CN1663971A - Conjugated polymer of silicon-containing heterocyclic pentylene and its use - Google Patents
Conjugated polymer of silicon-containing heterocyclic pentylene and its use Download PDFInfo
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- CN1663971A CN1663971A CN2005100331005A CN200510033100A CN1663971A CN 1663971 A CN1663971 A CN 1663971A CN 2005100331005 A CN2005100331005 A CN 2005100331005A CN 200510033100 A CN200510033100 A CN 200510033100A CN 1663971 A CN1663971 A CN 1663971A
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Abstract
The invention discloses a conjugated polymer of silicon-containing heterocyclic pentylene and its use in preparing light-emitting diode, panel display, solar energy photovoltaic cells and organic field-effect-transistors, wherein the polymers include a silicon heterocycte cyclopentadiene compound, and a compound selected from fluorenes, carbazoles and diazosulfide.
Description
Technical field
The present invention relates to a kind of polymkeric substance, more specifically relate to a kind of conjugated polymers of siliceous heterocyclic pentylene.
The invention still further relates to the application of this polymkeric substance in preparation photodiode, flat-panel monitor, solar-energy photo-voltaic cell, organic field effect tube.
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.
Conjugate polymer material is because outstanding advantage has started a revolution of photoelectron technology.In in the past 10 years, developed the conjugated polymers 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 polymer LED always, photovoltaic cell, and the method for field effect transistor performance, 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, and the polymkeric substance that the visible-range absorption bands is wide, carrier mobility is high.
Summary of the invention
The objective of the invention is to shortcoming at the prior art existence, a kind of conjugated polymers of siliceous heterocyclic pentylene is provided, this conjugated polymers has high-quantum efficiency, high color purity, permanent stability are good, try out in high resolving power, panchromatic flat pannel display, solar-energy photo-voltaic cell and organic field effect tube.
Another object of the present invention is in the active coating with the active coating of the luminescent layer of this polymer application in preparation luminescent material, photovoltaic material, photodiode, flat-panel monitor, solar-energy photo-voltaic cell and preparation organic field effect tube.
To achieve the above object of the invention, the present invention has taked following technical scheme:
The conjugated polymers of siliceous heterocyclic pentylene of the present invention has structure as follows:
R wherein
1Be C
1～C
18Alkyl, Ar1 and Ar2 are aromatic ring, and m, n, y are natural number.Ar1 has following a kind of structural unit:
R wherein
2Be C
1～C
18Alkyl, and Ar2 has following a kind of structural unit:
The conjugated polymers of siliceous heterocyclic pentylene is dissolvable in water general organic solvent, and as chloroform, toluene, tetrahydrofuran (THF) etc., its light emitting region is in 400～1100 nanometers.
The conjugated polymers of described siliceous heterocyclic pentylene can be applicable to prepare in the luminescent material.
The conjugated polymers of described siliceous heterocyclic pentylene can be applicable to prepare in the photovoltaic material.
The conjugated polymers of described siliceous heterocyclic pentylene can be applicable to prepare the luminescent layer in photodiode, the flat-panel monitor.
The conjugated polymers of described siliceous heterocyclic pentylene can be applicable to prepare in the active coating of solar-energy photo-voltaic cell.
The conjugated polymers of described siliceous heterocyclic pentylene can be applicable to prepare in the active coating of organic field effect tube.
The present invention is a kind of monomer with the derivative of siliceous heterocyclic pentylene, and the derivative of fluorenes, carbazole, diazosulfide is another kind of monomer, has synthesized a series of new multipolymers.Adopting this analog copolymer is luminescent layer, has made the photodiode of greater efficiency.Adopting this analog copolymer is the active coating component of solar-energy photo-voltaic cell, has made the photovoltaic cell of high-energy conversion efficiency.Adopting this analog copolymer is the active coating of organic field effect tube, has made the field-effect transistor that also can export saturation currnet under the high gate voltage, shows that novel material has higher mobility.Why novel material among the present invention can have good behaviour in multiple photoelectric device, reason just is to have had the new electronics energy gap of being made up of these two kinds of monomers by the novel material that the derivative of sila cyclopentadiene and fluorenes, carbazole, the derivative of diazosulfide are formed.
The present invention compared with prior art, the emission wavelength of novel material is regulated easily, the electroluminescent efficiency external quantum efficiency reaches 2%, has the potential using value, is expected to develop novel panchromatic demonstration with red, green, blue three-colour light-emitting material; The effciency of energy transfer of solar photovoltaic device reaches 2%, has the potential using value; The organic field effect tube device can obtain saturated drain current output under wide grid voltage, have the potential using value.
Description of drawings
Fig. 1 is the chemical structure synoptic diagram of the conjugated polymers of siliceous heterocyclic pentylene of the present invention;
Fig. 2 is the related transistorized output performance synoptic diagram of embodiment 43.
Embodiment
Come the monomer of the conjugated polymers of siliceous heterocyclic pentylene and the preparation of multipolymer thereof are further described below in conjunction with specific embodiment.But protection domain of the presently claimed invention is not limited to the related scope of embodiment.
Embodiment 1:
2, the preparation of 7-dibromo fluorenes
By world patent WO 99 05184 disclosed methods 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%).Warp
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.Warp
13C NMR 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
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%.Warp
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-n-hexyl 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-bromine normal hexanes (4.16 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%.Warp
1HNMR and GC-MASS test shows are target product 3,6-two bromo-N-n-hexyl 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:
2, the preparation of 7-dibromo carbazole
By " materials chemistry " (Chem.Mater.) 16 (2004) 4736 disclosed methods preparation 2,7-dibromo carbazole.The mixture of strong phosphoric acid that will contain (0.7 gram, 2.1 mmoles) and 15 milliliters backflow 24 hours under 190 degree.Product after filtration with the washing after, be dissolved in the toluene.This toluene solution is further purified with column chromatography, and the product behind the removal toluene through the mixed solution recrystallization of toluene and normal hexane, gets white solid again.Warp
13C NMR, GC-MASS and ultimate analysis show that gained is a target product 2,7-dibromo carbazole.
Embodiment 6:
2, the preparation of 7-two bromo-N-substituted carbazoles, its molecular structure is as shown in table 1.
To prepare 2,7-two bromo-N-n-hexyl carbazoles are that example is illustrated.By " materials chemistry " (Chem.Mater.) 16 (2004) 4736 disclosed methods preparation 2,7-two bromo-N-n-hexyl carbazoles.1.8 restrain 2,7-dibromo carbazole (5.5 mmole) is dissolved in 25 milliliters of acetone, adds phase-transfer catalyst [(C
4H
9)
4N] HSO
4(0.1 gram, 0.3 mmole), 1-bromine normal hexane (1.53 grams, 9.3 mmoles), KOH powder (0.5 gram, 8.9 mmoles) afterreaction refluxed 4 hours.After reaction product is removed acetone, add ether dissolution, filter out throw out, diethyl ether solution washes with water, again through dried over sodium sulfate.Product is further purified with column chromatography, obtains white solid.Warp
13C NMR, GC-MASS and ultimate analysis show that gained is a target product 2,7-two bromo-N-n-hexyl carbazoles.
2, substituting group comprises in the 7-two bromo-N-substituted carbazoles: n-hexyl, and n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 7:
4,7-two (5 '-bromo-2 '-thiophene phenyl)-2,1, the preparation of 3-diazosulfide, its molecular structure is as shown in table 1.
By " materials chemistry magazine " (J.Chem.Mater.) 12 (2002) 2887 disclosed methods preparation 4,7-two (5 '-bromine 2 '-thiophene phenyl)-2,1, the 3-diazosulfide.Under nitrogen protection, with 4,7-two (2 '-the thiophene base)-2,1; 3-diazosulfide (2 grams, 6.7 mmoles) is dissolved in the mixed solvent of chloroform (52 milliliters) and acetate (52 milliliters), adds NBS (2.5 grams then; 14.01 mmole), stopped reaction is spent the night in stirring under the room temperature.Filter, obtain the scarlet precipitation, use dimethyl formamide (DMF) recrystallization again, obtain red crystals.Warp
13C NMR, GC-MASS and ultimate analysis show that gained is a target product 4,7-two (5 '-bromo-2 '-thiophene phenyl)-2,1, the 3-diazosulfide.
Embodiment 8:
9,9-two replaces-2, the preparation of 7-hypoboric acid ester fluorenes, and its molecular structure is as shown in table 2.
Preparing 9,9-di-n-octyl-2,7-two (4,4,5,5-tetramethyl--1,3,2-second dioxy boric 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.Warp
13C NMR, GC-MASS and ultimate analysis show that gained is a target product 9,9-di-n-octyl-2,7-two (4,4,5,5-tetramethyl--1,3,2-second dioxy boric 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 9:
N-replaces-3, the preparation of 6-hypoboric acid ester carbazole, and its molecular structure is as shown in table 2.
To prepare 3, (4,4,5,5-tetramethyl--1,3,2-second dioxy boric acid ester)-N-n-hexyl carbazole is that example is illustrated to 6-two.Add 3 in there-necked flask, 6-two bromo-N-2-n-hexyl carbazoles (4.21 grams, 10.30 mmoles) and 80 milliliters of tetrahydrofuran (THF)s after stirring, are cooled to reaction solution-78 ℃, drip 14.5 milliliters of 2M n-Butyl Lithiums (29 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 50%.Warp
1HNMR,
13C NMR and GC-MASS test shows are target product 3,6-two (4,4,5,5-tetramethyl--1,3,2-dioxy boric acid ester)-N-n-hexyl 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.
Embodiment 10:
N-replaces-2, the preparation of 7-hypoboric acid ester carbazole, and its molecular structure is as shown in table 2.
To prepare 2, (4,4,5,5-tetramethyl--1,3,2-second dioxy boric acid ester)-N-n-hexyl carbazole is that example is illustrated to 7-two.Add 2 in there-necked flask, 7-two bromo-N-2-n-hexyl carbazoles (4.21 grams, 10.30 mmoles) and 80 milliliters of tetrahydrofuran (THF)s after stirring, are cooled to reaction solution-78 ℃, drip 14.5 milliliters of 2M n-Butyl Lithiums (29 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.Warp
1HNMR,
13C NMR and GC-MASS test shows are target product 2,7-two (4,4,5,5-tetramethyl--1,3,2-dioxy boric acid ester)-N-n-hexyl carbazole.
N-replaces-2, and substituting group comprises in the 7-hypoboric acid ester carbazole: n-hexyl, and n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 11:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two lithium sila cyclopentadiene
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two lithium sila cyclopentadiene are that example is illustrated.By " JACS " (J.Am.Chem.Soc.) 116 (1994) 11715 disclosed methods preparation 1,1-dimethyl-3,4-phenylbenzene-2,5-two lithium sila cyclopentadiene.Under inert atmosphere, metallic lithium (0.14 gram, 20 mmoles) be dissolved in naphthalene (3.33 grams, 26 mmoles) in the 12 milli tetrahydrofuran (THF)s and carry out reaction 3 hours under the room temperature, generate naphthalene lithium (LiNaph).After dimethyl tolane base silicon (1.3 gram, 5 mmoles) is dissolved in 5 milliliters of tetrahydrofuran (THF)s it is added drop-wise in the naphthalene lithium solution that has prepared, reaction is half an hour approximately, promptly generates 1,1-dimethyl-3,4-phenylbenzene-2,5-two lithium sila cyclopentadiene.This product solution needn't be purified through separating, and can directly apply to subsequent reactions.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in the 5-two lithium sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 12:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-hypoboric acid ester sila cyclopentadiene, its molecular structure is as shown in table 2.
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (4 ', 4 ', 5 ', 5 '-tetramethyl--1 ', 3 ', 2 '-the dioxy boric acid ester) the sila cyclopentadiene is that example is illustrated.Prepare 1 of 3 mmole amounts by the process among the embodiment 11,1-dimethyl-3,4-phenylbenzene-2,5-two lithium sila cyclopentadiene solution stir the 2-of property adding next time isopropoxy-4,4 at-78 ℃, 5,5-tetramethyl--1,3, (7.5 milliliters of 2-ethylenedioxy boric acid esters, 37 mmoles), 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 the back of desolvating and use recrystallizing methanol, remove most of naphthalene.Thick product gets white crystal with purifying for eluent carries out column chromatography with sherwood oil and methylene dichloride mixed solvent (3: 2).Warp
1HNMR and GC-MASS test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (4 ', 4 ', 5 ', 5 '-tetramethyl--1 ', 3 ', 2 '-the dioxy boric acid ester) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2,5-two (4 ', 4 ', 5 ', 5 '-tetramethyl--1 ', 3 ', 2 '-the dioxy boric acid ester) alkyl in the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl etc., but be not limited only to this.
Embodiment 13:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two zinc sila cyclopentadiene
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two zinc sila cyclopentadiene are that example is illustrated.By " European The Chemicals " (Chem.Eur.J.) 6 (2000) 1683 disclosed methods preparation 1,1-dimethyl-3,4-phenylbenzene-2,5-two zinc sila cyclopentadiene.Prepare 1 of 3 mmole amounts by the process among the embodiment 11,1-dimethyl-3,4-phenylbenzene-2,5-two lithium sila cyclopentadiene solution, this solution is cooled to 0 degree after, add zinc dichloride-N, N, N, N-tetramethyl-Edamine title complex (ZnCl
2-TMEDA) ((3 grams, 12 mmoles) add 20 milliliters of tetrahydrofuran (THF)s afterwards, obtain black suspension, are warming up under the room temperature again and stir 1 hour, obtain 1,1-dimethyl-3,4-phenylbenzene-2,5-two zinc sila cyclopentadiene.This product solution needn't be purified through separating, and can directly apply to subsequent reactions.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in the 5-two zinc sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 14:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two (2 '-thiophene phenyl) sila cyclopentadiene
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-thiophene phenyl) sila cyclopentadiene is that example is illustrated.By " European The Chemicals " (Chem.Eur.J.) 6 (2000) 1683 disclosed methods preparation 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-thiophene phenyl) the sila cyclopentadiene.Prepare 1 of 3 mmole amounts by the process among the embodiment 13,1-dimethyl-3,4-phenylbenzene-2,5-two zinc sila cyclopentadiene solution add PdCl continuously under the room temperature
2(PPh
3)
2(70 milligrams, 0.1 mmole) and 2-bromine thiophene phenol (1.27 the gram, 7.8 mmole), reaction is 24 hours under 30 degree, adds the aqueous hydrochloric acid of 100 milliliters of 1N, extracts with 100 milliliters of ether, after the diethyl ether solution that separation obtains washes with water, through dried over mgso, the thick product of removing after dissolving is purified for the eluent column chromatography with sherwood oil and tetracol phenixin mixed solvent (3: 1), obtains the yellow-green colour solid.Warp
1HNMR,
13CNMR, GC-MASS and ultimate analysis test shows are target product 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-thiophene phenyl) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in 5-two (2 '-thiophene phenyl) the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 15:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two (2 '-furyl) sila cyclopentadiene
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-furyl) sila cyclopentadiene is that example is illustrated.Method only needs to replace 2-bromine thiophene phenol with 2-bromine furans (1.15 grams, 7.8 mmoles) with embodiment 14, and product is the yellow-green colour solid.Warp
1HNMR,
13CNMR, GC-MASS and ultimate analysis test shows are target product 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-furyl) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in 5-two (2 '-furyl) the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 16:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two (2 '-thiazolyl) sila cyclopentadiene
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-thiazolyl) sila cyclopentadiene is that example is illustrated.Method only needs to replace 2-bromine thiophene phenol with 2-bromo thiazole (1.28 grams, 7.8 mmoles) with embodiment 14, and product is the yellow-green colour solid.Warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (2 '-thiazolyl) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in 5-two (2 '-thiazolyl) the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 17:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two (2 '-thiadiazolyl group) sila cyclopentadiene
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-thiadiazolyl group) sila cyclopentadiene is that example is illustrated.Method is with embodiment 14.Only need to replace 2-bromine thiophene phenol with 2-bromo thiazole (1.29 grams, 7.8 mmoles), product is the yellow-green colour solid.Warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (2 '-thiadiazolyl group) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in 5-two (2 '-thiadiazolyl group) the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 18:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two (4 '-bromophenyl) sila cyclopentadiene, its molecular structure is as shown in table 3.
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (4 '-bromophenyl) sila cyclopentadiene is that example is illustrated.Method is with embodiment 14.Only need to replace 2-bromine thiophene phenol with 4-bromo-iodobenzene (1.7 grams, 6 mmoles), product is the yellow-green colour solid.Warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (4 '-bromophenyl) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in 5-two (4 '-bromophenyl) the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 19:
1,1-dialkyl group-3,4-phenylbenzene-2,5-two (4 " bromo-4 '-xenyl) preparation of sila cyclopentadiene, its molecular structure is as shown in table 3.
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (4 " bromo-4 '-xenyl) the sila cyclopentadiene is that example is illustrated.Method is with embodiment 14.Only need with 4 '-bromine 4-iodine biphenyl (2.15 grams, 6 mmoles) replacement 2-bromine thiophene phenol, product is the yellow-green colour solid.Warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (4 " bromo-4 '-biphenyl) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2,5-two (4 " bromo-4 '-biphenyl) alkyl in the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 20:
1,1-dialkyl group-3,4-phenylbenzene-2,5-two (2 '-5 ', 2 " the Lian thiophene phenyl) preparation of sila cyclopentadiene
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-5 ', 2 " the Lian thiophene phenyl) the sila cyclopentadiene is that example is illustrated.Method is with embodiment 14.Only need with 5-bromo-2,2 '-Lian thiophene phenol (1.91 grams, 7.8 mmoles) replaces 2-bromine thiophene phenol.Gained solid sample warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (2 '-5 ', 2 " the Lian thiophene phenyl) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2,5-two (2 '-5 ', 2 " the Lian thiophene phenyl) alkyl in the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 21:
1,1-dialkyl group-3,4-phenylbenzene-2,5-two (2 '-5 ', 2 " the Lian furyl) preparation of sila cyclopentadiene
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-5 ', 2 " the Lian furyl) the sila cyclopentadiene is that example is illustrated.Method is with embodiment 14.Only need with 5-bromo-2,2 '-Lian furans (1.66 grams, 7.8 mmoles) replaces 2-bromine thiophene phenol.Gained solid sample warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (2 '-5 ', 2 " the Lian furyl) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2,5-two (2 '-5 ', 2 " the Lian furyl) alkyl in the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 22:
1,1-dialkyl group-3,4-phenylbenzene-2,5-two (2 '-5 ', 2 " the Lian thiazolyl) preparation of sila cyclopentadiene
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-5 ', 2 " the Lian thiazolyl) the sila cyclopentadiene is that example is illustrated.Method is with embodiment 14.Only need with 5-bromo-2,2 '-Lian thiazole (1.93 grams, 7.8 mmoles) replaces 2-bromine thiophene phenol.Gained solid sample warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (2 '-5 ', 2 " the Lian thiazolyl) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2,5-two (2 '-5 ', 2 " the Lian thiazolyl) alkyl in the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 23:
1,1-dialkyl group-3,4-phenylbenzene-2,5-two (2 '-5 ', 2 " the Lian thiadiazolyl group) preparation of sila cyclopentadiene
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-5 ', 2 " the Lian thiadiazolyl group) the sila cyclopentadiene is that example is illustrated.Method is with embodiment 14.Only need with 5-bromo-2,2 '-Lian thiadiazoles (1.93 grams, 7.8 mmoles) replaces 2-bromine thiophene phenol.Gained solid sample warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (2 '-5 ', 2 " the Lian thiadiazolyl group) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2,5-two (2 '-5 ', 2 " the Lian thiadiazolyl group) alkyl in the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 24:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two (2 '-5 ', 2 ", 5 ", 2 -three thiophene phenyl) sila cyclopentadiene
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-5 ', 2 ", 5 ", 2 -three thiophene phenyl) sila cyclopentadiene is that example is illustrated.Method is with embodiment 14.Only need with 5-bromo-2,2 ', 5 ', 2 " three thiophene phenol (1.93 grams, 7.8 mmoles) replace 2-bromine thiophene phenol.Gained solid sample warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (2 '-5 ', 2 ", 5 ", 2 -three thiophene phenyl) and the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in 5-two (2 '-5 ', 2 ", 5 ", 2 -three thiophene phenyl) the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 25:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two (2 '-5 ', 2 ", 5 ", 2 -three furyl) sila cyclopentadiene
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-5 ', 2 ", 5 ", 2 -three thiophene phenyl) sila cyclopentadiene is that example is illustrated.Method is with embodiment 14.Only need with 5-bromo-2,2 ', 5 ', 2 " three furans (2.18 grams, 7.8 mmoles) replace 2-bromine thiophene phenol.Gained solid sample warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (2 '-5 ', 2 ", 5 ", 2 -three furyl) and the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in 5-two (2 '-5 ', 2 ", 5 ", 2 -three furyl) the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 26:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two (2 '-5 ', 2 ", 5 ", 2 -three thiadiazolyl group) sila cyclopentadiene
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-5 ', 2 ", 5 ", 2 -three thiadiazolyl group) sila cyclopentadiene is that example is illustrated.Method is with embodiment 14.Only need with 5-bromo-2,2 ', 5 ', 2 " three thiadiazoles (2.6 grams, 7.8 mmoles) replace 2-bromine thiophene phenol.Gained solid sample warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (2 '-5 ', 2 ", 5 ", 2 -three thiadiazolyl group) and the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in 5-two (2 '-5 ', 2 ", 5 ", 2 -three thiadiazolyl group) the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 27:
1,1-dialkyl group-3,4-phenylbenzene-2,5-two (5 '-bromo-2 '-thiophene phenyl) preparation of sila cyclopentadiene, its molecular structure is as shown in table 3.
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (5 '-bromo-2 '-thiophene phenyl) the sila cyclopentadiene is that example is illustrated.783.2 milligrams N-bromosuccinimide (NBS) (4.4 mmole) are dissolved in 20 milliliters the dry DMF, slowly be added drop-wise to by be prepared among the embodiment 14 1,1-dimethyl-3,4-phenylbenzene-2, (853 milligrams of 5-two (2 '-thiophene phenyl) sila cyclopentadiene, 2 mmoles) in 25 milliliters of THF solution, be reflected under the condition of lucifuge.After 15 minutes, solution is poured in the beaker that 100 milliliters of frozen water are housed, with (40 milliliters of dichloromethane extractions, 2 times), become a cadre the thick product of solvent with the mixed solvent (5: 1) of sherwood oil and chloroform for the purification of eluent column chromatography, obtain yellow solid, productive rate 45%.
1HNMR,
13CNMR, GC-MASS and ultimate analysis test shows are target product 1,1-dimethyl-3,4-phenylbenzene-2,5-two (5 '-bromo-2 '-thiophene phenyl) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2,5-two (5 '-bromo-2 '-thiophene phenyl) alkyl in the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 28:
1,1-dialkyl group-3,4-phenylbenzene-2,5-two (5 '-bromo-2 '-furyl) preparation of sila cyclopentadiene, its molecular structure is as shown in table 3.
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (5 '-bromo-2 '-furyl) the sila cyclopentadiene is that example is illustrated.Method is with embodiment 27.Only need with 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-furyl) sila cyclopentadiene (820 milligrams, 2 mmoles) replacement 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-thiophene phenyl) the sila cyclopentadiene, product is the yellow-green colour solid.Warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (5 '-bromo-2 '-furyl) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2,5-two (5 '-bromo-2 '-furyl) alkyl in the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 29:
1,1-dialkyl group-3,4-phenylbenzene-2,5-two (5 '-bromo-2 '-thiazolyl) preparation of sila cyclopentadiene, its molecular structure is as shown in table 3.
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (5 '-bromo-2 '-thiazolyl) the sila cyclopentadiene is that example is illustrated.Method is with embodiment 27.Only need with 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-thiazolyl) sila cyclopentadiene (861 milligrams, 2 mmoles) replacement 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-thiophene phenyl) the sila cyclopentadiene, product is a yellow solid.Warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (5 '-bromo-2 '-thiazolyl) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2,5-two (5 '-bromo-2 '-thiazolyl) alkyl in the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 30:
1,1-dialkyl group-3,4-phenylbenzene-2,5-two (5 '-bromo-2 '-thiadiazolyl group) preparation of sila cyclopentadiene, its molecular structure is as shown in table 3.
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (5 '-bromo-2 '-thiadiazolyl group) the sila cyclopentadiene is that example is illustrated.Method is with embodiment 27.Only need with 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-thiadiazolyl group) sila cyclopentadiene (869 milligrams, 2 mmoles) replacement 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-thiophene phenyl) the sila cyclopentadiene, product is a yellow solid.Warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (5 '-bromo-2 '-thiadiazolyl group) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2,5-two (5 '-bromo-2 '-thiadiazolyl group) alkyl in the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 31:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two (2 '-5 " bromo-5 ', 2 " Lian thiophene phenyl) sila cyclopentadiene, its molecular structure is as shown in table 3.
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-5 " bromo-5 ', 2 " Lian thiophene phenyl) sila cyclopentadiene is that example is illustrated.Method is with embodiment 27.Only need with 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-5 ', 2 " the Lian thiophene phenyl) sila cyclopentadiene (1.18 grams, 2 mmoles) replacement 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-thiophene phenyl) the sila cyclopentadiene.Gained solid sample warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (2 '-5 " bromo-5 ', 2 " and the Lian thiophene phenyl) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in 5-two (2 '-5 " bromo-5 ', 2 " Lian thiophene phenyl) the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 32:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two (2 '-5 " bromo-5 ', 2 " Lian furyl) sila cyclopentadiene, its molecular structure is as shown in table 3.
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-5 " bromo-5 ', 2 " Lian furyl) sila cyclopentadiene is that example is illustrated.Method is with embodiment 27.Only need with 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-5 ', 2 " the Lian furyl) sila cyclopentadiene (1.05 grams, 2 mmoles) replacement 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-thiophene phenyl) the sila cyclopentadiene.Gained solid sample warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (2 '-5 " bromo-5 ', 2 " and the Lian furyl) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in 5-two (2 '-5 " bromo-5 ', 2 " Lian furyl) the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 33:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two (2 '-5 " bromo-5 ', 2 " Lian thiazolyl) sila cyclopentadiene, its molecular structure is as shown in table 3.
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-5 " bromo-5 ', 2 " Lian thiazolyl) sila cyclopentadiene is that example is illustrated.Method is with embodiment 27.Only need with 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-5 ', 2 " the Lian thiazolyl) sila cyclopentadiene (1.19 grams, 2 mmoles) replacement 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-thiophene phenyl) the sila cyclopentadiene.Gained solid sample warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (2 '-5 " bromo-5 ', 2 " and the Lian thiazolyl) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in 5-two (2 '-5 " bromo-5 ', 2 " Lian thiazolyl) the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 34:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two (2 '-5 " bromo-5 ', 2 " Lian thiadiazolyl group) sila cyclopentadiene, its molecular structure is as shown in table 3.
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-5 " bromo-5 ', 2 " Lian thiadiazolyl group) sila cyclopentadiene is that example is illustrated.Method is with embodiment 27.Only need with 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-5 ', 2 " the Lian thiadiazolyl group) sila cyclopentadiene (1.2 grams, 2 mmoles) replacement 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-thiophene phenyl) the sila cyclopentadiene.Gained solid sample warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (2 '-5 " bromo-5 ', 2 " and the Lian thiadiazolyl group) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in 5-two (2 '-5 " bromo-5 ', 2 " Lian thiadiazolyl group) the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 35:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two (2 '-5 -bromo-5 ', 2 ", 5 ", 2 -three thiophene phenyl) sila cyclopentadiene, its molecular structure is as shown in table 3.
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-5 -bromo-5 ', 2 ", 5 ", 2 -three thiophene phenyl) sila cyclopentadiene is that example is illustrated.Method is with embodiment 27.Only need with 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-5 ', 2 ", 5 ", 2 -three thiophene phenyl) and sila cyclopentadiene (1.51 grams, 2 mmoles) replacement 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-thiophene phenyl) the sila cyclopentadiene.Gained solid sample warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (2 '-5 -bromo-5 ', 2 ", 5 " and, 2 -three thiophene phenyl) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in 5-two (2 '-5 -bromo-5 ', 2 ", 5 ", 2 -three thiophene phenyl) the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 36:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two (2 '-5 -bromo-5 ', 2 ", 5 ", 2 -three furyl) sila cyclopentadiene, its molecular structure is as shown in table 3.
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-5 -bromo-5 ', 2 ", 5 ", 2 -three furyl) sila cyclopentadiene is that example is illustrated.Method is with embodiment 27.Only need with 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-5 ', 2 ", 5 ", 2 -three furyl) and sila cyclopentadiene (1.32 grams, 2 mmoles) replacement 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-thiophene phenyl) the sila cyclopentadiene.Gained solid sample warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (2 '-5 -bromo-5 ', 2 ", 5 " and, 2 -three furyl) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in 5-two (2 '-5 " bromo-5 ', 2 ", 5 ", 2 -three furyl) the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Embodiment 37:
1,1-dialkyl group-3,4-phenylbenzene-2, the preparation of 5-two (2 '-5 -bromo-5 ', 2 ", 5 ", 2 -three thiadiazolyl group) sila cyclopentadiene, its molecular structure is as shown in table 3.
Preparing 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-5 -bromo-5 ', 2 ", 5 ", 2 -three thiadiazolyl group) sila cyclopentadiene is that example is illustrated.Method is with embodiment 27.Only need with 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-5 ', 2 ", 5 ", 2 -three thiadiazolyl group) and sila cyclopentadiene (1.53 grams, 2 mmoles) replacement 1,1-dimethyl-3,4-phenylbenzene-2,5-two (2 '-thiophene phenyl) the sila cyclopentadiene.Gained solid sample warp
1HNMR,
13CNMR and ultimate analysis test shows are target product 1,1-dimethyl-3, and 4-phenylbenzene-2,5-two (2 '-5 -bromo-5 ', 2 ", 5 " and, 2 -three thiadiazolyl group) the sila cyclopentadiene.
1,1-dialkyl group-3,4-phenylbenzene-2, the alkyl in 5-two (2 '-5 -bromo-5 ', 2 ", 5 ", 2 -three thiadiazolyl group) the sila cyclopentadiene comprises: methyl, n-hexyl, n-octyl, 2-ethylhexyl etc., but be not limited only to this.
Below be polyreaction embodiment, but the present invention will be not limited to listed example
Embodiment 38:
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 39:
Contain the preparation of carbazole multipolymer, its molecular structure is as shown in table 4.
Method is with embodiment 38.Replace-3 with N-, 6-carbazole hypoboric acid ester replaces 9, and 9-two replaces-2,7-fluorenes hypoboric acid ester.
Embodiment 40:
Contain the preparation of diazosulfide multipolymer, its molecular structure is as shown in table 4.
Reaction flask takes by weighing dibromide monomer 0.5 mmole of diazosulfide, dibromide monomer 4.5 mmoles of sila cyclopentadiene, catalyst n i (COD) with the flushing of dry argon gas stream several times
2Bipyridyl complexes 0.08 mmole adds refining exsiccant N, and 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 embodiment is the explanation to the element manufacturing and the characteristic of luminescent material proposed by the invention, photovoltaic material.But the present invention will be not limited to listed example
Embodiment 41:
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 I0 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, perhaps the Ba/Al metal.Apply positive bias between ITO and metal electrode, the characteristic of test component under about 5 milliamperes of electric current.
ITO noted earlier refers to indium tin oxide-coated glass; PEDT refers to polyethylene dioxy base thiophene; PVK refers to Polyvinyl carbazole.
Embodiment 42:
The preparation of polymer solar cell device and performance
Ito glass is handled with oxygen-Plasma through after the ultrasonic cleaning, and the square resistance of ito glass is 10 Ω/.Spin coating PEDT on ito glass, spin coating is 1: 4 solution by polymer P in the table 4-10 and PCBM ratio again.Steam at last and go up the Ba/Al metal electrode.Under the irradiation of the AMI.5 of every square centimeter of 100 milliwatt simulated solar irradiation, measure its battery behavior.0.65 volt of open circuit voltage, 8.67 milliamperes every square centimeter of short-circuit current, packing factor 35.8%, effciency of energy transfer 2%.
Foregoing PCBM is the abbreviation of English " methanofullerene[6,6]-phenyl C61-butyric acidmethyl ester ".
Following embodiment is the explanation to the element manufacturing and the characteristic of organic field effect tube proposed by the invention.But the present invention will be not limited to listed example
Embodiment 43:
The organic field effect tube preparation of devices
Ito glass is handled with oxygen-Plasma through after the ultrasonic cleaning, and the square resistance of ito glass is 10g/.With ITO is grid, spin coating one deck polypropylene eyeball on ITO, and spin on polymers P-10 makes source electrode and drain electrode thereon again, and material therefor is gold.Transistorized output performance is seen Fig. 2.
Subordinate list:
Table 1
2,7-two bromo-9,9-two substituted fluorenes 3,6-two bromo-N-substituted carbazoles
M-1 R
2＝-CH
2(CH
2)
4CH
3 M-5 R
2＝-CH
2(CH
2)
4CH
3
M-2 R
2＝-CH
2(CH
2)
6CH
3 M-6 R
2＝-CH
2(CH
2)
6CH
3
M-3 R
2＝- M-7 R
2＝-
CH
2CH(CH
2CH
3)CH
2(CH
2)
2CH
3?CH
2CH(CH
2CH
3)CH
2(CH
2)
2CH
3
M-4 R
2＝-CH
2(CH
2)
7CH
3
2,7-two bromo-N-substituted carbazoles 4,7-two (5 '-bromo-2 '-thiophene phenyl)-2,1,3-
Diazosulfide
M-11
M-8 R
2＝-CH
2(CH
2)
4CH
3
M-9 R
2＝-CH
2(CH
2)
6CH
3
M-10?R
2＝-
CH
2CH(CH
2CH
3)CH
2(CH
2)
2CH
3
Table 2
9,9-two replaces-2, and 7-hypoboric acid ester fluorenes N-replaces-3,6-hypoboric acid ester carbazole
M-12 R
2＝-CH
2(CH
2)
4CH
3 M-16 R
2＝-CH
2(CH
2)
4CH
3
M-13 R
2＝-CH
2(CH
2)
6CH
3 M-17 R
2＝-CH
2(CH
2)
6CH
3
M-14 R
2＝- M-18 R
2＝-
CH
2CH(CH
2CH
3)CH
2(CH
2)
2CH
3 CH
2CH(CH
2CH
3)CH
2(CH
2)
2CH
3
M-15 R
2＝-CH
2(CH
2)
8CH
3
N-replaces-2,7-hypoboric acid ester carbazole 1, and 1-dialkyl group-3,4-phenylbenzene-2,5-two
Boric acid ester sila cyclopentadiene
M-19 R
2＝-CH
2(CH
2)
4CH
3 M-22 R
1＝-CH
3
M-20 R
2＝-CH
2(CH
2)
6CH
3 M-23 R
1＝-CH
2(CH
2)
4CH
3
M-21 R
2＝- M-24 R
1＝-CH
2(CH
2)
6CH
3
CH
2CH(CH
2CH
3)CH
2(CH
2)
2CH
3
Table 3
The dibromide monomer of sila cyclopentadiene
M-25 R
1＝-CH
3 M-29 R
1＝-CH
3
M-26 R
1＝-CH
2(CH
2)
4CH
3 M-30 R
1＝-CH
2(CH
2)
4CH
3
M-27 R
1＝-CH
2(CH
2)
6CH
3 M-31 R
1＝-CH
2(CH
2)
6CH
3
M-28 R
1＝- M-32 R
1＝-
CH
2CH(CH
2CH
3)CH
2(CH
2)
2CH
3 CH
2CH(CH
2CH
3)CH
2(CH
2)
2CH
3
M-33 R
1＝-CH
3 M-37 R
1＝-CH
3
M-34 R
1＝-CH
2(CH
2)
4CH
3 M-38 R
1＝-CH
2(CH
2)
4CH
3
M-35 R
1＝-CH
2(CH
2)
6CH
3 M-39 R
1＝-CH
2(CH
2)
6CH
3
M-36 R
1＝- M-40 R
1＝-
CH
2CH(CH
2CH
3)CH
2(CH
2)
2CH
3 CH
2CH(CH
2CH
3)CH
2(CH
2)
2CH
3
M-41?R
1＝-CH
3 M-45?R
1＝-CH
3
M-42?R
1＝-CH
2(CH
2)
4CH
3 M-46?R
1＝-CH
2(CH
2)
4CH
3
M-43?R
1＝-CH
2(CH
2)
6CH
3 M-47?R
1＝-CH
2(CH
2)
6CH
3
M-44?R
1＝- M-48?R
1＝-
CH
2CH(CH
2CH
3)CH
2(CH
2)
2CH
3 CH
2CH(CH
2CH
3)CH
2(CH
2)
2CH
3
M-49?R
1＝-CH
3 M-53?R
1＝-CH
3
M-50?R
1＝-CH
2(CH
2)
4CH
3 M-54?R
1＝-CH
2(CH
2)
4CH
3
M-51?R
1＝-CH
2(CH
2)
6CH
3 M-55?R
1＝-CH
2(CH
2)
6CH
3
M-52?R
1＝- M-56?R
1＝-
CH
2CH(CH
2CH
3)CH
2(CH
2)
2CH
3 CH
2CH(CH
2CH
3)CH
2(CH
2)
2CH
3
M-57?R
1＝-CH
3 M-61?R
1＝-CH
3
M-58?R
1＝-CH
2(CH
2)
4CH
3 M-62?R
1＝-CH
2(CH
2)
4CH
3
M-59?R
1＝-CH
2(CH
2)
6CH
3 M-63?R
1＝-CH
2(CH
2)
6CH
3
M-60?R
1＝- M-64?R
1＝-
CH
2CH(CH
2CH
3)CH
2(CH
2)
2CH
3 CH
2CH(CH
2CH
3)CH
2(CH
2)
2CH
3
M-65?R
1＝-CH
3 M-69?R
1＝-CH
3
M-66?R
1＝-CH
2(CH
2)
4CH
3 M-70?R
1＝-CH
2(CH
2)
4CH
3
M-67?R
1＝-CH
2(CH
2)
6CH
3 M-71?R
1＝-CH
2(CH
2)
6CH
3
M-68?R
1＝- M-72?R
1＝-
CH
2CH(CH
2CH
3)CH
2(CH
2)
2CH
3 CH
2CH(CH
2CH
3)CH
2(CH
2)
2CH
3
M-73?R
1＝-CH
3
M-74?R
1＝-CH
2(CH
2)
4CH
3
M-75?R
1＝-CH
2(CH
2)
6CH
3
M-76?R
1＝-
CH
2CH(CH
2CH
3)CH
2(CH
2)
2CH
3
Table 4
The polymkeric substance of fluorenes and carbazole
Polymerization hypoboric acid ester dibromo chemical combination film ultraviolet film PL film EL PL is imitated EL and is imitated
Thing (mole%) thing absorbs peak-to-peak (nm) peak (nm) rate (%) rate (%)
(mole％) (nm)
P-1 M-13 M-25 383 531 528 55 0.76
(100) (100)
P-2 M-13 M-2(40) 385 524 534 77 0.97
(100) M-25
(60)
P-3 M-13 M-2(70) 382 513 528 70 2.13
(100) M-25
(30)
P-4 M-13 M-2(80) 387 501 528 84 1.54
(100) M-25
(20)
P-5 M-13 M-2(90) 386 450,51 528 65 1.13
(100) M-25 3
(10)
P-6 M-13 M-2(98) 385 458,510 556 15.2 0.21
(100) M-33(2)
P-7 M-13 M-2(90) 385 458， 585 24.8 0.39
(100) M-33 549
(10)
P-8 M-13 M-2(80) 385 557 586 20.0 0.28
(100) M-33
(20)
P-9 M-13 M-2(60) 496 562 590 12.1 0.11
(100) M-33
(40)
P-10 M-13 M-33 520 591， 590， 6.4 0.01
(100) (100) 616 633
P-11 M-16 M-5(90) 311 529 535 15.6 0.03
(100) M-25
(10)
P-12 M-16 M-5(80) 311 532 536 18.5 0.09
(100) M-25
(20)
P-13 M-16 M-5(60) 308 535 560 44.0 0.80
(100) M-25
(40)
P-14 M-16 M-5(40) 301 541 565 40.5 0.84
(100) M-25
(60)
P-15 M-16 M-25 298,370 543 570 0.64
(100) (100) 35.5
Claims (10)
1, a kind of conjugated polymers of siliceous heterocyclic pentylene is characterized in that this polymkeric substance has following chemical structural formula:
Wherein, R
1Be C
1～C
18Alkyl, m, n, y are natural number.
2, the conjugated polymers of siliceous heterocyclic pentylene according to claim 1 is characterized in that described Ar1 has a kind of in the following structural unit:
3, the conjugated polymers of siliceous heterocyclic pentylene according to claim 2 is characterized in that R
2Be C
1～C
18Alkyl.
4, the conjugated polymers of siliceous heterocyclic pentylene according to claim 1 is characterized in that described Ar2 has a kind of in the following structural unit:
5, the conjugated polymers of siliceous heterocyclic pentylene according to claim 1, the mol ratio that it is characterized in that sila cyclopentadiene and Ar1 is 1: 99～95: 5.
6, the application of the conjugated polymers of each described siliceous heterocyclic pentylene in the preparation luminescent material in the claim 1～5.
7, the application of the conjugated polymers of each described siliceous heterocyclic pentylene in the preparation photovoltaic material in the claim 1～5.
8, the application in the luminescent layer of the conjugated polymers of each described siliceous heterocyclic pentylene in preparation photodiode, flat-panel monitor in the claim 1～5.
9, the application of the conjugated polymers of each described siliceous heterocyclic pentylene in the active coating of preparation solar-energy photo-voltaic cell in the claim 1～5.
10, the application of the conjugated polymers of each described siliceous heterocyclic pentylene in the active coating of preparation organic field effect tube in the claim 1～5.
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