by three ring iridium metals coordination reactions.Coordination reaction has bibliographical information (I.D.Parker.et al., J.Appl.Phys.1994,75:1656-1666; K.Dedeian, P.I.Djurovich, F.O.Garces, et al.Inorg.Chem.1991,30:1685-1687).The most frequently used is the method for making solvent and iridium triacetylacetonate reaction of glycerine, and example is as follows:
The solvent that reacts used is a glycerine.This reaction advantage is a primary first-order equation, and step is few, and aftertreatment is also simpler.Shortcoming is under the reflux temperature (270-280 ℃) at glycerine, part and raw material Ir (acac) to take place easily
3Oxidation, decomposition reaction.Carry out even show as under nitrogen protection, also the black tarry matters might occur.Therefore we have carried out the condition experiment under the differing temps.Oxidation, the decomposition of raw material take place in discovery easily under reflux temperature; Temperature of reaction is lower than 200 ℃, and target product is difficult to generate.It is preferable that temperature of reaction is controlled at 220 ℃ of left and right sides.
Embodiment 7
Three [2-(3-bromobenzene) yl pyridines] close iridium Ir (BrPPy)
3Synthetic
In the there-necked flask that prolong, thermometer 100ml are housed, add dehydration glycerine 15ml, whole system argon shield.Add three (acetyl acetone iridium) 0.1 gram (0.2mmol) and 2-(3-bromobenzene) yl pyridines, 0.28 gram (1.2mmol) then.Stirring, heating remain on about 220 ℃ temperature, continue reaction 12 hours.Cool to room temperature adds hydrochloric acid soln (1M) 40ml.Stir evenly solid and generated gained solid water and methanol wash behind the suction filtration.Get the sap green pressed powder after the drying.Cross post with 200-300 order silica gel, eluent is a methylene dichloride.80 milligrams in yellow solid powder will be obtained behind the solvent evaporate to dryness.
1HNMR and ultimate analysis test shows are target product.
Embodiment 8
Three (5-bromo-2-phenylpyridines) close iridium Ir (PPyBr)
3Synthetic
Reaction is with embodiment 7
Embodiment 9
Reference literature [C.Coudret., S.Fraysse, J-P.Launay; Chem.Commun.1998,663] three ring title complexs can obtain encircling coordination compound monomers with three of bromine atoms with bromo-succinimide (NBS) bromination.
The bromination of closing iridium with three ring title complexs three (2-phenylpyridine) is that example is illustrated:
In there-necked flask, add the title complex of a molar equivalent, and be dissolved in the methylene dichloride.The NBS that adds four molar equivalents.At room temperature lucifuge stirs after 24 hours and boils off solvent.After acetone is washed, use methylene dichloride: sherwood oil=1: 1 mistake silicagel column.Distillation, drying get faint yellow solid.Warp
13CNMR and GC-MASS test shows are target product.
2) Fourth Ring metalloporphyrin complex (Pt, Zn, Cu) is synthetic with reference to [Callor, par H.J.Bul.Soc.Chim. France 1974,7-8,1492-1496] method.
Embodiment 10
5,10,15,20-four (p-iodophenyl)-porphyrin platinum synthetic
In the 100ml there-necked flask, argon shield adds PtCl down
20.6 gram, benzene nitrile 10ml.After 1 hour, add 5,10,15,20-four (p-iodophenyl)-porphyrin 0.2 gram/benzene nitrile solution 5ml in reaction under 100 ℃.Be chilled to room temperature in reaction under 190 ℃ after 10 hours.Reaction solution poured into obtain red precipitate in the methyl alcohol.Filter the back with 300-400 order silica gel/toluene column chromatography, use CH then
2Cl
2/ recrystallizing methanol.Productive rate: 45%.
Embodiment 11
2,7,12,17-tetrabromo-5,10,15,20-phenyl porphyrin zinc (copper) synthetic
With 2,7,12,17-tetrabromo-5,10,15, the example that synthesizes of 20-phenyl porphyrin zinc is given explanation
In the 100ml there-necked flask, argon shield adds Zn (OAc) down
2.2 H
2O 0.9 gram, methyl alcohol 50ml.Slowly drip 2,7,12,17-tetrabromo-5,10,15,20-phenyl porphyrin 1 gram/chloroformic solution.At room temperature reacted 5 hours.With the solvent evaporate to dryness in the reaction solution, product 300-400 order silica gel/methylene dichloride column chromatography, recrystallizing methanol.
Three) by following example the synthetic of other conjugative monomers outside the coordination compound monomer is further described.
Following example will be to the explanation of monomer proposed by the invention, but the present invention will be not limited to listed example.
Embodiment 12
2, the preparation of 7-dibromo fluorenes
Press world patent (WO 99 05184) and Chem.Mater.11 (1997), 11083 method preparation:
In 250 milliliters of there-necked flasks, add 100 milliliters of fluorenes 16.6 grams (0.1 mole), iron powder 88 milligrams (1.57 mmole), trichloromethanes.The ice-water bath cooling, 35 milliliters of dripping bromine 35.2 gram (0.22 mole)/trichloromethane mixing solutionss.The interior temperature of bottle is no more than 5 ℃ during dropping.Reaction finishes, and filtration, chloroform recrystallization get white crystal 26.9 grams, productive rate 83%.
13C NMR and GC-MASS test shows are target product.
Embodiment 13
2,7-two bromo-9, the preparation of 9-dialkyl substituted fluorene
To prepare 2,7-two bromo-9,9-di-n-octyl fluorenes are that example is illustrated
In there-necked flask, add 2,7-dibromo fluorenes 9.7 grams (0.03 mole), benzyltriethylammoinium chloride 0.07 gram (0.3 mmole), 90 milliliters, 45 milliliters aqueous sodium hydroxide solutions of dimethyl sulfoxide (DMSO) (50%).Vigorous stirring forms suspension under the room temperature.Slowly drip 1-bromine octane 12.5 grams (65 mmole), continue to stir after 3 hours, use extracted with diethyl ether.With saturated sodium-chloride water solution washing ether phase, anhydrous magnesium sulfate drying.Boil off solvent, product is made the eluent column chromatography with sherwood oil and is purified, and gets white crystals.
13CNMR and GC-MASS test shows are target product.
Embodiment 14
9, the 9-dialkyl group replaces-2, the preparation of 7-hypoboric acid ester fluorenes
Press Macromolecules 30 (1997) 7686 disclosed methods, with 9,9-di-n-octyl-2,7-hypoboric acid ester fluorenes be prepared as example illustrated.
In 500 milliliters of there-necked flasks, add 2,7-two bromo-9,130 milliliters of 9-di-n-octyl fluorenes 5.6 grams (10.22 mmole), anhydrous tetrahydro furans.In the time of-78 ℃, drip n-Butyl Lithium/hexane solution (1.6M) 20 milliliters (32 mmole) under the argon shield, stirred 2 hours down at-78 ℃.Add 2-isopropoxy-4,4,5 subsequently fast, 5-tetramethyl--1,3,25 milliliters of 2-ethylenedioxy boric acid esters (123 mmole) continue down to stir 2 hours at-78 ℃.Reaction mixture rises to room temperature gradually, stirring reaction 36 hours.Reaction mixture is poured in ether/water, with extracted with diethyl ether, NaCl solution washing, anhydrous magnesium sulfate drying.Boil off solvent, resistates is with tetrahydrofuran (THF)/recrystallizing methanol, further purifies (sherwood oil: ethyl acetate=9: 1 be an eluent) with silica gel column chromatography, must white solid.
1H NMR, GC-MASS analysis revealed gained are target product.
Embodiment 15
3, the preparation of 6-dibromo carbazole
In 500 milliliters of there-necked flasks, add 24 milliliters of carbazole 13 grams (75 mmole), 300 milliliters of dithiocarbonic anhydride and anhydrous pyridines.With the frozen water cooling, at 0 ℃ of down slow dropping liquid bromine 28 gram (177 mmole)/dithiocarbonic anhydride solution (75 milliliters).Remove refrigerating unit after dripping off, be warming up to 15 ℃ gradually.Keep 15 ℃ to stir 4 hours down.Reaction solution is poured in 400 milliliters of dilute hydrochloric acid, had faint yellow precipitation to generate.Filter, wash 3 times, be washed with distilled water to neutrality again, add anhydrous magnesium sulfate drying with diluted sodium hydroxide solution.Product gets white needle-like crystals, productive rate 83% with ethyl alcohol recrystallization, oven dry.
1H NMR and GC-MASS test shows are target product.
Embodiment 16
3, the preparation of 6-two bromo-N-alkyl replacement-carbazoles
With 3,6-two bromo-N-2-ethylhexyl-carbazoles be prepared as example illustrated
In 250 ml flasks, under nitrogen protection, add 25 milliliters of sodium hydride (60%) 1.2 gram (27.6 mmole), tetrahydrofuran (THF)s.Slowly drip 3,6-dibromo carbazole 5 gram (15.4 mmole)/tetrahydrofuran solutions (25 milliliters).Have this moment small bubbles to generate, solution is also by the thin out green of canescence.Stir after 2 hours under the room temperature, temperature is risen to the solution reflux temperature.Add 1-bromo-2-ethyl hexane 5 grams (25.2 mmole), back flow reaction 24 hours.Boil off solvent, add methylene chloride/the water extraction.With distilled water wash organic layer, anhydrous magnesium sulfate drying.Remove and desolvate, get faint yellow viscous liquid.Product is made the eluent column chromatography with ethyl acetate/sherwood oil (1: 10), gets white crystal, productive rate 75%.
1H NMR and GC-MASS test shows are target product.
Embodiment 17
The N-alkyl replaces-3, the preparation of 6-hypoboric acid ester carbazole
Preparing 3,6-two (4,4,5,5-tetramethyl--1,3,2-dioxy boric acid ester)-N-(2 '-ethylhexyl) carbazole is that example is illustrated and adds 3 in there-necked flask, 80 milliliters of 6-two bromo-N-2-ethylhexyl carbazoles 4.5 grams (10.3 mmole), tetrahydrofuran (THF)s.Reaction solution is cooled to-78 ℃, slowly drips 24 milliliters of n-Butyl Lithiums (2M) (48 mmole), continue down to stir 2 hours at-78 ℃.Disposable then adding 2-isopropoxy-(4,4,5, the 5-tetramethyl-)-1,3,25 milliliters of 2-ethylenedioxy boric acid esters (123 mmole) stirred 2 hours at-78 ℃.Temperature was risen to room temperature reaction 36 hours.Use extracted with diethyl ether, saturated common salt water washing 4 times, use anhydrous magnesium sulfate drying.Distillation removes and desolvates, and product is purified for the eluent column chromatography with ethyl acetate/sherwood oil (1: 9), gets white crystal, productive rate 45%.
1H NMR and GC-MASS test shows are target product.
Embodiment 18
2, the preparation of 5-two iodo-(1, the 4-dialkyl group replaces)-benzene
To prepare 2,5-two iodo-(1-methyl-4-n-octyl)-benzene is that example is illustrated
In the 250ml there-necked flask, add 1-methyl-4 n-octyl 9 grams, potassium periodate 10 grams, iodine 12 grams, Glacial acetic acid 100ml, vitriol oil 4ml and distilled water 8ml.Stir, heat, reacted 24 hours down at 90 ℃.Reaction finishes the back product is poured into the middle stirring of 200ml sodium sulfite aqueous solution (30%) 30-90 minute.Filtration, adding distil water washing are removed inorganic salt for several times, use the dehydrated alcohol recrystallization then, get crude product., make eluent with sherwood oil, silica gel column chromatography is purified, and gets white crystals.H
1NMR and GC-MASS test shows are target product.
Embodiment 19
2,5-two bromo-(1,4-two hexyloxy)-benzene preparation
1) in the 250ml there-necked flask, adds Resorcinol 6.6 grams, sodium methylate 10 grams, dehydrated alcohol 50ml, be heated to backflow.After one hour, slowly drip 1-bromo-normal hexane 37.6 grams, back flow reaction 10 hours.With the solvent evaporate to dryness, product extracted with ether and water after reaction finished.Organic layer is washed till neutrality with distilled water, and anhydrous magnesium sulfate drying spends the night.Distillation after product ethyl alcohol recrystallization gets white plates crystal 15 grams, and productive rate is 75%.
2) in the 250ml there-necked flask, add two hexyloxy benzene, 10.6 grams, CCl
4100ml stirs, dissolves.Slow dropping liquid bromine 4.8ml/CCl
4(50ml) solution.After at room temperature reacting 20 hours, reaction solution is poured termination reaction in the 80ml aqueous sodium hydroxide solution (10%) into.Use extracted with diethyl ether, organic layer with alkali cleaning, be washed to neutrality, anhydrous magnesium sulfate drying spends the night.Steam solvent, the product ethyl alcohol recrystallization gets white crystal 14 grams, and productive rate is 85%.
1H NMR and GC-MASS test shows are target product.
Embodiment 20
2, the preparation of 5-(1,4-two hexyloxy) benzene-hypoboric acid propyl ester
1) in the 250ml there-necked flask, adds 2,130 milliliters of 5-two bromo-(1,4-two hexyloxy) benzene 4.36 grams (10 mmole), anhydrous tetrahydro furans.Under argon shield, in the time of-78 ℃, slowly drip n-Butyl Lithium/hexane solution (1.6M) 15 milliliters (24 mmole).Reaction mixture stirred 2 hours down at-78 ℃, added 15 milliliters of trimethyl borates (130 mmole) subsequently fast, continued to stir 2 hours down at-78 ℃.Reaction mixture is risen to room temperature gradually, stirring reaction 36 hours.Under 0-5 ℃, in reaction mixture, drip 50 milliliters of concentrated hydrochloric acids subsequently, continue reaction 24 hours.Reaction mixture with extracted with diethyl ether, the NaCl aqueous solution wash earlier, anhydrous magnesium sulfate drying.Boil off solvent, obtain 2,5-(1,4-two hexyloxy) benzene-hypoboric acid.Be white solid 1.4 grams behind the recrystallization in acetone/hydrochloric acid, productive rate is 34%.
2) add 2 in the 250ml there-necked flask, 5-(1,4-two hexyloxy) benzene-hypoboric acid 3.7 grams (10 mmole), propylene glycol 2.3 restrain 100 milliliters of (30 mmole), toluene.Heating for dissolving after 24 hours, slowly is warming up to 130-150 ℃ 110 ℃ of following back flow reaction, and distillation divides water.Product is purified (ethyl acetate: sherwood oil=1: 15 is an eluent) with silica gel column chromatography, obtains a kind of white crystals.
1HNMR and GC-MASS test shows are target product.
Four) by following embodiment the synthetic of over-branched phosphorescent polymer is further described.Following example will be to the explanation of hyperbranched polymer proposed by the invention, but the present invention will be not limited to listed example.
Below be polyreaction embodiment
1) presses the preparation of world patent WO 99 05184 disclosed methods
Embodiment 21
The preparation of carbazoles hyperbranched polymer
In the 250ml there-necked flask, add 3,70 milligrams of the bromide monomer of 6-(N-2-ethyl-hexyl)-carbazole hypoboric acid ester 5 mmoles, equivalent (3,6-(N-2-ethyl-hexyl)-dibromo carbazole, an amount of three ring coordination compound monomers), triphenyl phosphorus palladiums.Under nitrogen protection, inject 30 milliliters of toluene, 2 milliliters of phase-transfer catalysts (ALIQUAT 336), 20 milliliters of aqueous sodium carbonates (2M).Mixture heating up is to refluxing stirring reaction 48 hours.Add 0.5 gram phenylo boric acid, 1 milliliter of bromobenzene end-blocking then successively, and continue reaction 8 hours respectively.With reaction mixture cooling, under agitation slowly in 1 liter of the impouring methyl alcohol.Powdered or the fibrous polymer that filter, collecting precipitation goes out.With methanol wash, drying.Product silica gel column chromatography, toluene are made eluent and are purified.Concentrate eluant is under agitation slowly in 1 liter of methyl alcohol of impouring.Filtration, vacuum-drying get multipolymer.The ratio of components of partial polymer, the ultraviolet absorption peak of film, photoluminescence spectra peak, electroluminescent spectrum peak, photoluminescence efficiency and electroluminescent efficiency etc. are listed in table 4.
Embodiment 22
The preparation method of fluorenes class hyperbranched polymer is with embodiment 21
With 9,9-two replaces-2, and 7-fluorenes hypoboric acid ester replaces N-to replace-3,6-carbazole hypoboric acid ester.The bromide monomer of equivalent (9,9-two replaces-2,7-dibromo fluorenes, an amount of three ring coordination compound monomers).
Embodiment 23
To the preparation method of benzene class hyperbranched polymer with embodiment 21
With 1 (4)-(two)-replacement-2,5-benzene hypoboric acid ester replaces N-to replace-3, and 6-carbazole hypoboric acid ester, 1 (4)-(two)-replacement-2,5-dibromobenzene replace N-to replace-3,6-two bromo-carbazoles.
Contain the preparation of the hyperbranched polymer of Fourth Ring title complex
Embodiment 24
The coordination compound monomer process for copolymerization is with embodiment 21.
With 2,7-two-(4,4,5,5-tetramethyl--1,3,2-two oxa-borines)-9, and the bromide monomer of 9-dioctyl fluorene, equivalent (2,7-two bromo-9,9-dioctyl fluorene, 2,7,12,17-tetrabromo-(5,10,15, the 20-tetraphenyl)-porphyrin platinum) be dissolved in toluene and 2MNa with different proportionings
2CO
3In the aqueous solution, and then add (PPh
3)
4Pd (O) (0.5%) and Aliquat336.Under Ar atmosphere, reflux 48 hours afterreaction liquid with methanol extraction, washing with acetone, remove oligopolymer and catalyst residue.Product vacuum-drying 24 hours obtains serial target product.
Productive rate: 60%.
Embodiment 25
The macromole coordination method
1) synthetic method of polymkeric substance Fourth Ring part is with embodiment 21
With 2,7-two (4,4,5,5-tetramethyl--1,3,2-two oxa-borines-)-9,9-dioctyl fluorene, 2,7-two bromo-9,9-dioctyl fluorene and 2,7,12,17-tetrabromo-5,10,15, the 20-tetraphenylporphyrin is dissolved in toluene and 2M Na with different proportionings
2CO
3In the aqueous solution, and then add (PPh
3)
4Pd (0.5%) and Aliquat336 are after refluxing 48 hours under the Ar atmosphere, with methanol extraction, washing with acetone, to remove oligopolymer and catalyst residue.Under the vacuum dry 24 hours, obtain a series of polymkeric substance Fourth Ring part.
2) coordination method of polymkeric substance Fourth Ring part is with embodiment 10,11
Platinum coordination reaction with the polymkeric substance part that contains the Fourth Ring porphyrin is that example is illustrated
In the 100ml there-necked flask, argon shield adds PtCl down
2, the benzene nitrile, after 1 hour, add the benzene nitrile solution of polymkeric substance Fourth Ring part 100 ℃ of reactions, be chilled to room temperature 190 ℃ of reactions after 10 hours, the solution of reaction is poured into is obtained precipitation in the methyl alcohol.Filter the back with 300-400 order silica gel/toluene column chromatography, use the toluene and methanol reprecipitation then.Productive rate: 41-50%.
2) press the preparation of Prog.Polym.Sci.17 (1992) 1153-1205 disclosed method
Embodiment 26
Preparation to benzene class hyperbranched polymer
The exsiccant reaction flask with the argon gas stream flushing several times.The catalyst n i (COD) of mole (6.5 mmole) such as in glove box, take by weighing respectively
2, cyclooctadiene (COD) and 2,2 '-dipyridyl.Use purified N, 8 milliliters of dissolvings of dinethylformamide.80 ℃ of down reactions after 0.5 hour, the dry toluene solution of 4 mmoles [1 (4)-(two)-replace-2,5-dibromobenzene and three an amount of ring coordination compound monomers] is injected in the catalyst solution.Under nitrogen protection, be warming up to 90 ℃ of stirring reactions after 72 hours, add 1 milliliter of bromobenzene end-blocking, continue reaction 12 hours.With reaction mixture cooling, under agitation slowly in 1 liter of methanol solution of impouring.Powdered or the fibrous polymer that filter, collecting precipitation goes out.Use methanol wash, drying.Use silica gel column chromatography, toluene is made eluent and is purified.Concentrate eluant under agitation slowly in 1 liter of methanol solution of impouring, filters out throw out, and vacuum-drying gets multipolymer.The ratio of components of partial polymer, the ultraviolet absorption peak of film, photoluminescence efficiency and electroluminescent efficiency etc. are listed in table 5.
Embodiment 27
The preparation method of carbazoles hyperbranched polymer is with embodiment 26
Replace-3 with N-, 6-dibromo carbazole replaces 1, and 4-two replaces-2, the 5-dibromobenzene.
Embodiment 28
The preparation method of fluorenes class hyperbranched polymer is with embodiment 26
With 9,9-two replaces-2, and 7-dibromo fluorenes replaces 1, and 4-two replaces-2, the 5-dibromobenzene.
Embodiment 29
The preparation method of hyperbranched polymer who contains the Fourth Ring title complex is with embodiment 26
Replace three ring coordination compound monomers with the Fourth Ring coordination compound monomer
Following example is to the luminescent material made device proposed by the invention and the explanation of characteristic, but the present invention will be not limited to listed example.
Five) preparation of polymer electroluminescent device
Ito glass is handled with oxygen-Plasma through after the ultrasonic cleaning, the square resistance of ito glass be 10 Ω/.The hole injection layer polymkeric substance is PEDT or PVK, and luminescent layer adopts above institute synthetic polymer, can also increase electron transfer layer.Luminescence polymer can with electron transport material blend such as PBD.Hole injection layer and polymer light-emitting layer all adopt the mode of spin coating to make.Cathode electrode adopts Ca/Al respectively, the Ba/Al metal.Apply positive bias between ITO and metal electrode, obtain 100Cd/m
2The characteristic of luminous intensity test component.
Subordinate list
| Table 4 | ||||||||
| The carbazoles hyperbranched polymer | ||||||||
| Polymkeric substance | Dibromide (mole%) | Hypoboric acid ester (mole%) | Three ring coordination compound monomers (mole%) | Film uv-absorbing (nm) | Film PL peak (nm) | Film EL peak (nm) | PL efficient (%) | EL efficient (%) |
| P-1 P-2 P-3 P-4 P-5 | M-3(97) M-3(94) M-3(90) M-3(80) M-3(70)+ M-43(20) | M-63(100) M-63(100) M-63(100) M-63(100) M-63(100) | M-95(2) M-95(4) M-95(6.6) M-95(13.4) M-95(6.6) | 300 300 300 300 300 | 530 530 530 530 530 | 530 530 530 530 530 | 53 53 58 62 82 | 3.0 3.5 6.0 1.4 14 |
| Table 5 | |||||||
| Poly-to benzene class hyperbranched polymer | |||||||
| Polymkeric substance | Dibromo compound (mole%) | Three ring coordination compound monomers (mole%) | Film ultraviolet absorption peak (nm) | Film PL peak (nm) | Film EL peak (nm) | PL efficient (%) | EL efficient (%) |
| P-6 P-7 P-8 P-9 | M-25(99.5 ) M-25(99) M-18(98) M-17(97) | M-95(05) M-95(1) M-95(2) M-95(3) | 330 330 290 325 | 420,520 420,520 420,520 530 | 520 520 520 530 | 33 22 29 17 | 1.5 14 0.4 0.7 |
Claims (5)
1, be the over-branched phosphorescent conjugated polymer of nuclear with the metal complexes, the branches that it is characterized in that over-branched phosphorescent conjugated polymer is 3, and described over-branched phosphorescent conjugated polymer has following chemical structural formula:
Described n
1, n
2, n
3, n
4, n
5, n
6, n
7And n
8Be all natural number;
Described M is the iridium metal complex with following chemical structural formula:
Or
Wherein, R is the side chain of alkyl or alkoxyl group;
Described A is the conjugated structure unit, has following one or more chemical structure:
Wherein, Ar is fragrant heterocyclic units; R
1, R
2Be C
1～C
10Alkyl or the side chain of alkoxyl group; M is an integer.
2, according to claim 1 is the over-branched phosphorescent conjugated polymer of nuclear with the metal complexes, it is characterized in that metal complexes shared molecular fraction in over-branched phosphorescent conjugated polymer is 0.1～20%.
3, be the over-branched phosphorescent conjugated polymer of nuclear with the metal complexes, the branches that it is characterized in that over-branched phosphorescent conjugated polymer is 4, and described over-branched phosphorescent conjugated polymer has following chemical structural formula:
n
1, n
2, n
3, n
4And n
13Be all natural number;
Described M is the metalloporphyrin title complex with following chemical structural formula:
Described M ' is Pt, Zn or Cu;
Described A has following one or more chemical structures:
Wherein, Ar is fragrant heterocyclic units; R
1, R
2Be C
1～C
10Alkyl or the side chain of alkoxyl group; M is an integer.
4, according to claim 3 is the over-branched phosphorescent conjugated polymer of nuclear with the metal complexes, it is characterized in that metal complexes shared molecular fraction in over-branched phosphorescent conjugated polymer is 0.1～20%.
5, one of claim 1～4 is described is the application of over-branched phosphorescent conjugated polymer in the active coating of the luminescent layer of photodiode, flat-panel monitor or solar-energy photo-voltaic cell of nuclear with the metal complexes.
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|---|---|---|---|---|
| JP2002003569A (en) * | 2000-04-17 | 2002-01-09 | National Institute Of Advanced Industrial & Technology | Monomer containing azide group and polybranched polymer |
| CN1381545A (en) * | 2001-03-08 | 2002-11-27 | 香港大学 | Light-emitting organic metal material |
| WO2004029134A1 (en) * | 2002-09-25 | 2004-04-08 | Isis Innovation Limited | Fluorene-containing dendrimers |
| CN1492904A (en) * | 2001-02-20 | 2004-04-28 | ϣ | Metal-containing dendrimers |
| WO2004076531A1 (en) * | 2003-02-27 | 2004-09-10 | Kanagawa Academy Of Science And Technology | Phenylazomethine dendrimer containing metal or metal cluster and method for preparation thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002003569A (en) * | 2000-04-17 | 2002-01-09 | National Institute Of Advanced Industrial & Technology | Monomer containing azide group and polybranched polymer |
| CN1492904A (en) * | 2001-02-20 | 2004-04-28 | ϣ | Metal-containing dendrimers |
| CN1381545A (en) * | 2001-03-08 | 2002-11-27 | 香港大学 | Light-emitting organic metal material |
| WO2004029134A1 (en) * | 2002-09-25 | 2004-04-08 | Isis Innovation Limited | Fluorene-containing dendrimers |
| WO2004076531A1 (en) * | 2003-02-27 | 2004-09-10 | Kanagawa Academy Of Science And Technology | Phenylazomethine dendrimer containing metal or metal cluster and method for preparation thereof |
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