CN100558766C - Contain the polymkeric substance and the application in the preparation luminescent material thereof of selenium heterocyclic compound - Google Patents
Contain the polymkeric substance and the application in the preparation luminescent material thereof of selenium heterocyclic compound Download PDFInfo
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Abstract
The present invention relates to contain the polymkeric substance and the application in the preparation luminescent material thereof of selenium heterocyclic compound, comprise one or more the heteroaromatic compounds that contains elemental selenium in the polymkeric substance; Can also comprise another component as, poly-fluorenes, poly-to benzene, p-phenylene vinylene, poly-SPIRO-to benzene, trapezoidal poly-to benzene (ladder-PPP) conjugated polymers one or more.The polymkeric substance that contains selenium heterocyclic compound provided by the invention has high-quantum efficiency, high color purity, and permanent stability are good, are applicable to high resolving power, panchromatic flat panel display device, photoelectric devices such as photovoltaic device.
Description
Technical field
The present invention relates to polymkeric substance, contain the polymkeric substance of selenium heterocyclic compound in more detail.
The invention still further relates to the application of this polymkeric substance in luminous, photovoltaic material of preparation or device.
Background technology
Since Japanese scientist Bai Chuanying tree in 1977 is found the polyacetylene conduction, this being called as the conductive polymers of " the 4th generation polymer " material attracted numerous scientists to study with its outstanding photoelectric properties.Conducting polymer is compared with the inorganic materials with identical or close purposes, and it is low to have density, and advantages such as range of choice is wide are synthesized in easily processing.Because the conjugate property of this class material structure, make its can transmission charge, stimulated luminescence, thus can or potential may on many electronics or opto-electronic device, being applied, for example comprise 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, comprise 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,, give off energy, 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.
The luminous high polymer material is because outstanding advantage has started a revolution of electronic display technology.In in the past 10 years, developed the luminescence polymer of One's name is legion.Making can commercial luminescent device, the illuminant colour coordinate of material, and luminous quantum efficiency, operating voltage (power consumption), the life-time service stability of device all must optimized choice.The researchist is making great efforts to seek to improve the method for polymer LED performance always, and material is one of most important factor.So being devoted to exploitation always, many research groups have high-quantum efficiency, high color purity, the luminescence polymer that permanent stability are good.
Summary of the invention
The object of the present invention is to provide a kind of polymkeric substance that contains selenium heterocyclic compound, this polymkeric substance has high-quantum efficiency, high color purity, and permanent stability are good, are applicable to that high resolving power, panchromatic plane show.
The invention still further relates to the application of polymkeric substance in the preparation luminescent material that contains selenium heterocyclic compound; Contain the application of polymkeric substance in the preparation photovoltaic material of selenium heterocyclic compound.Application in the luminescent layer of the polymkeric substance that contains selenium heterocyclic compound in preparation photodiode, flat-panel monitor.Contain the application of polymkeric substance in the active coating of preparation solar cell of selenium heterocyclic compound.
The polymer monomer that contains selenium heterocyclic compound of the present invention comprises the heterogeneous ring compound that contains elemental selenium.
The described heterogeneous ring compound that contains elemental selenium has following one or more structural units:
R wherein
1, R
2Be H, C
1-C
20Alkyl;
The heterogeneous ring compound that contains elemental selenium accounts for the 0.1-100% mole in polymkeric substance.
The polymkeric substance that contains selenium heterocyclic compound also comprise another component gather fluorenes, poly-to benzene, p-phenylene vinylene, poly-SPIRO-to benzene, trapezoidal poly-to benzene (ladder-PPP) conjugated polymers one or more, the heterogeneous ring compound that wherein contains elemental selenium accounts for the 0.1-99% mole in polymkeric substance, the molecular structure of another component is as follows:
Poly-fluorenes:
R wherein
1, R
2Be H, C
1-C
20Alkyl;
Poly-to benzene:
R wherein
1, R
2Be H, C
1-C
20Alkyl, alkoxyl group;
The p-phenylene vinylene:
R wherein
1, R
2Be H, C
1-C
20Alkoxyl group;
Poly-SPIRO-is to benzene:
R wherein
1, R
2Be H, C
1-C
20Alkyl;
Trapezoidal poly-to benzene (ladder-PPP):
R wherein
1, R
2, R
3, R
4, R
5, R
6Be H, C
1-C
20Alkyl.
The polymer light-emitting scope that contains selenium heterocyclic compound dissolves in common organic solvents in the 400-1100 nanometer.
The described polymkeric substance that contains selenium heterocyclic compound is used in the preparation luminescent material.
The described polymkeric substance that contains selenium heterocyclic compound is used in the preparation photovoltaic material.
Use in the luminescent layer of the described polymkeric substance that contains selenium heterocyclic compound in preparation photodiode, flat-panel monitor.
The described application of polymkeric substance in the active coating of preparation solar cell that contains selenium heterocyclic compound.
The present invention is to contain selenium heterocyclic compound, and selenole and selenophen and their derivative are monomer, has synthesized a series of brand-new multipolymers.The selenole of serial alkyl replacement and the homopolymer of selenophen have also been synthesized simultaneously.Adopting this base polymer is luminescent layer, makes polymer LED, has studied their photoelectric property.Selenium atom and sulphur atom belong to the 6th main group, and selenium is compared with sulphur, and nonmetal character weakens, and metallicity strengthens.The atomic radius of selenium (116pm) is than the big 13pm of atomic radius (103pm) of sulphur, and divalence negative ion radius (198pm) is than the big 14pm of sulphur (184pm), and the electron affinity and first ionization energy also have tangible reduction.Ionic radius increases, and causes sterically hindered increase, makes the interchain interaction force weaken, and may weaken the generation that swashs the ground state complex compound, helps the raising of luminous efficiency.On the other hand, polymer light-emitting of the present invention (comparing with sulphur compound) red shift of wavelength can be applied aspect the near-infrared luminous device.
The material that can be used as the main body of multipolymer in the present invention will be not limited to poly-fluorenes.The material of main part that all had been reported in the document may be used to and the copolymerization that contains selenium heterocyclic compound.For example, poly-to benzene, the p-phenylene vinylene, poly-SPIRO-PPP, trapezoidal poly-to benzene (ladder-PPP) etc.We particularly point out by we propose first as the resulting multipolymer of main body good characteristics (Huang et al, Macromolecules, in press) are arranged with the prepared conjugation polycarbazole of SUZUKI method.Compare with fluorenes, because of replaced carbon atom with nitrogen-atoms on 9, polycarbazole is a kind of good hole mobile material, and the homopolymer of carbazole itself is a blue light-emitting.When carbazole during with selenole and selenophen and derivative copolymerization thereof, can change level structure, the further red shift of emission wavelength also is a kind of luminescent material that potential using value is arranged.
One of them method of polymkeric substance that preparation contains selenium heterocyclic compound is to be the basic structure monomer with selenole and selenophen, synthetic a series of derivatives that contain selenium diazole and selenophen structure, all polymerizations on this basis, and with alkyl substituted fluorene and carbazole copolymerization, synthesized the conjugate light-emitting polymer that contains selenium diazole and selenophen structure on the main chain.Its emission wavelength can be regulated at whole visible region.Be expected to be used for the luminescent layer of polymer LED (PLED), be widely used in electronic instrument, the flat-panel screens of PDA(Personal Digital Assistant) and laptop computer etc. in the future.
The present invention compared with prior art has following advantage:
Institute of the present invention synthetic polymkeric substance, the electroluminescent external quantum efficiency has reached 1%, has the potential using value, and the emission wavelength red shift is expected to develop and novel panchromatic demonstration with red, green, blue three-colour light-emitting material.
Embodiment
By monomer and the multipolymer of following embodiment to the conjugate light-emitting macromolecular material that contains selenium diazole and selenophen derivative on the main chain, the preparation of homopolymer is further described.
Following examples will be to the explanation of monomer proposed by the invention.But the present invention will be not limited to listed example.
Embodiment 1:2, the preparation of 7-dibromo fluorenes, its molecular structure is as shown in table 1.
By world patent WO9905184 disclosed method in 1997 and " chemical material " (Chem.Mater) 11 (1997) 11083 disclosed methods preparation 2,7-dibromo fluorenes.Take by weighing fluorenes (16.6 grams, 0.1 mole), (88 milligrams of iron powders, 1.57 mmole) pour in the there-necked flask, add 100 milliliters of trichloromethanes, the ice-water bath cooling is from constant pressure funnel dripping bromine (35.2 grams, 0.22 mole) and the mixing solutions of 35 milliliters of trichloromethanes, the interior temperature of bottle should be above 5 ℃ during dropping.Reaction finishes, and filters, and uses the chloroform recrystallization, gets white crystal (26.9 grams, 83%).
13C NMR and GC-MASS test shows are target product 2,7-dibromo fluorenes.
Embodiment 2:2,7-two bromo-9, the preparation of 9-two substituted fluorenes, its molecular structure is as shown in table 1.
To prepare 2,7-two bromo-9,9-di-n-octyl fluorenes are that example is illustrated.By world patent WO 9905184 disclosed methods in 1997 and " chemical material " (Chem.Mater) 11 (1997) 11083 disclosed methods preparation 2,7-two bromo-9,9-di-n-octyl fluorenes.Get embodiment 1 gained 2,7-dibromo fluorenes (9.72 grams, 0.03 mole), benzyltriethylammoinium chloride (0.07 gram, 0.3 mmole) is poured in the there-necked flask, adds 90 milliliters of dimethyl sulfoxide (DMSO), the aqueous sodium hydroxide solution of 45 milliliters of weight ratios 50%, vigorous stirring forms suspension under the room temperature, drips 1-bromine octane (12.5 grams, 65 mmoles), continue to stir 3 hours, use extracted with diethyl ether then, merge the ether phase, with saturated sodium-chloride water solution washing, anhydrous magnesium sulfate drying.Boil off solvent, make the eluent column chromatography with normal hexane and purify, get white crystals.
13CNMR and GC-MASS test shows are target product 2,7-two bromo-9,9-di-n-octyl fluorenes.
2,7-two bromo-9, substituting group comprises in 9-two substituted fluorenes: n-hexyl, n-octyl, the 2-ethylhexyl, decyl etc., but be not limited only to this.
Embodiment 3:3, the preparation of 6-dibromo carbazole, its molecular structure is as shown in table 1.
In 1000 milliliters of there-necked flasks, add carbazole (12.54 grams, 75 mmoles), 375 milliliters of refining dithiocarbonic anhydride and 24 milliliters of anhydrous pyridines, cool off with frozen water while stirring with mechanical stirrer, when being cooled to 0 ℃, begin to drip the liquid bromine (28.30 grams, 177 mmoles) that is dissolved in 75 milliliters of dithiocarbonic anhydride, dripped approximately 1 hour.Remove refrigerating unit after dripping off, rise to 15 ℃ gradually, keep 15 ℃ to stir 2.5 hours down, reaction finishes.Reaction solution is poured in 400 milliliters of dilute hydrochloric acid, had faint yellow precipitation to generate, filter,, be washed with distilled water to neutrality again, drying with rare sodium hydroxide solution washing 3 times.Use the dehydrated alcohol recrystallization, oven dry gets white needle-like crystals, productive rate 83%.
1HNMR and GC-MASS test shows are target product 3,6-dibromo carbazole.
Embodiment 4:3, the preparation of 6-two bromo-N-substituted carbazoles, its molecular structure is as shown in table 1.
To prepare 3,6-two bromo-N-2-ethylhexyl carbazoles are that example is illustrated.Under nitrogen protection; (1.104 grams of the sodium hydride of adding 60% in 250 ml flasks; 27.6 mmole) and 25 milliliters of tetrahydrofuran (THF)s; drip while stirring and be dissolved in 3 of 25 milliliters of tetrahydrofuran (THF)s; 6-dibromo carbazole (5 grams; 15.4 solution mmole); there are this moment small bubbles to generate; solution is also by the thin out green of canescence, and stirring at normal temperature rose to solution with temperature of reaction and refluxes after for some time; add 4.5 milliliters of 1-bromo-2-ethyl hexanes (4.86 grams; 25.2 mmole), reaction is 24 hours under refluxing, and finishes reaction.Boil off solvent, adding methylene dichloride and water extracts, wash organic layer with water 4 times, add anhydrous magnesium sulfate drying, remove and desolvate, get faint yellow viscous liquid, it is further refining to make the eluent column chromatography with ethyl acetate and normal hexane mixed solvent (1: 10), obtain white crystal, productive rate 75%.
1HNMR and GC-MASS test shows are target product 3,6-two bromo-N-2-ethylhexyl carbazoles.
3, substituting group comprises in the 6-two bromo-N-substituted carbazoles: n-hexyl, and n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 5:9,9-two replaces-2, the preparation of 7-hypoboric acid ester fluorenes, its molecular structure is as shown in table 2.
Preparing 9,9-di-n-octyl-2,7-hypoboric acid ester fluorenes is that example is illustrated.By " macromole " (Macromolecules) 30 (1997) 7686 disclosed methods preparation 9,9-di-n-octyl-2,7-hypoboric acid ester fluorenes.Get embodiment 2 gained exsiccant 2; 7-two bromo-9; 9-di-n-octyl fluorenes (5.6 grams; 10.22 mmole) be dissolved in refining dried 130 milliliters of tetrahydrofuran (THF)s (THF); the dry argon gas protection drips 20 milliliters of n-Butyl Lithiums (1.6 mol, normal hexane are solvent, 32 mmoles) down in the time of-78 ℃; drip and finish; reaction mixture stirred 1.5 hours down at-78 ℃ at least, added 2-isopropoxy-4,4 subsequently fast; 5; 5-tetramethyl--1,3, (25 milliliters of 2-ethylenedioxy boric acid esters; 123.24 mmole), continue down to stir 2 hours at-78 ℃.Allow reaction mixture rise to room temperature gradually then, stirring reaction at least 36 hours.Reaction mixture is poured in the water subsequently, use extracted with diethyl ether, merge the ether phase, also use anhydrous magnesium sulfate drying with the salt water washing, boil off solvent, resistates is with tetrahydrofuran (THF) and recrystallizing methanol, further with column chromatography purification (silica gel, normal hexane: ethyl acetate=9: 1 is an eluent), white solid.
13CNMR, GC-MASS and ultimate analysis show that gained is a target product 9,9-di-n-octyl-2,7-hypoboric acid ester fluorenes.
9,9-two replaces-2, and substituting group comprises in the 7-hypoboric acid ester fluorenes: n-hexyl, and n-octyl, the 2-ethylhexyl, decyl, but be not limited only to this.
Embodiment 6:N-replaces-3, the preparation of 6-hypoboric acid ester carbazole, and its molecular structure is as shown in table 2.
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.Add 3 in there-necked flask, 6-two bromo-N-2-ethylhexyl carbazoles (4.5 grams, 10.30 mmoles) and 80 milliliters of tetrahydrofuran (THF)s after stirring, are cooled to reaction solution-78 ℃, drip 24 milliliters of 2M n-Butyl Lithiums (48 mmole).After dropwising, continue to stir disposable then adding 2-isopropoxy-4 2 hours at-78 ℃, 4,5,5-tetramethyl--1,3, (25 milliliters of 2-ethylenedioxy boric acid esters, 123.24 mmole), continue to stir 2 hours, then temperature of reaction is risen to room temperature at-78 ℃, reacted 36 hours, and finished reaction.Use extracted with diethyl ether, saturated common salt water washing 4 times, with organic layer with anhydrous magnesium sulfate drying after, remove and to desolvate, purify for the eluent column chromatography with ethyl acetate and normal hexane mixed solvent (1: 9), must white crystal, productive rate 45%.
1HNMR and GC-MASS test shows are target product 3,6-two (4,4,5,5-tetramethyl--1,3,2-dioxy boric acid ester)-N-(2 '-ethylhexyl) carbazole.
N-replaces-3, and substituting group comprises in the 6-hypoboric acid ester carbazole: n-hexyl, and n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Below be the preparation of selenole and selenophen and derivatives monomer thereof:
Embodiment 7:4,7-two bromo-2,1, the preparation of 3-selenole, its molecular structure is as shown in table 3.
Method A
By " chemistry meeting will " (J.Chem.Soc.) (1963) 4767 disclosed methods preparation 4,7-two bromo-2,1,3-selenole.Take by weighing 2,1,3-selenole (1.83 grams, 0.01 mole), Sulfuric acid disilver salt (3.12 grams, 0.01 mole), be dissolved in 20 milliliters of vitriol oils, stir, dripping bromine (3.2 grams, 0.02 mole), finish, reaction is 75 minutes under the room temperature, elimination Silver monobromide precipitation, in the filtrate impouring frozen water, use 450 milliliters of re-crystallizing in ethyl acetate then, get golden yellow needle crystal.Warp
1HNMR, GC-MASS, ultimate analysis is indicated as target product 4,7-two bromo-2,1,3-selenole.
Method B
By " organise association will " (J.Org.Chem.) 57, (1992) 6749-6755 disclosed method preparation 4,7-two bromo-2,1,3-selenole.Bromination 2,1, the 3-diazosulfide gets 4,7-two bromo-2,1,3-diazosulfide, productive rate 95%.Take by weighing 4,7-two bromo-2,1,3-diazosulfide (5.88 grams, 0.02 mole) adds 190 milliliters of ethanol, form suspension, drip sodium borohydride (14 grams, 0.37 mole) in the time of 0 ℃, the mixture stirring reaction is 20 hours under the room temperature, boils off solvent, gets 3,6-two bromo-1,2-phenylenediamine (4.5 gram), faint yellow solid, productive rate 85%.Get 3,6-two bromo-1,2-phenylenediamine (2.7 restrain 10 mmoles), 55 milliliters of ethanol reflux, and drip tin anhydride (1.17 grams, the 10.5 mmoles) aqueous solution (22 milliliters of hot water), and reaction mixture refluxed 2 hours is filtered, and gets yellow mercury oxide 3 grams, productive rate 88%.Warp
1HNMR, GC-MASS, ultimate analysis is indicated as target product 4,7-two bromo-2,1,3-selenole.
Embodiment 8:2, the preparation of 5-dibromo selenophen, its molecular structure is as shown in table 3.
By " Chemica Scripta " 7 (1975) 111-119 disclosed methods preparation 2,5-dibromo selenophen.Take by weighing selenophen (5 grams, 38.2 mmoles), add 10 milliliters of acetate, logical nitrogen also is cooled near 0 ℃, the mixing solutions of dripping bromine (13.2 grams, 82.6 mmoles) and 8 milliliters of acetate.Reacted 24 hours, temperature rising reflux 3 hours, reaction solution are poured in the saturated sodium bisulfite frozen water solution, extracted with diethyl ether, and with refrigerated 2N aqueous sodium hydroxide solution neutralization, water washing, the Calcium Chloride Powder Anhydrous drying, underpressure distillation promptly gets target product 2,5-dibromo selenophen.
Embodiment 9:4,7-two bromo-5-methyl-2,1, the preparation of 3-selenole, its molecular structure is as shown in table 3.
Take by weighing 3,4-diaminotoluene (4.88 grams, 0.04 mole), be dissolved in 18 milliliters of ethanol, reflux drips tin anhydride (4.66 grams, the 0.042 mole) aqueous solution (10 milliliters of hot water), dropwise, reflux half an hour, the normal hexane recrystallization gets needle-like white crystals 5-methyl-2,1, the 3-selenole.Press embodiment 6 these products of method A bromination.Take by weighing 5-methyl-2,1,3-selenole (1.97 grams, 0.01 mole), Sulfuric acid disilver salt (3.12 grams, 0.01 mole), be dissolved in 20 milliliters of vitriol oils, stir, dripping bromine (3.2 grams, 0.02 mole), finish, reaction is 75 minutes under the room temperature, elimination Silver monobromide precipitation, in the filtrate impouring frozen water, use 450 milliliters of re-crystallizing in ethyl acetate then, get golden yellow needle crystal.Warp
1HNMR, GC-MASS, ultimate analysis is indicated as target product 4,7-two bromo-5-methyl-2,1,3-selenole.
Embodiment 10:4,7-two bromo-5,6-dimethyl-2,1, the preparation of 3-selenole, its molecular structure is as shown in table 3.
Take by weighing 4,5-dimethyl-1,2-phenylenediamine (5.45 grams, 0.04 mole) is dissolved in 18 milliliters of ethanol, and reflux drips tin anhydride (4.66 grams, the 0.042 mole) aqueous solution (10 milliliters of hot water), dropwises, and refluxes half an hour.The normal hexane recrystallization gets the slightly yellow crystallization 5 of needle-like white, 6-dimethyl-2,1,3-selenole.Press embodiment 6 these products of method A bromination.Take by weighing 5,6-dimethyl-2,1,3-selenole (2.11 grams, 0.01 mole), Sulfuric acid disilver salt (3.12 grams, 0.01 mole), be dissolved in 20 milliliters of vitriol oils, stir, dripping bromine (3.2 grams, 0.02 mole) finishes, reaction is 75 minutes under the room temperature, and elimination Silver monobromide precipitation is in the filtrate impouring frozen water, use 450 milliliters of re-crystallizing in ethyl acetate then, get golden yellow needle crystal.Warp
1H NMR, GC-MASS, ultimate analysis is indicated as target product 4,7-two bromo-5,6-dimethyl-2,1,3-selenole.
Embodiment 11:4,7-two bromo-5-alkyl-2,1, the preparation of 3-selenole, its molecular structure is as shown in table 3.
Preparing 4,7-two bromo-5-n-octyls-2,1, the 3-selenole is that example is illustrated.Take by weighing 4-chloro-1,2-phenylenediamine (5.70 grams, 0.04 mole) is dissolved in 20 milliliters of ethanol, and reflux drips tin anhydride (4.66 grams, the 0.042 mole) aqueous solution (10 milliliters of hot water), dropwises, and refluxes one hour.(normal hexane: ethyl acetate=9: 1) recrystallization gets canescence tabular crystal 5-chloro-2,1, the 3-selenole with mixed solvent.
Get 1-bromine octane (2.90 gram, 15 mmoles), magnesium powder (0.41 gram, 17 mmoles) places there-necked flask, adds 10 milliliters of tetrahydrofuran (THF)s after the no water treatment, is back to the magnesium powder and reacts and remain little.In another there-necked flask, take by weighing dried 5-chloro-2,1,3-selenole (2.17 grams, 0.01 mole) adds 50 milliliters of anhydrous tetrahydro furans, drip Grignard reagent n-octyl bromination magnesium, reacted 24 hours, reactant is poured in the water then, use extracted with diethyl ether, merge the ether phase, anhydrous magnesium sulfate drying, boil off solvent, recrystallization gets 5-n-octyl-2,1, the 3-selenole.
Take by weighing 5-n-octyl-2,1,3-selenole (2.95 grams, 0.01 mole), Sulfuric acid disilver salt (3.12 grams, 0.01 mole), be dissolved in 20 milliliters of vitriol oils, stir, dripping bromine (3.2 grams, 0.02 mole), finish, reaction is 90 minutes under the room temperature, elimination Silver monobromide precipitation, in the filtrate impouring frozen water, use 500 milliliters of re-crystallizing in ethyl acetate then, get needle crystal.Warp
1HNMR, GC-MASS, ultimate analysis is indicated as target product 4,7-two bromo-5-n-octyls 2,1,3-selenole.
4,7-two bromo-5-alkyl-2,1, substituting group comprises in the 3-selenole: n-hexyl, n-octyl, the 2-ethylhexyl, decyl, but be not limited only to this.
Embodiment 12:4,7-two bromo-5,6-dialkyl group-2,1, the preparation of 3-selenole, its molecular structure is as shown in table 3.
To prepare 4,7-two bromo-5,6-di-n-octyl-2,1,3-selenole are that example is illustrated.Take by weighing 4,5-two chloro-1,2-phenylenediamine (7.08 grams, 0.04 mole) is dissolved in 20 milliliters of ethanol, and reflux drips tin anhydride (4.66 grams, the 0.042 mole) aqueous solution (10 milliliters of hot water), dropwises, and refluxes 1.5 hours.(normal hexane: ethyl acetate=9: 1) recrystallization gets canescence tabular crystal 5,6-two chloro-2,1,3-selenole with mixed solvent.
Get 1-bromine octane (4.83 gram, 25 mmoles) magnesium powder (0.65 gram, 27 mmoles) and place there-necked flask, add 10 milliliters of tetrahydrofuran (THF)s after the no water treatment, back flow reaction to magnesium powder remains little.In another there-necked flask, take by weighing dried 5,6-two chloro-2,1,3-selenole (2.52 grams, 0.01 mole), add 50 milliliters of anhydrous tetrahydro furans, drip Grignard reagent n-octyl bromination magnesium, reacted 24 hours, reactant is poured in the water then, uses extracted with diethyl ether, merges the ether phase, anhydrous magnesium sulfate drying boils off solvent, and recrystallization gets 5,6-di-n-octyl-2,1, the 3-selenole.
Take by weighing 5,6-di-n-octyl-2,1,3-selenole (4.07 grams, 0.01 mole), Sulfuric acid disilver salt (3.12 grams, 0.01 mole), be dissolved in 20 milliliters of vitriol oils, stir, dripping bromine (3.2 grams, 0.02 mole) finishes, reaction is 120 minutes under the room temperature, and elimination Silver monobromide precipitation is in the filtrate impouring frozen water, use 500 milliliters of re-crystallizing in ethyl acetate then, get needle crystal.Warp
1H NMR, GC-MASS, ultimate analysis is indicated as target product 4,7-two bromo-5,6-di-n-octyl 2,1,3-selenole.
4,7-two bromo-5,6-dialkyl group-2,1, substituting group comprises in the 3-selenole: n-hexyl, n-octyl, the 2-ethylhexyl, but be not limited only to this.
Embodiment 13:4,9-two bromo-6, the preparation of 7-selenium dialkyl diazole quinoxaline, its molecular structure is as shown in table 3.
Take by weighing 5,6-dinitrobenzene-2,1, (546 milligrams of 3-selenoles, 2.0 mmole), iron powder (1.33 grams, 24.0 mmoles) is dissolved in 40 milliliters of acetate, stirs 4 hours down at 30 ℃, reaction mixture is poured in 50 milliliters of 5% cold sodium hydroxide solutions then, there is precipitation to separate out solution extracted with diethyl ether, organic layer salt water washing, dried over sodium sulfate, boil off solvent under the decompression, residuum is purified (eluent dichloromethane) with silica gel column chromatography, and recrystallization gets diamine compound in trichloromethane then.
Get above gained 5,6-diamino-2,1,3-selenole 0.1-0.2 mmole, 1.4 times 2,3-dihydroxyl-1,4-dioxan (the product alkyl is a hydrogen), or 1.6-2.0 doubly 1, (dimethyl diketone, product alkyl are methyl to the 2-diketone; 7,8-tetradecyl diketone, product alkyl are hexyl), mix, at room temperature stirred 10 minutes, boil off solvent under the decompression, residuum adopts column chromatography and recrystallization to purify.
Take by weighing above-mentioned product 6,7-selenium dialkyl diazole quinoxaline (0.01 mole), Sulfuric acid disilver salt (0.01 mole) is dissolved in 20 milliliters of vitriol oils, stir, dripping bromine (0.02 mole) finishes, and reaction is 100 minutes under the room temperature, elimination Silver monobromide precipitation, in the filtrate impouring frozen water, use 450 milliliters of re-crystallizing in ethyl acetate then, get needle crystal.Warp
1H NMR, GC-MASS, ultimate analysis is indicated as target product 4,9-two bromo-6,7-selenium dialkyl diazole quinoxaline.
Embodiment 14:5 ', 5 " two bromo-6,7-dialkyl group-4,9-(2 ', the preparation of 2 ")-dithienyl selenium diazole quinoxalines, its molecular structure is as shown in table 3., its molecular structure is as shown in table 3.
Take by weighing 4,7-two bromo-5,6-dinitrobenzene-2,1,3-selenole (4.27 grams, 9.9 mmoles), tributyl-2-thienyl tin (8.51 grams, 22.8 mmoles) is dissolved in 30 milliliters of tetrahydrofuran (THF)s, adds PdCl subsequently
2(PPh
3)
2(143 milligrams, 2mol%), mixture back flow reaction 3 hours, solid is separated out in cooling, filters, with acetonitrile washing and collection, recrystallization in tetrahydrofuran (THF) then.
Get above gained dinitro compound (874 milligrams, 2.0 mmoles), iron powder (1.33 grams, 24.0 mmole) be dissolved in 40 milliliters of acetate, stirred 4 hours down at 30 ℃, reaction mixture is poured in 50 milliliters of 5% cold sodium hydroxide solutions then, has precipitation to separate out, the solution extracted with diethyl ether, organic phase salt water washing, dried over sodium sulfate boils off solvent under the decompression, residuum is purified (eluent methylene dichloride) with silica gel column chromatography, and recrystallization gets diamine compound in trichloromethane then.
Take by weighing above gained diamine compound 0.1-0.2 mmole, 1.4 times 2,3-dihydroxyl-1,4-dioxan (the product alkyl is a hydrogen), or 1.6-2.0 doubly 1, (dimethyl diketone, product alkyl are methyl to the 2-diketone; 7,8-tetradecyl diketone, product alkyl are hexyl), mix, at room temperature stirred 10 minutes, boil off solvent under the decompression, residuum adopts column chromatography and recrystallization to purify.
Take by weighing above-mentioned product 6,7-dialkyl group-4,9-(2 ', 2 ")-and dithienyl selenium diazole quinoxaline (0.01 mole), Sulfuric acid disilver salt (0.01 mole) is dissolved in 20 milliliters of vitriol oils; stir; dripping bromine (0.02 mole), finish, and reaction is 100 minutes under the room temperature; elimination Silver monobromide precipitation; in the filtrate impouring frozen water, use 450 milliliters of re-crystallizing in ethyl acetate then gets needle crystal.Warp
1H NMR, GC-MASS, ultimate analysis be indicated as target product 5 ', 5 " two bromo-6,7-dialkyl group-4,9-(2 ', 2 ")-dithienyl selenium diazole quinoxalines.
Embodiment 15:5 ', 5 " two bromo-6,7-dialkyl group-4,9-(2 ', the preparation of 2 ")-two-N-methylpyrrole base selenium diazole quinoxaline, its molecular structure is as shown in table 3.
Method is with embodiment 14.Take by weighing 4,7-two bromo-5,6-dinitrobenzene-2,1,3-selenole (3.02 grams, 7.0 mmoles), tributyl-2-N-methylpyrrole base tin (5.75 grams, 15.5 mmoles), PdCl
2(PPh
3)
2(98 milligrams, 2mol%), be dissolved in 20 milliliters of tetrahydrofuran (THF)s, mixture back flow reaction 3 hours, solid is separated out in cooling, filters, with acetonitrile washing and collection, recrystallization in tetrahydrofuran (THF) then.
Get above gained dinitro compound (861.5 milligrams, 2.0 mmoles), iron powder (1.33 grams, 24.0 mmole) be dissolved in 40 milliliters of acetate, stirred 4 hours down at 30 ℃, reaction mixture is poured in 50 milliliters of 5% cold sodium hydroxide solutions then, has precipitation to separate out, the solution extracted with diethyl ether, organic phase salt water washing, dried over sodium sulfate boils off solvent under the decompression, residuum is purified (eluent methylene dichloride) with silica gel column chromatography, and recrystallization gets diamine compound in trichloromethane then.
Take by weighing above gained diamine compound 0.1-0.2 mmole, 1.4 times 2,3-dihydroxyl-1,4-dioxan (the product alkyl is a hydrogen), 1.6-2.0 doubly 1, (dimethyl diketone, product alkyl are methyl to the 2-diketone; 7,8-tetradecyl diketone, product alkyl are hexyl), mix, at room temperature stirred 10 minutes, boil off solvent under the decompression, residuum adopts column chromatography and recrystallization to purify.
Take by weighing above-mentioned product 6,7-dialkyl group-4,9-(2 ', 2 ")-and two-N-methylpyrrole base selenium diazole quinoxaline (0.01 mole), Sulfuric acid disilver salt (0.01 mole) is dissolved in 20 milliliters of vitriol oils; stir; dripping bromine (0.02 mole), finish, and reaction is 100 minutes under the room temperature; elimination Silver monobromide precipitation; in the filtrate impouring frozen water, use 450 milliliters of re-crystallizing in ethyl acetate then gets needle crystal.Warp
1H NMR, GC-MASS, ultimate analysis be indicated as target product 5 ', 5 " two bromo-6,7-dialkyl group-4,9-(2 ', 2 ")-two-N-methylpyrrole base selenium diazole quinoxaline.
Embodiment 16:5 ', 5 " two bromo-6,7-dialkyl group-4,9-(2 ', the preparation of 2 ")-two selenophen base selenium diazole quinoxalines, its molecular structure is as shown in table 3.
Method is with embodiment 14.Take by weighing 4,7-two bromo-5,6-dinitrobenzene-2,1,3-selenole (3.02 grams, 7.0 mmoles), tributyl-2-selenophen base tin (6.50 grams, 15.5 mmoles), PdCl
2(PPh
3)
2(98 milligrams, 2mol%), be dissolved in 20 milliliters of tetrahydrofuran (THF)s, mixture back flow reaction 3 hours, solid is separated out in cooling, filters, with acetonitrile washing and collection, recrystallization in tetrahydrofuran (THF) then.
Get above gained dinitro compound (1.06 grams, 2.0 mmoles), iron powder (1.33 grams, 24.0 mmole) be dissolved in 40 milliliters of acetate, stirred 4 hours down at 30 ℃, reaction mixture is poured in 50 milliliters of 5% cold sodium hydroxide solutions then, has precipitation to separate out, the solution extracted with diethyl ether, organic phase salt water washing, dried over sodium sulfate boils off solvent under the decompression, residuum is purified (eluent methylene dichloride) with silica gel column chromatography, and recrystallization gets diamine compound in trichloromethane then.
Take by weighing above gained diamine compound 0.1-0.2 mmole, 1.4 times 2,3-dihydroxyl-1,4-dioxan (the product alkyl is a hydrogen), 1.6-2.0 doubly 1, (dimethyl diketone, product alkyl are methyl to the 2-diketone; 7,8-tetradecyl diketone, product alkyl are hexyl), mix, at room temperature stirred 10 minutes, boil off solvent under the decompression, residuum adopts column chromatography and recrystallization to purify.
Take by weighing above-mentioned product 6,7-dialkyl group-4,9-(2 ', 2 " selenophen base selenium diazole quinoxaline (0.01 mole))-two, Sulfuric acid disilver salt (0.01 mole) is dissolved in 20 milliliters of vitriol oils; stir; dripping bromine (0.02 mole), finish, reaction is 100 minutes under the room temperature; elimination Silver monobromide precipitation; in the filtrate impouring frozen water, use 450 milliliters of re-crystallizing in ethyl acetate then, needle crystal.Warp
1H NMR, GC-MASS, ultimate analysis be indicated as target product 5 ', 5 " two bromo-6,7-dialkyl group-4,9-(2 ', 2 ")-two selenophen base selenium diazole quinoxalines.
Embodiment 17:4,8-two bromo-2,1, the preparation of the two selenium diazole of 3-(5,6,7)-benzo, its molecular structure is as shown in table 3.
Take by weighing 5,6-diamino-2,1,3-selenole (8.52 grams, 40 mmoles) is dissolved in 20 milliliters of ethanol, refluxes, and drips tin anhydride (4.66 grams, the 42 mmoles) aqueous solution of heat, finishes, and refluxes 1 hour, and the normal hexane recrystallization is purified.Press embodiment 6 these products of method A bromination, get 4,8-two bromo-2,1, the two selenium diazole of 3-(5,6,7)-benzo.
Embodiment 18:4,8-two bromo-6-sulfo-s-2,1, the preparation of the two selenium diazole of 3-benzo, its molecular structure is as shown in table 3.
Method A
Take by weighing 4,7-two bromo-5,6-dinitrobenzene benzo thiadiazoles (3.84 grams, 10 mmoles) is dissolved in the acetate, with iron powder (6.72 grams, 120 mmoles) reduction, gets 4,7-two bromo-5,6-diamino benzo thiadiazoles.Get this diamine compound (3.24 grams, 10 mmoles), be dissolved in 5 milliliters of ethanol, reflux, add tin anhydride (1.22 grams of heat, 11 mmoles) aqueous solution dropwises, and refluxes 1 hour, and re-crystallizing in ethyl acetate is purified, get 4,8-two bromo-6-sulfo-s-2,1, the two selenium diazole of 3-benzo.
Method B
Take by weighing 4,7-two bromo-5,6-dinitrobenzene benzo selenium diazole (4.31 grams, 10 mmoles) is dissolved in the acetate, with iron powder (6.72 grams, 120 mmoles) reduction, gets 4,7-two bromo-5,6-diamino benzo selenium diazole.Get this diamine compound (1.11 grams, 3.0 mmoles), (834 milligrams of thionyl anilines, 6.0 mmole), trimethylchlorosilane (592 milligrams, 5.4 mmoles), be dissolved in 15 milliliters of pyridines, 80 ℃ of following stirring reactions 24 hours add 50 milliliters of tetracol phenixin then, produce solid precipitation, filter and collecting precipitation, purify 4,8-two bromo-6-sulfo-s-2,1, the two selenium diazole of 3-benzo.
Embodiment 19:5 ', 5 " two bromo-4,8-(2 ', 2 ")-dithienyls-2,1, the preparation of the two selenium diazole of 3-(5,6,7)-benzo, its molecular structure is as shown in table 3.
Take by weighing 5,6-diamino-4,7-(2 ', 2 ")-dithienyls-2,1; 3-selenole (3.77 grams, 10 mmoles) are dissolved in 5 milliliters of ethanol, reflux, and add tin anhydride (1.22 grams; the 11 mmoles) aqueous solution of heat, dropwise, and reflux 1 hour, and the normal hexane recrystallization is purified.Press embodiment 6 these products of method A bromination, 5 ', 5 " two bromo-4,8-(2 ', 2 ")-dithienyls-2,1, the two selenium diazole of 3-(5,6,7)-benzo.
Embodiment 20:5 ', 5 " two bromo-4,8-(2 ', 2 ")-two-N-methylpyrrole base-2,1, the preparation of the two selenium diazole of 3-(5,6,7)-benzo, its molecular structure is as shown in table 3.
Method is with embodiment 19.Take by weighing 5,6-diamino-4,7-(2 ', 2 ")-two-N-methylpyrrole base-2,1; 3-selenole (3.71 grams, 10 mmoles) are dissolved in 5 milliliters of ethanol, reflux, and add tin anhydride (1.22 grams; the 11 mmoles) aqueous solution of heat, dropwise, and reflux 1 hour, and the normal hexane recrystallization is purified.Press embodiment 6 these products of method A bromination, 5 ', 5 " two bromo-4,8-(2 ', 2 ")-two-N-methylpyrrole base-2,1, the two selenium diazole of 3-(5,6,7)-benzo.
Embodiment 21:5 ', 5 " two bromo-4,8-(2 ', 2 ")-two selenophen bases-2,1, the preparation of the two selenium diazole of 3-(5,6,7)-benzo, its molecular structure is as shown in table 3.
Method is with embodiment 19.Take by weighing 5,6-diamino-4,7-(2 ', 2 ")-two selenophen bases-2,1; 3-selenole (4.71 grams, 10 mmoles) are dissolved in 5 milliliters of ethanol, reflux, and add tin anhydride (1.22 grams; the 11 mmoles) aqueous solution of heat, dropwise, and reflux 1 hour, and the normal hexane recrystallization is purified.Press embodiment 6 these products of method A bromination, 5 ', 5 " two bromo-4,8-(2 ', 2 ")-two selenophen bases-2,1, the two selenium diazole of 3-(5,6,7)-benzo.
Embodiment 22:5 ', 5 " two bromo-4,8-(2 ', 2 ")-dithienyl-6-sulfo--2,1, the preparation of the two selenium diazole of 3-benzo, its molecular structure is as shown in table 3.
Take by weighing 5,6-diamino-4,7-(2 ', 2 ")-dithienyls-2,1; 3-diazosulfide (990 milligrams, 3.0 mmoles) are dissolved in 3 milliliters of ethanol, reflux, and add tin anhydride (0.35 gram; the 3.1 mmoles) aqueous solution of heat, dropwise, and reflux 1 hour, and the normal hexane recrystallization is purified.Press embodiment 6 these products of method A bromination, 5 ', 5 " two bromo-4,8-(2 ', 2 ")-dithienyl-6-sulfo--2,1, the two selenium diazole of 3-benzo.
Embodiment 23:5 ', 5 " two bromo-4,8-(2 ', 2 ")-two-N-methylpyrrole base-6-sulfo--2,1, the preparation of the two selenium diazole of 3-benzo, its molecular structure is as shown in table 3.
Method is with embodiment 22.Take by weighing 5,6-diamino-4,7-(2 ', 2 ")-two-N-methylpyrrole base-2,1; 3-diazosulfide (3.24 grams, 10 mmoles) are dissolved in 5 milliliters of ethanol, reflux, and add tin anhydride (1.22 grams; the 11 mmoles) aqueous solution of heat, dropwise, and reflux 1 hour, and the normal hexane recrystallization is purified.Press embodiment 6 these products of method A bromination, 5 ', 5 " two bromo-4,8-(2 ', 2 ")-two-N-methylpyrrole base-6-sulfo--2,1, the two selenium diazole of 3-benzo.
Embodiment 24:5 ', 5 " two bromo-4,8-(2 ', 2 ")-two selenophen base-6-sulfo-s-2,1, the preparation of the two selenium diazole of 3-benzo, its molecular structure is as shown in table 3.
Method is with embodiment 22.Take by weighing 5,6-diamino-4,7-(2 ', 2 ")-two selenophen bases-2,1; 3-diazosulfide (4.24 grams, 10 mmoles) are dissolved in 5 milliliters of ethanol, reflux, and add tin anhydride (1.22 grams; the 11 mmoles) aqueous solution of heat, dropwise, and reflux 1 hour, and the normal hexane recrystallization is purified.Press embodiment 6 these products of method A bromination, 5 ', 5 " two bromo-4,8-(2 ', 2 ")-two selenophen base-6-sulfo-s-2,1, the two selenium diazole of 3-benzo.
Embodiment 25:5 ', 5 " two bromo-4,7-(2 ', 2 ")-two selenophen bases-2,1, the preparation of 3-diazosulfide, its molecular structure is as shown in table 3.
Take by weighing 4,7-two bromo-2,1,3-diazosulfide (4.41 grams, 15.0 mmoles), tributyl-2-selenophen base tin (15.1 grams, 36.1 mmoles) is dissolved in 100 milliliters of tetrahydrofuran (THF)s, adds PdCl
2(PPh
3)
2(213 milligrams, 2mol%).Reaction mixture refluxed 10 hours, pressure reducing and steaming solvent, residuum adopt silica gel column chromatography purification (eluent, methylene dichloride/normal hexane, 1: 1), recrystallization in ethanol-toluene mixed solvent then, bromination, separate to purify, target product 5 ', 5 " two bromo-4; 7-(2 '; 2 " )-two selenophen base-2,1, the 3-diazosulfide.
Embodiment 26:5 ', 5 " two bromo-4,7-(2 ', 2 ")-dithienyls-2,1, the preparation of 3-selenole, its molecular structure is as shown in table 3.
Method is with embodiment 25.Take by weighing 4,7-two bromo-2,1,3-selenole (5.1 grams, 15.0 mmoles), tributyl-2-thienyl tin (13.47 grams, 36.1 mmoles) is dissolved in 100 milliliters of tetrahydrofuran (THF)s, adds PdCl
2(PPh
3)
2(213 milligrams, 2mol%).Reaction mixture refluxed 10 hours, pressure reducing and steaming solvent, residuum adopt silica gel column chromatography purification (eluent, methylene dichloride/normal hexane, 1: 1), recrystallization in ethanol-toluene mixed solvent then, bromination, separate to purify, target product 5 ', 5 " two bromo-4; 7-(2 '; 2 " )-dithienyl-2,1, the 3-selenole.
Embodiment 27:5 ', 5 " two bromo-4,7-(2 ', 2 ")-two-N-methylpyrrole base-2,1, the preparation of 3-selenole, its molecular structure is as shown in table 3.
Method is with embodiment 25.Take by weighing 4,7-two bromo-2,1,3-selenole (5.1 grams, 15.0 mmoles), tributyl-2-N-methylpyrrole base tin (13.35 grams, 36.1 mmoles) is dissolved in 100 milliliters of tetrahydrofuran (THF)s, adds PdCl
2(PPh
3)
2(213 milligrams, 2mol%).Reaction mixture refluxed 10 hours, pressure reducing and steaming solvent, residuum adopt silica gel column chromatography purification (eluent, methylene dichloride/normal hexane, 1: 1), recrystallization in ethanol-toluene mixed solvent then, bromination, separate to purify, target product 5 ', 5 " two bromo-4; 7-(2 '; 2 " )-two-N-methylpyrrole base-2,1, the 3-selenole.
Embodiment 28:5 ', 5 " two bromo-4,7-(2 ', 2 ")-two selenophen bases-2,1, the preparation of 3-selenole, its molecular structure is as shown in table 3.
Method is with embodiment 25.Take by weighing 4,7-two bromo-2,1,3-selenole (5.1 grams, 15.0 mmoles), tributyl-2-selenophen base tin (15.15 grams, 36.1 mmoles) is dissolved in 100 milliliters of tetrahydrofuran (THF)s, adds PdCl
2(PPh
3)
2(213 milligrams, 2mol%).Reaction mixture refluxed 10 hours, pressure reducing and steaming solvent, residuum adopt silica gel column chromatography purification (eluent, methylene dichloride/normal hexane, 1: 1), recrystallization in ethanol-toluene mixed solvent then, bromination, separate to purify, target product 5 ', 5 " two bromo-4; 7-(2 '; 2 " )-two selenophen base-2,1, the 3-selenole.
Embodiment 29:5 ', 5 " two bromo-2,3-dialkyl group-5,8-(2 ', the preparation of 2 ")-two selenophen base quinoxalines, its molecular structure is as shown in table 3.
Take by weighing 4,7-two bromo-2,1,3-diazosulfide (4.41 grams, 15.0 mmoles), tributyl-2-selenophen base tin (15.15 grams, 36.1 mmoles) is dissolved in 100 milliliters of tetrahydrofuran (THF)s, adds PdCl
2(PPh
3)
2(213 milligrams, 2mol%).Reaction mixture refluxed 10 hours, pressure reducing and steaming solvent, residuum adopt silica gel column chromatography purification (eluent, methylene dichloride/normal hexane, 1: 1), recrystallization in ethanol-toluene mixed solvent gets 4 then, 7-(2 ', 2 " selenophen base-2,1)-two, the 3-diazosulfide.
Take by weighing 4,7-(2 ', 2 ")-two selenophen bases-2,1,3-diazosulfide (394 milligrams, 1.00 mmoles), zinc powder (1.33 grams, 20.3 mmoles) is dissolved in 15 milliliters of acetate, refluxes 25 minutes.Reaction mixture filters, residuum washs with ether, in filtrate, add 100 milliliters of ether, and use 5% sodium hydroxide and salt water washing, organic layer dried over mgso respectively, boil off solvent, adopt silica gel column chromatography to purify (eluent methylene dichloride), get 1,2-diamino-3,6-(2 ', 2 ")-two selenophen base benzene.
Get 1,2-diamino-3,6-(2 ', 2 ")-two selenophen base benzene (136 milligrams, 0.37 mmole), 1.0-1.5 doubly 1, (dimethyl diketone, product alkyl are methyl to the 2-diketone; 7,8-tetradecyl diketone, product alkyl are hexyl), be dissolved in 5 milliliters of acetate, stirring reaction is 20 minutes under the room temperature, boils off solvent under the decompression, and residuum adopts column chromatography and recrystallization to purify.Bromination, separate purify target product 5 ', 5 " two bromo-2,3-dialkyl group-5,8-(2 ', 2 ")-two selenophen base quinoxalines.
Embodiment 30:5 ', 5 " two bromo-2,3,7,8-tetramethyl--5,10-(2 ', the preparation of 2 ")-two selenophen base pyrazines and quinoxaline, its molecular structure is as shown in table 3.
Take by weighing 5,6-dinitrobenzene-4,7-(2 ', 2 " selenophen base diazosulfide (247 milligrams, 0.51 mmole))-two, zinc powder (693 milligrams; 10.6 mmoles) is dissolved in 5 milliliters of acetate, 60 ℃ of following stirring reactions 1 hour; be chilled to room temperature, two butanone (0.35 gram, 4.1 mmoles) add in the reaction flask; mixture restir 1 hour; decompression boils off solvent down, and residuum adopts silica gel column chromatography purification (eluent methylene dichloride), uses the tetrahydrofuran (THF) recrystallization then; bromination, separate purify target product 5 ', 5 " two bromo-2,3; 7; 8-tetramethyl--5,10-(2 ', 2 ")-two selenophen base pyrazine and quinoxalines.
Embodiment 31:5 ', 5 " two bromo-2,3-dialkyl group-5,7-(2 ', the preparation of 2 ")-two selenophen base thieno-pyrazines, its molecular structure is as shown in table 3.
Take by weighing 2,5-two bromo-3,4-dinitro thiophene (5.01 grams, 15.1 mmoles), tributyl-2-selenophen base tin (15.15 grams, 36.1 mmoles) is dissolved in 100 milliliters of tetrahydrofuran (THF)s, adds PdCl
2(PPh
3)
2(108 milligrams, 1mol%).Mixture refluxed 20 hours, cooled off, and under reduced pressure concentrated, and added normal hexane in the residuum, produced precipitation and also filtered, and used the normal hexane washing precipitation, and recrystallization in methyl alcohol-toluene mixed solvent gets dinitro compound.
Get this dinitro compound (3.91 grams, 9.05 mmole), in 30 milliliters of ethanol and 60 milliliters of concentrated hydrochloric acids, form suspension, drip anhydrous tindichloride (51.20 grams, 270 mmoles) ethanolic soln (60 milliliters), mixture, are poured in 200 milliliters of 25% cold sodium hydroxide solutions after 18 hours at 30 ℃ of following stirring reactions, add 100 milliliters of toluene, acutely rock reaction mixture, by diatomite filtration, be separated then, water layer extracts with toluene, organic layer salt water washing, dried over sodium sulfate boils off solvent under the decompression, ethyl alcohol recrystallization gets diamino compounds.
Get this diamino compounds 0.1-0.2 mmole, 1.4 times 2,3-dihydroxyl-1,4-dioxan (the product alkyl is a hydrogen), or 1.2-2.0 doubly 1, (dimethyl diketone, product alkyl are methyl to the 2-diketone; 7,8-tetradecyl diketone, product alkyl are hexyl), mix, in 60 ℃ of following 5-10 ml methanol solution, stirred 2 hours, boil off solvent under the decompression, crude product adopts column chromatography and recrystallization to purify.Bromination separate to be purified, target product 5 ', 5 " two bromo-2,3-dialkyl group-5,7-(2 ', 2 ")-two selenophen base thieno-pyrazines.
Embodiment 32:5 ', 5 " two bromo-2,3-dialkyl group-5,7-(2 ', the preparation of 2 ")-dithienyl selenophens and pyrazine, its molecular structure is as shown in table 3.
Method is with embodiment 31.Take by weighing 2,5-two bromo-3,4-dinitrobenzene selenophen (5.72 grams, 15.1 mmoles), tributyl 2-thienyl tin (13.47 grams, 36.1 mmoles) is dissolved in 100 milliliters of tetrahydrofuran (THF)s, adds PdCl
2(PPh
3)
2(108 milligrams, 1mol%).Mixture refluxed 16 hours, cooled off, and under reduced pressure concentrated, and added normal hexane in the residuum, produced precipitation and also filtered, and used the normal hexane washing precipitation, and recrystallization in methyl alcohol-toluene mixed solvent gets dinitro compound.
Get this dinitro compound (3.49 grams, 9.05 mmole), in 30 milliliters of ethanol and 60 milliliters of concentrated hydrochloric acids, form suspension, drip anhydrous tindichloride (51.20 grams, 270 mmoles) ethanolic soln (60 milliliters), mixture, are poured in 200 milliliters of 25% cold sodium hydroxide solutions after 18 hours at 30 ℃ of following stirring reactions, add 100 milliliters of toluene, acutely rock reaction mixture, by diatomite filtration, be separated then, water layer extracts with toluene, organic layer salt water washing, dried over sodium sulfate boils off solvent under the decompression, ethyl alcohol recrystallization gets diamino compounds.
Get this diamino compounds 0.1-0.2 mmole, 1.4 times 2,3-dihydroxyl-1,4-dioxan (the product alkyl is a hydrogen), or 1.2-2.0 doubly 1, (dimethyl diketone, product alkyl are methyl to the 2-diketone; 7,8-tetradecyl diketone, product alkyl are hexyl), mix, in 60 ℃ of following 5-10 ml methanol solution, stirred 2 hours, boil off solvent under the decompression, crude product adopts column chromatography and recrystallization to purify.Bromination separate to be purified, target product 5 ', 5 " two bromo-2,3-dialkyl group-5,7-(2 ', 2 ")-dithienyl selenophen and pyrazines.
Embodiment 33:5 ', 5 " two bromo-2,3-dialkyl group-5,7-(2 ', the preparation of 2 ")-two selenophen base selenophens and pyrazine, its molecular structure is as shown in table 3.
Method is with embodiment 31.Take by weighing 2,5-two bromo-3,4-dinitrobenzene selenophen (5.72 grams, 15.1 mmoles), tributyl-2-selenophen base tin (15.15 grams, 36.1 mmoles) is dissolved in 100 milliliters of tetrahydrofuran (THF)s, adds PdCl
2(PPh
3)
2(108 milligrams, 1mol%).Mixture refluxed 20 hours, cooled off, and under reduced pressure concentrated, and added normal hexane in the residuum, produced precipitation and also filtered, and used the normal hexane washing precipitation, and recrystallization in methyl alcohol-toluene mixed solvent gets dinitro compound.
Get this dinitro compound (4.34 grams, 9.05 mmole), in 30 milliliters of ethanol and 60 milliliters of concentrated hydrochloric acids, form suspension, drip anhydrous tindichloride (51.20 grams, 270 mmoles) ethanolic soln (60 milliliters), mixture, are poured in 200 milliliters of 25% cold sodium hydroxide solutions after 18 hours at 30 ℃ of following stirring reactions, add 100 milliliters of toluene, acutely rock reaction mixture, by diatomite filtration, be separated then, water layer extracts with toluene, organic layer salt water washing, dried over sodium sulfate boils off solvent under the decompression, ethyl alcohol recrystallization gets diamino compounds.
Get this diamino compounds 0.1-0.2 mmole, 1.4 times 2,3-dihydroxyl-1,4-dioxan (the product alkyl is a hydrogen), or 1.2-2.0 doubly 1, (dimethyl diketone, product alkyl are methyl to the 2-diketone; 7,8-tetradecyl diketone, product alkyl are hexyl), mix, in 60 ℃ of following 5-10 ml methanol solution, stirred 2 hours, boil off solvent under the decompression, crude product adopts column chromatography and recrystallization to purify.Bromination separate to be purified, target product 5 ', 5 " two bromo-2,3-dialkyl group-5,7-(2 ', 2 ")-two selenophen base selenophen and pyrazines.
Embodiment 34:5 ', 5 " two bromo-2,3-dialkyl group-5,7-(2 ', the preparation of 2 ")-two-N-methylpyrrole base selenophen and pyrazine, its molecular structure is as shown in table 3.
Method is with embodiment 31.Take by weighing 2,5-two bromo-3,4-dinitrobenzene selenophen (5.72 grams, 15.1 mmoles), tributyl-2-N-methylpyrrole base tin (13.35 grams, 36.1 mmoles) is dissolved in 100 milliliters of tetrahydrofuran (THF)s, adds PdCl
2(PPh
3)
2(108 milligrams, 1mol%).Mixture refluxed 18 hours, cooled off, and under reduced pressure concentrated, and added normal hexane in the residuum, produced precipitation and also filtered, and used the normal hexane washing precipitation, and recrystallization in methyl alcohol-toluene mixed solvent gets dinitro compound.
Get this dinitro compound (3.43 grams, 9.05 mmole), in 30 milliliters of ethanol and 60 milliliters of concentrated hydrochloric acids, form suspension, drip anhydrous tindichloride (51.20 grams, 270 mmoles) ethanolic soln (60 milliliters), mixture, are poured in 200 milliliters of 25% cold sodium hydroxide solutions after 18 hours at 30 ℃ of following stirring reactions, add 100 milliliters of toluene, acutely rock reaction mixture, by diatomite filtration, be separated then, water layer extracts with toluene, organic layer salt water washing, dried over sodium sulfate boils off solvent under the decompression, ethyl alcohol recrystallization gets diamino compounds.
Get this diamino compounds 0.1-0.2 mmole, 1.4 times 2,3-dihydroxyl-1,4-dioxan (the product alkyl is a hydrogen), or 1.2-2.0 doubly 1, (dimethyl diketone, product alkyl are methyl to the 2-diketone; 7,8-tetradecyl diketone, product alkyl are hexyl), mix, in 60 ℃ of following 5-10 ml methanol solution, stirred 2 hours, boil off solvent under the decompression, crude product adopts column chromatography and recrystallization to purify.Bromination separate to be purified, target product 5 ', 5 " two bromo-2,3-dialkyl group-5,7-(2 ', 2 ")-two-N-methylpyrrole base selenophen and pyrazine.
Embodiment 35:4, the preparation of 6-dibromo selenophen and selenium diazole, its molecular structure is as shown in table 3.
Take by weighing 2,5-two bromo-3,4-diamino selenophen (3.19 grams, 10 mmoles), be dissolved in 5 milliliters of ethanolic solns, reflux, drip tin anhydride (1.22 grams of heat, 11 mmoles) aqueous solution, drip and finish, reflux half an hour normal hexane-re-crystallizing in ethyl acetate, get target product 4,6-dibromo selenophen and selenium diazole.
Embodiment 36:4, the preparation of 6-dibromo selenophen and thiadiazoles, its molecular structure is as shown in table 3.
Method is with embodiment 35.Take by weighing 2,5-two bromo-3,4-diamino selenophen (3.19 grams, 10 mmoles) is dissolved in 7 milliliters of pyridines, reflux, drip thionyl aniline (2.78 grams, 20 mmoles), drip and finish, reflux half an hour, normal hexane-re-crystallizing in ethyl acetate gets target product 4,6-dibromo selenophen and thiadiazoles.
Embodiment 37:4, the preparation of 6-dibromo thiophene and selenium diazole, its molecular structure is as shown in table 3.
Method is with embodiment 35.Take by weighing 2,5-two bromo-3,4-diamino thiophene (2.72 grams, 10 mmoles), be dissolved in 6 milliliters of ethanolic solns, reflux, drip tin anhydride (1.22 grams of heat, 11 mmoles) aqueous solution, drip and finish, reflux half an hour normal hexane-re-crystallizing in ethyl acetate, get target product 4,6-dibromo thiophene and selenium diazole.
Embodiment 38:2, the preparation of 5-two bromo-3-alkyl selenophens, its molecular structure is as shown in table 3.
Take by weighing 3-bromine selenophen (2.10 gram, 10 mmoles), magnesium powder (0.26 gram, 11 mmoles) adds 5 milliliters of tetrahydrofuran (THF)s, and nitrogen protection treats that reactive magnesium near fully the time, drips bromoalkane (10 mmole), and column chromatography and recrystallization are purified.Bromination is separated and is purified, and gets 2,5-two bromo-3-alkyl selenophens.
Alkyl has: n-hexyl, and n-octyl, the 2-ethylhexyl, cyclohexyl aligns octyl phenyl, etc.
Embodiment 39:2,5-two bromo-3, the preparation of 4-dialkyl group selenophen, its molecular structure is as shown in table 3.
Method is with embodiment 38.Take by weighing 3-alkyl selenophen, 4 brominations get 3-bromo-4-alkyl selenophen, use Grignard reagent 3 replacements then, get 3,4-dialkyl group selenophen.2,5-position bromination is separated and is purified, and gets target product 2,5-two bromo-3,4-dialkyl group selenophen.
Alkyl has: 3-methyl-4-cyclohexyl, and 3, the 4-dioctyl, etc.
Embodiment 40:5,5 '-two bromo-2,2 '-preparation of Lian selenophen, its molecular structure is as shown in table 3.
Take by weighing 2-bromine selenophen (2.10 grams, 10 mmoles), magnesium (0.26 gram, 11 mmoles) adds 5 milliliters of tetrahydrofuran (THF)s, makes Grignard reagent, drips the tetrahydrofuran solution of 2-bromine selenophen (2.10 grams, 10 mmoles) in reaction mixture, column chromatography.Bromination separate to be purified, target product 5,5 '-two bromo-2,2 '-the Lian selenophen.
Embodiment 41:5,5 '-two bromo-1 '-sulfo--2,2 '-preparation of Lian selenophen, its molecular structure is as shown in table 3.
Method is with embodiment 40.Take by weighing 2-bromothiophene (1.63 grams, 10 mmoles), magnesium (0.26 gram, 11 mmoles) adds 5 milliliters of tetrahydrofuran (THF)s, makes Grignard reagent, drips the tetrahydrofuran solution of 2-bromine selenophen (2.10 grams, 10 mmoles) in reaction mixture, column chromatography.Bromination separate to be purified, target product 5,5 '-two bromo-1 '-sulfo--2,2 '-the Lian selenophen.
Embodiment 42:5 ', 5 " two bromo-2,5-(2 ', the preparation of 2 ")-dithienyl selenophens, its molecular structure is as shown in table 3.
Method is with embodiment 40.Take by weighing 2-bromothiophene (3.59 grams, 22 mmoles), magnesium (0.58 gram, 24 mmoles) adds 10 milliliters of tetrahydrofuran (THF)s, makes Grignard reagent, drips 2 in reaction mixture, the tetrahydrofuran solution of 5-dibromo selenophen (2.10 grams, 10 mmoles), column chromatography.Bromination separate to be purified, target product 5 ', 5 " two bromo-2,5-(2 ', 2 ")-dithienyl selenophens.
Embodiment 43:5 ', 5 " two bromo-2,5-(2 ', the preparation of 2 ")-two selenophen base thiophene, its molecular structure is as shown in table 3.
Method is with embodiment 40.Take by weighing 2-bromine selenophen (4.62 grams, 22 mmoles), magnesium (0.58 gram, 24 mmoles) adds 10 milliliters of tetrahydrofuran (THF)s, makes Grignard reagent, drips 2 in reaction mixture, the tetrahydrofuran solution of 5-dibromo thiophene (1.63 grams, 10 mmoles), column chromatography.Bromination separate to be purified, target product 5 ', 5 " two bromo-2,5-(2 ', 2 ")-two selenophen base thiophene.
Embodiment 44:4,9-two bromo-2,1, the preparation of 3-naphtho-selenium diazole, its molecular structure is as shown in table 3.
2,3-diaminonaphthalene recrystallization in hot water obtains white crystal.Take by weighing 2,3-diaminonaphthalene recrystallized product (0.513 gram, 3.20 mmoles) places 50 milliliters of there-necked flasks, adds 15 milliliters of Glacial acetic acid, and magnetic agitation makes it dissolving.Other gets bromine (1.07 grams, 6.7 mmole) be dissolved in 3 milliliters of Glacial acetic acid, it is splashed in the glacial acetic acid solution of diaminonaphthalene, and vigorous stirring dropwises the back and continues to stir 15 minutes simultaneously, there is this moment the brown precipitation to occur, filter and use successively 15 milliliters of Glacial acetic acid, 80 milliliter of 2% sodium carbonate solution and the washing of 50 ml distilled waters leach the thing color and become pink, put into 40 ℃ of dryings of vacuum drying oven 24 hours, and got crude product two bromo diaminonaphthalenes 0.91 gram.
Get thick product 0.9 gram (2.83 mmole) of two bromo diaminonaphthalenes and be dissolved in 100 milliliters of ethanol, filter and obtain the scarlet settled solution, solution is transferred in 500 ml beakers that have mechanical stirrer.Tin anhydride (0.33 gram, 3.0 mmole) be dissolved in 10 ml distilled waters,, have a large amount of purple precipitations to occur immediately with tin anhydride solution impouring beaker in vigorous stirring, continue to stir 30 minutes after-filtration, recrystallization obtains purple floss 0.61 gram in ethyl acetate.After testing, be target product 4,9-two bromo-2,1,3-naphtho-selenium diazole.
Embodiment 45:4,7-two bromo-2,1, the preparation of 3-diazosulfide, its molecular structure is as shown in table 3.
By " heterocyclization association will " (J.Heterocycl.Chem.) 7 (1970) 629 disclosed methods preparation 4,7-two bromo-2,1,3-diazosulfide.Take by weighing diazosulfide (13.6 grams, 0.1 mole), be dissolved in 20 milliliter of 45% Hydrogen bromide, heated and stirred is to refluxing dripping bromine (48 grams, 0.3 mole).Dropwise, add 10 milliliters of Hydrogen bromides and continue and refluxed 2.5 hours.The reaction mixture filtered while hot, cooling refilters, water washing, drying, the chloroform recrystallization gets 4,7-two bromo-2,1,3-diazosulfide.
Embodiment 46:4,9-two bromo-2,1, the preparation of 3-naphtho-thiadiazoles, its molecular structure is as shown in table 3.
Method is with embodiment 44.2,3-diaminonaphthalene recrystallization in hot water obtains white crystal.Take by weighing 2,3-diaminonaphthalene recrystallized product (0.513 gram, 3.20 mmoles) places 50 milliliters of there-necked flasks, adds 15 milliliters of Glacial acetic acid, and magnetic agitation makes it dissolving.Other gets bromine (1.07 grams, 6.7 mmole) be dissolved in 3 milliliters of Glacial acetic acid, bromine is splashed in the glacial acetic acid solution of diaminonaphthalene, vigorous stirring dropwises the back and continues to stir 15 minutes simultaneously, there is this moment the brown precipitation to occur, filter and use successively 15 milliliters of Glacial acetic acid, 80 milliliter of 2% sodium carbonate solution and the washing of 50 ml distilled waters leach the thing color and become pink, put into 40 ℃ of vacuum-dryings of vacuum drying oven 24 hours, get crude product two bromo diaminonaphthalenes 0.91 gram.
Get thick product 0.9 gram (2.83 mmole) of two bromo diaminonaphthalenes, thionyl aniline (0.79 gram, 5.66 mmoles), trimethylchlorosilane (587 milligrams, 5.4 mmoles) is dissolved in 15 milliliters of pyridines, 80 ℃ of following stirring reactions 24 hours, add 50 milliliters of tetracol phenixin then, produce solid precipitation, filter and collecting precipitation, purify 4,9-two bromo-2,1,3-naphtho-thiadiazoles.
Below be polyreaction embodiment:
Embodiment 47: contain the preparation of fluorene copolymer, its molecular structure is as shown in table 4.
Get 9,9-two replaces-2,7-fluorenes hypoboric acid ester 5 mmoles, and dibromo compound 5 mmoles are dissolved in 30 milliliters of toluene, add 5 milliliters of phase-transfer catalyst ALIQUAT 336, triphenyl phosphorus palladium 70-80 milligram, 10 milliliters of 2M aqueous sodium carbonates under nitrogen protection.Mixture heating up is to refluxing, and stirring reaction 48 hours adds 1 milliliter of bromobenzene end-blocking then, continues reaction 3 hours.Reaction mixture cooling under agitation slowly in 1 liter of methanol solution of impouring, is filtered the fibrous polymer that collecting precipitation goes out.With the washing of 300 ml methanol, drying is dissolved in 150 milliliters of toluene then, adopts silica gel column chromatography, makes eluent with toluene and purifies.Concentrate eluant under agitation slowly in 1 liter of methanol solution of impouring, filters out precipitation, pours in 500 milliliters of acetone, stirs 5 hours, filters, and is dry under the vacuum, multipolymer.The ratio of components of partial polymer, the ultraviolet absorption peak of film, the photoluminescence spectra peak, the electroluminescent spectrum peak, photoluminescence efficiency, electroluminescent efficiency etc. are listed in table 4.
Embodiment 48: contain the preparation of carbazole multipolymer, its molecular structure is as shown in table 4.
Method is with embodiment 47.Replace-3 with N-, 6-carbazole hypoboric acid ester replaces 9, and 9-two replaces-2,7-fluorenes hypoboric acid ester.
Embodiment 49: contain the preparation (preparation of selenole and selenophen derivative homopolymer) of selenium heterocycle conjugation homopolymer, its molecular structure is as shown in table 4.
Reaction flask takes by weighing dibromo alkyl substituted benzene and selenium diazole (or the dibromo alkyl replaces selenophen) 5 mmoles, catalyst n i (COD) with the flushing of dry argon gas stream several times
2Connect pyridine complex 0.08 mmole, add refining exsiccant N, 8 milliliters of the mixed solvents of dinethylformamide and toluene were warming up to 90 ℃ of stirring reactions 48 hours, added 10 milliliters of toluene midway in batches at every turn.Reaction mixture is poured in 200 milliliters of chloroformic solutions, filters, and boils off solvent under the decompression, adopts toluene to make the eluent column chromatography, removes and desolvates, and washing with acetone is collected vacuum-drying.
Following example is to the element manufacturing of luminescent material made proposed by the invention and the explanation of characteristic.But the present invention will be not limited to listed example
Embodiment 50: the preparation of polymer electroluminescent device
Ito glass is handled with oxygen-Plasma through after the ultrasonic cleaning, and the square resistance of ito glass is 10 Ω/.The hole injection layer polymkeric substance is PEDT or PVK, and luminescent layer adopts above institute synthetic polymer.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.
ITO noted earlier refers to indium tin oxide-coated glass; PEDT refers to polyethylene dioxy base thiophene; PVK refers to Polyvinyl carbazole.
Subordinate list:
Table 1 table 1
Table 2 table 2
Table 3
Table 4
Claims (5)
1, a kind of polymkeric substance that contains selenium heterocyclic compound, the light emitting region that it is characterized in that described polymkeric substance is in the 400-1100 nanometer, be dissolved in organic solvent, be included in the heterocycle component that contains elemental selenium that accounts for the 0.1-99.9% mole in the polymkeric substance, the described heterocycle component that contains elemental selenium has following structural unit:
R wherein
1, R
2Be H, C
1-C
20Alkyl, alkoxyl group;
This polymkeric substance comprises that also another structural unit gathers fluorenes, and its molecular structure is as follows:
2, the application of the described polymkeric substance of claim 1 in the preparation luminescent material.
3, the application of the described polymkeric substance of claim 1 in the preparation photovoltaic material.
4, the application in the luminescent layer of the described polymkeric substance of claim 1 in preparation photodiode, flat-panel monitor.
5, the application of the described polymkeric substance of claim 1 in the active coating of preparation solar cell.
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| CN 201010244975 Division CN101885836B (en) | 2002-06-20 | 2002-06-20 | Polymer of selenium-contained heterocyclic compound and application thereof in preparation of luminescent material |
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| CN100341906C (en) * | 2004-11-25 | 2007-10-10 | 中国科学院化学研究所 | Polyethylene acetylene, its production and use thereof |
| EP1856178A1 (en) * | 2005-03-11 | 2007-11-21 | Merck Patent GmbH | Monomers, oligomers and polymers comprising thiophene and selenophene |
| CN101429210B (en) * | 2008-11-05 | 2011-06-15 | 江苏工业学院 | Synthesis of esterifiable fluorene diborate |
| JP5976675B2 (en) | 2011-01-05 | 2016-08-24 | 日東電工株式会社 | Wavelength-converting perylene diester chromophore and luminescent film |
| US8940411B2 (en) * | 2011-04-25 | 2015-01-27 | General Electric Company | Materials for optoelectronic devices |
| CN102285944B (en) * | 2011-06-13 | 2014-12-03 | 暨南大学 | Benzoselenadiazole derivatives with antitumor and antioxidation activities, and preparation and application thereof |
| JP2014185192A (en) * | 2011-08-03 | 2014-10-02 | Lg Chem Ltd | Copolymer, organic solar cell using the same and manufacturing method thereof |
| KR101844880B1 (en) * | 2011-09-26 | 2018-04-03 | 닛토덴코 가부시키가이샤 | Highly-fluorescent and photo-stable chromophores for enhanced solar harvesting efficiency |
| WO2013052381A2 (en) | 2011-10-05 | 2013-04-11 | Nitto Denko Corporation | Wavelength conversion film having pressure sensitive adhesive layer to enhance solar harvesting efficiency |
| EP2788450B1 (en) | 2011-12-06 | 2017-06-21 | Nitto Denko Corporation | Wavelength conversion material as encapsulant for solar module systems to enhance solar harvesting efficiency |
| JP5881402B2 (en) * | 2011-12-14 | 2016-03-09 | 株式会社日本触媒 | Benzobisthiadiazole compounds |
| EP2941474B1 (en) * | 2013-01-04 | 2018-02-28 | Nitto Denko Corporation | Highly-fluorescent and photo-stable chromophores for wavelength conversion |
| CN104072735B (en) * | 2013-03-29 | 2016-05-18 | 海洋王照明科技股份有限公司 | Selenophen-benzo two (selenole) copolymer material and its preparation method and application |
| CN104072731B (en) * | 2013-03-29 | 2016-02-10 | 海洋王照明科技股份有限公司 | Containing the multipolymer and its preparation method and application of thiophene-benzo two (selenole) |
| CN104744676B (en) * | 2015-03-30 | 2017-04-05 | 华南理工大学 | Conjugated polymer containing 7H-pyrrolo- [3,4-g]-6,8-diketone of quinoxaline and application |
| CN106905513A (en) * | 2017-02-28 | 2017-06-30 | 华南理工大学 | Based on two heteroaromatics and 3,7 S, the conjugated polymer of S dioxydibenze bithiophene units and preparation method and application |
| KR102005860B1 (en) * | 2018-01-31 | 2019-07-31 | 광운대학교 산학협력단 | conjugated copolymer using selenazole monomer and manufacturing method thereof |
| CN110655638A (en) * | 2018-06-29 | 2020-01-07 | 华南理工大学 | Polymers based on benzoselenadiazole derivative unit and preparation method and application thereof |
| CN115611827A (en) * | 2021-07-15 | 2023-01-17 | 中国科学院化学研究所 | Fluorescent sensing material, preparation method thereof and application thereof in organic arsenic detection |
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| DE4436773A1 (en) * | 1994-10-14 | 1996-04-18 | Hoechst Ag | Conjugated polymers with spirocenters and their use as electroluminescent materials |
| SG100772A1 (en) * | 2000-12-06 | 2003-12-26 | Sumitomo Chemical Co | Polymeric fluorescent substance and polymer light-emiting device using the same |
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