CN103373990A - Chromophore molecule containing triptycene rigid stereochemical structure, and synthetic method and application thereof - Google Patents
Chromophore molecule containing triptycene rigid stereochemical structure, and synthetic method and application thereof Download PDFInfo
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Abstract
The invention relates to a chromophore molecule containing a triptycene rigid stereochemical structure and a synthetic method thereof, and an application of the chromophore molecule containing the triptycene rigid stereochemical structure in a polymer electrooptical material. According to the chromophore molecule and the synthetic method thereof provided by the invention, the chromophore molecule containing the triptycene rigid stereochemical structure as shown in specification can be obtained by virtue of a cycloaddition reaction of N-phenylmaleimide and anthracene and then by connecting an electron bridge part with a structure like carbon-carbon double bonds or thiophene and an electron acceptor part with a structure like tricyano furan or tricyano pyrroline. The chromophore molecule containing the triptycene rigid stereochemical structure provided by the invention is doped with a polymer (such as amorphous polycarbonate (APC)), and the mixture is subjected to polarization treatment so that a high-performance polymer electrooptical material can be obtained. The chromophore molecule containing the triptycene rigid stereochemical structure provided by the invention is easy to synthesize and separate.
Description
Technical field
The present invention relates to contain chromophore molecule and the synthetic method thereof of triptycene rigidity three-dimensional arrangement, and this contains the application of chromophore molecule in polymer as electro-optical material of triptycene rigidity three-dimensional arrangement.
Background technology
The nonlinear optics of material (NLO) performance refers to material and can under the effect of laser, be created under the optical electric field and shift with respect to atomic charge, thereby frequency-doubled effect occur, electrooptic effect, optical frequency mixing, a series of optical phenomenas such as multiphoton absorption.Electrooptic effect (EO) is exactly a kind of typical second order nonlinear optical effect, is material can be realized self specific refractory power under extra electric field variation.Utilize this character, can realize that intensity by changing extra electric field to the control of the phase place of the light wave that transmits in the material, has namely realized the modulation of electrical signal to optical signal.The device of realizing this function is called as electrooptic modulator.
Under the background of information age today, the electronic information type of transmission can not satisfy the requirement of desired high rate data transmission of information age and processing and the computing of vast capacity information, and the develop rapidly of photonics provides huge potentiality for satisfying this requirement.Compare with the electric transmission mode, photon transfer has many advantages, disturbs etc. such as good parallelism, high frequency, wide bandwidth, high-speed, high-density and anti-electromagnetic wave.In early days the research of nonlinear optical material mainly concentrated on mineral crystal and the semiconductor material, such as Lithium niobium trioxide (LiNbO
3) etc., the outstanding material of this wherein some has been widely used in optoelectronic areas.And compare inorganic materials, the organic polymer electrooptical material has obvious performance advantage and application prospect widely, for example, higher electro-optic coefficient value, faster response speed, higher bandwidth and more outstanding processability.Therefore, over past ten years, scientist all over the world has very widely research in non-linear polymer electrooptical material field, and more high performance electro-optical activity molecule is synthesized in design, and updating of polymer materials become study hotspot.How can on existing Research foundation, the electro-optical activity molecular structures is improved innovation, thereby the non-linear electro-optic response of more efficient lifting material remain one and have challenging problem.Such as document: Burland, D.Optical Nonlinearities In Chemistry:Introduction., Chemical Reviews, 1994,94 (1), 1-2.; Chang, C.C., C.P.Chen, et al.Polymers for electro-optical modulation.Journal of Macromolecular Science-Polymer Reviews C, 2005,45 (2), 125-170.
The performance of polymer as electro-optical material is used electro-optic coefficient r usually
33Characterize, obtain higher electro-optic coefficient value, can by optimizing chromophoric structure, promote the second nonlinear electro-optical activity of molecular scale on the one hand; Can improve on the other hand the efficient of material polarization process, better the electro-optical activity of microcosmic is converted to the electro-optic coefficient value of material macroscopic view.In recent years, aspect creation novel high-performance chromophore molecule, researchist both domestic and external has had many outstanding achievements in research, and this case contriver also has some progress (CN101497785 (organic second order non-linear optical chromophore of group containing dendritic structured tricyano pyrroline receptor and preparation method and use thereof) in this respect; CN101845040A (organic second order non-linear optical chromophore and the preparation method and use thereof with D-π-A structure of dendroid base group modification)).
Triptycene and derivative thereof are the compounds that a class has unique three-dimensional rigid structure, received the very large concern of people in their in the past more than 20 years, and within comprising many fields such as molecule machine, materials chemistry and supramolecular chemistry, be widely used.And in the polymer as electro-optical material field, the research of relevant triptycene also rarely has report.Triptycene not only has unique three-dimensional rigid structure, can hinder the congregation between the chromophore molecule, but also have abundant reaction site, can introduce by reaction the functional group of difference in functionality, or realize chromophoric group articulating on polymer chain.The present invention is exactly on existing basis, laboratory, chromophoric electron donor(ED) part-structure is improved, introduced the rigid structure of triptycene, can effectively hinder the dipolar interaction between the chromophoric group, improve polarization efficiency, thereby promote the electro-optic coefficient of material.
Summary of the invention
One of purpose of the present invention is to provide and is easy to purifying, and can introduce various functional functional groups by reaction the performance of material is carried out an improved class is connected with triptycene rigidity three-dimensional arrangement to the body end chromophore molecule.
Two of purpose of the present invention is to provide a kind of synthetic method of the chromophore molecule that contains triptycene rigidity three-dimensional arrangement of synthesis step simple and effective.
Three of purpose of the present invention is to provide the application of the chromophore molecule that contains triptycene rigidity three-dimensional arrangement in polymer as electro-optical material.
The synthetic method of the chromophore molecule that contains triptycene rigidity three-dimensional arrangement of the present invention be characterized as the cycloaddition reaction of utilizing N-phenylmaleimide and anthracene, connect by reaction again as the electronic bridge part of " carbon-carbon double bond " or " thiophene-based " structure and as the electron acceptor moiety of " tricyano furans " or " tricyano pyrroline " structure, obtain containing the chromophore molecule of triptycene Three-dimensional Rigidity three-dimensional arrangement.The chromophore molecule that contains triptycene rigidity three-dimensional arrangement of the present invention is doped in the polymkeric substance (such as unformed polycarbonate APC), processes through polarization, can obtain the high performance polymer electrooptical material.The chromophore molecule that contains triptycene rigidity three-dimensional arrangement of the present invention is easy to synthesize and separate, contained triptycene rigidity three-dimensional arrangement is conducive to improve the polarization efficiency of resulting polymers electrooptical material and the electro-optic coefficient of material, and the resulting polymers electrooptical material can be used for the core material in the device of the electrooptic modulator in the communication field.
The chromophore molecule that contains triptycene rigidity three-dimensional arrangement of the present invention has following formula:
Wherein:
The structure of electron donor(ED) part is:
B is electronic bridge, common are carbon-carbon double bond or thiophene etc.; Structure is as follows:
A is electron acceptor(EA), and common is tricyano furans structure or tricyano pyrroline class formation:
The synthetic route that contains the chromophore molecule of triptycene rigidity three-dimensional arrangement of the present invention is:
B is electronic bridge, common are carbon-carbon double bond or thiophene etc.; Structure is as follows:
A is electron acceptor(EA), and common structure is tricyano furans structure or tricyano pyrroline class formation, and is as follows:
Synthetic method is:
(1) N-phenylmaleimide and anthracene are dissolved in the dry dichloromethane solvent take the ratio of mol ratio as 1: 1, heated and stirred to reflux temperature carries out cycloaddition reaction (time of general reaction is 24～48 hours); After reaction is finished, steam the part methylene chloride solvent, make the volume of solution be concentrated into 2/5 to 1/5 of the rear gained liquor capacity of reaction, remove by filter filtrate, obtain containing the reacting precursor (compound 1 in the synthetic route) of electron donor(ED) of the chromophore molecule of triptycene Three-dimensional Rigidity three-dimensional arrangement;
The reacting precursor of the electron donor(ED) of the chromophore molecule that (2) step (1) is obtained is dissolved in the dry dichloromethane solvent, (wherein, the volume ratio of better ether and methylene dichloride is 1.5～2.5: 1) slowly to drip reacting precursor molar ratio with the electron donor(ED) of chromophore molecule under the room temperature and be the diethyl ether solution of 2～3 tetrahydrochysene lithium aluminium; Stirring reaction is 6～12 hours under the room temperature, then be taken up in order of priority adding ethyl acetate and water with stopped reaction, remove by filter precipitation, filtrate drying agent (such as anhydrous sodium sulphate) drying, remove by filter siccative, steam the electron donor(ED) part (compound 2 in the synthetic route) desolventize the chromophore molecule that obtains containing triptycene Three-dimensional Rigidity three-dimensional arrangement;
The electron donor(ED) of the chromophore molecule that contains triptycene Three-dimensional Rigidity three-dimensional arrangement that (3) step (2) is obtained is partially soluble in dry N-N ' the dimethoxy methane amide, be that 0～5 ℃ of lower molar ratio that drips with the electron donor(ED) part of the chromophore molecule that contains triptycene Three-dimensional Rigidity three-dimensional arrangement is 1.1～1.5 phosphorus oxychloride and stirs in temperature, dripping the complete rear maintenance temperature of phosphorus oxychloride is 0～5 ℃ of lower reaction 0.5～1 hour, and then be warming up to temperature be 60～70 ℃ the reaction 3～5 hours, stopped reaction, add the acid that generates in the aqueous solution neutralization reaction of sodium bicarbonate, filter and remove filtrate, (stationary phase is 200～300 purpose silica gel to crude product through column chromatography, moving phase is the mixed solution of sherwood oil and acetone, sherwood oil: the volume ratio of acetone is 3: 1) separate, obtain containing the reacting precursor (compound 3 in the synthetic route) of formyl radical;
(4) under the room temperature, the reacting precursor that contains formyl radical that step (3) is obtained and electron acceptor(EA) are tricyano furans or tricyano pyrroline according to mol ratio is that 1: 1.1～1.2 ratio is mixed and is dissolved in the methyl alcohol, be warming up to 60～70 ℃ of stirring reactions and filter removal filtrate after 1～2 hour, (stationary phase is 200～300 purpose silica gel to crude product through column chromatography, moving phase is the mixed solution of sherwood oil and acetone, sherwood oil: the volume ratio of acetone is 3: 1) separate, obtain containing the chromophore molecule that contains triptycene rigidity three-dimensional arrangement (compound 4 in the synthetic route) of carbon-carbon double bond electronic bridge;
Or
The reacting precursor that contains formyl radical that step (3) is obtained and bromo thiophene methyl triphenyl phosphine are that 1: 1～1.1 ratio is mixed in the anhydrous diethyl ether solvent according to mol ratio, and add the sodium hydride of 15～25 times of molar weights of the reacting precursor contain formyl radical, under being 20～50 ℃, temperature stirred 18～50 hours, reaction product is poured in the frozen water, separatory, the extracted with diethyl ether water, merge organic phase, carry out drying (available anhydrous magnesium sulfate carries out drying) with siccative, remove by filter siccative, (stationary phase is 200～300 purpose silica gel to crude product with the column chromatography separation, moving phase is the mixed solution of sherwood oil and acetone, sherwood oil: the volume ratio of acetone is 4: 1), can obtain containing the compound (compound 5 in the synthetic route) of thiophene electronic bridge;
The compound that gained is contained the thiophene electronic bridge is dissolved in dry N-N ' the dimethoxy methane amide, under temperature is 0～5 ℃, drip with the molar ratio that contains the compound of thiophene electronic bridge and be 1.1～1.5 phosphorus oxychloride and stir, dripping the complete rear maintenance temperature of phosphorus oxychloride is 0～5 ℃ of lower reaction 0.5～1 hour, and then be warming up to temperature be 60～70 ℃ the reaction 3～6 hours, cooling after reaction finishes, add the acid that generates in the aqueous solution neutralization reaction of sodium bicarbonate, use extracted with diethyl ether, merge organic phase, carry out drying (available anhydrous magnesium sulfate carries out drying) with siccative, remove by filter siccative, (stationary phase is 200～300 purpose silica gel to crude product with column chromatography, moving phase is the mixed solution of sherwood oil and acetone, sherwood oil: the volume ratio of acetone is 2: 1) separate, obtain containing the reacting precursor (compound 6 in the synthetic route) of thiophene electronic bridge;
Be tricyano furans or tricyano pyrroline according to mol ratio with the reacting precursor that contains the thiophene electronic bridge that obtains and electron acceptor(EA) be that 1: 1.1～1.2 ratio is mixed and is dissolved in the ethanol, be warming up to 60～70 ℃ of stirring reactions and filter removal filtrate after 1～2 hour, (stationary phase is 200～300 purpose silica gel to crude product through column chromatography, moving phase is the mixed solution of sherwood oil and acetone, sherwood oil: the volume ratio of acetone is 3: 1) separate, obtain having the chromophore molecule that contains triptycene rigidity three-dimensional arrangement (compound 7 in the synthetic route) of thiophene electronic bridge.
The chromophore molecule that contains triptycene rigidity three-dimensional arrangement of the present invention can be used for preparing polymer as electro-optical material.
The described chromophore molecule that contains triptycene rigidity three-dimensional arrangement can be used for preparing polymer as electro-optical material, be with the described chromophore molecule that contains triptycene rigidity three-dimensional arrangement and unformed polycarbonate or the polymethylmethacrylate preparation polar polymer that mixes, the core material that the polar polymer that obtains can be used as in the device of electrooptic modulator uses.
Described doping is that to contain the chromophore molecule of triptycene rigidity three-dimensional arrangement and unformed polycarbonate or polymethylmethacrylate be 1: 1～10 to mix according to mass ratio.
The present invention also tests the electro-optic coefficient of the polymer as electro-optical material of the chromophore molecule that contains triptycene rigidity three-dimensional arrangement for preparing.This polymer as electro-optical material can be prepared as the device of electrooptic modulator and is applied to the aspects such as telecommunication, data storing.
Advantage of the present invention can be summarized as:
1. the triptycene structure is introduced in chromophoric D-π-A structure first, and synthesis step is few, productive rate is high, is easy to purifying.
2. designed the chromophoric group that contains multiple electronic bridge and electron acceptor(EA) structure, for thinking has been widened in the improvement of material property.
3. after tested, the chromophore molecule that contains this three-dimensional rigid structure obviously is better than common molecule in the test of material property, and chromophoric group ZFS is when doping reaches 16wt% in unformed polycarbonate (APC), electro-optic coefficient r
33Value can reach 35pm/V.
Description of drawings
Fig. 1. the EI spectrogram of the embodiment of the invention 1 and 2 compound 2.
Fig. 2. the EI spectrogram of the embodiment of the invention 1 and 2 compound 3.
Fig. 3. the MALDI-TOF spectrogram of the compound 5 (ZFS) of the embodiment of the invention 1.
Fig. 4. the compound 5 (ZFS) of the embodiment of the invention 1
1The H-NMR spectrogram.
Embodiment
Embodiment 1.
Electronic bridge B is carbon-carbon double bond, and when electron acceptor(EA) A was dimethyl tricyano furans (TCF), structure and the synthetic route of chromophore molecule were as follows:
Synthetic method is:
1. compound 1 is synthetic
N-phenylmaleimide 3.5g (0.02mol) and anthracene 3.6g (0.02mol) are dissolved in the methylene dichloride of 50mL drying, heated and stirred to 60 ℃ reflux temperature carried out cycloaddition reaction 36 hours, be cooled to room temperature, rotary evaporation is concentrated into surplus solution and is about 15mL, removes by filter filtrate.Product is washed three times with sherwood oil, gets white powder crystal 5 .8g, productive rate about 81%.
2. compound 2 is synthetic
3.5g compound 1 (0.01mol) is dissolved in the methylene dichloride of 50mL drying and at normal temperatures and stirs, slowly drip the diethyl ether solution 100mL that contains 1g tetrahydrochysene lithium aluminium (0.025mol).In stirring at room 8 hours, then successively add 10mL ethyl acetate and 5mL water, and stir 0.5 hour with stopped reaction after dropwising.Remove by filter precipitation, filtrate is washed 3 times with saturated common salt, separatory, and organic phase is spent the night with anhydrous sodium sulfate drying.Remove by filter siccative, rotary evaporation is removed solvent, gets white powder solid 2.4g, productive rate about 75%.
MS (EI) m/z:323 (M
+); See Fig. 1.
3. compound 3 is synthetic
0.65g compound 2 (2mmol) is dissolved in the N-N ' of 10mL drying-dimethyl formamide (DMF), bathes with cryosel and be cooled to 0 ℃; Then slowly drip 0.37g phosphorus oxychloride (2.4mmol), kept 0 ℃ of lower continuation stirring reaction of temperature 1 hour, remove cryosel and bathe, be warming up to 65 ℃ of reactions 4 hours.Add the acid that generates in the aqueous solution neutralization reaction of about 40mL sodium bicarbonate, stirred 0.5 hour, remove by filter filtrate, getting crude product is yellow solid.Crude product separates through column chromatography (stationary phase is 200～300 purpose silica gel, and moving phase is the mixed solution of sherwood oil and acetone, sherwood oil: the volume ratio of acetone is 3: 1), gets 0.43g pure compound 3, productive rate about 61%.
MS (EI) m/z:351 (M
+); See Fig. 2.
4. compound 4 (TCF electron acceptor(EA)) is synthetic
Reference: S.Liu, M.A.Haller, H.Ma, L.R.Dalton, S.H.Jang, A.K.Y.Jen.Focused Microwave-Assisted Synthesis of 2,5-Dihydrofuran Derivatives as Electron Acceptors for Highly Efficient Nonlinear Optical Chromophores, Advanced Materials, 2003,15,603-607.
5. compound 5 (chromophoric group ZFS) is synthetic
0.35g (1mmol) compound 3 is dissolved in the 20mL methyl alcohol with 0.22g (1.1mmol) compound 4 (TCF), is heated to 60 ℃ of stirring reactions 8 hours, remove by filter filtrate, it is colourless that crude product is washed till filtrate with cold methanol.Crude product gets 0.3g purple powder (compound 5), productive rate 54% through column chromatography (stationary phase is 200～300 purpose silica gel, and moving phase is the mixed solution of sherwood oil and acetone, sherwood oil: the volume ratio of acetone is 3: 1) separation and purification.
MS (MALDI-TOF) m/z:533 (M+1)
+, 555 (M+Na
+);
1H NMR (400MHz, CD
3COCD
3), δ: 7.91 (d, 1H ,-CH=CH-), 7.64 (d, 2H,-N-Ar-H), 7.36 (m, 4H ,-Ar-H), 7.14 (t, 2H ,-Ar-H), 7.00 (t, 2H ,-Ar-H), 6.91 (d, 1H ,-CH=CH-), 6.49 (d, 2H,-N-Ar-H), 4.44 (s, 2H, Ar-CH-Ar), 3.62 (t, 2H ,-CH-CH-), 3.09 (m, 4H ,-N-CH
2-), 1.82 (s, 6H ,-C-CH
3); See Fig. 3 and Fig. 4.
Electronic bridge B is thiophene, and when electron acceptor(EA) A was tricyano pyrroline (TCP), structure and the synthetic route of chromophore molecule were as follows:
Synthetic method is:
1. compound 1 is synthetic
N-phenylmaleimide 3.5g (0.02mol) and anthracene 3.6g (0.02mol) are dissolved in the methylene dichloride of 50mL drying, heated and stirred to 60 ℃ reflux temperature carried out cycloaddition reaction 36 hours, be cooled to room temperature, rotary evaporation is concentrated into the residual solvent volume and is about 15mL, removes by filter filtrate.Product is washed three times with sherwood oil, gets white powder crystal 5 .8g, productive rate about 81%.
2. compound 2 is synthetic
3.5g compound 1 (0.01mol) is dissolved in the methylene dichloride of 50mL drying and at normal temperatures and stirs, slowly drip the diethyl ether solution 100mL that contains 1g tetrahydrochysene lithium aluminium (0.025mol).Stirred 8 hours in room temperature (25 ℃) after dropwising, then successively add 10mL ethyl acetate and 5mL water, and stir 0.5 hour with stopped reaction.Remove by filter precipitation, filtrate is washed 3 times with saturated common salt, separatory, and organic phase is spent the night with anhydrous sodium sulfate drying.Remove by filter siccative, rotary evaporation is removed solvent, gets white powder solid product 2.4g, productive rate about 75%.
MS (EI) m/z:323 (M
+); See Fig. 1.
3. compound 3 is synthetic
0.65g compound 2 (2mmol) is dissolved in the N-N ' of 10mL drying-dimethyl formamide (DMF), bathes with cryosel and be cooled to 0 ℃; Then slowly drip 0.37g phosphorus oxychloride (2.4mmol), kept 0 ℃ of lower continuation stirring reaction of temperature 1 hour, remove cryosel and bathe, be warming up to 65 ℃ of reactions 4 hours.Add the acid that generates in the aqueous solution neutralization reaction of about 40mL sodium bicarbonate, stirred 0.5 hour, remove by filter filtrate, getting crude product is yellow solid.Crude product separates through column chromatography (stationary phase is 200～300 purpose silica gel, and moving phase is the mixed solution of sherwood oil and acetone, sherwood oil: the volume ratio of acetone is 3: 1), gets 0.43g pure compound 3, productive rate about 61%.
MS (EI) m/z:351 (M
+); See Fig. 2.
4. compound 4 is synthetic
1.1g thiophen(e)alcohol (0.01mol) and 3.4g hydrogen bromide triphenylphosphine (0.01mol) are dissolved in the 50mL chloroform, be heated to 60 ℃ of reactions 3 hours, the cooling stopped reaction, steam solvent, add the 200mL anhydrous diethyl ether, stir, remove by filter filtrate, the residue yellow solid is compound 4, need not purifying and can carry out next step reaction.
5. compound 5 is synthetic
0.44g compound 4 (1mmol) and 0.35g compound 3 (1.1mmol) are dissolved in the 100mL anhydrous diethyl ether, and adding 0.5g sodium hydride (21mmol), (25 ℃) stirred 48 hours under the room temperature, reaction is poured product in the 200mL frozen water into after finishing, separatory, with 50mL extracted with diethyl ether water, merge organic phase, use the anhydrous magnesium sulfate drying organic phase, remove by filter siccative, revolve to steam and remove ether, (stationary phase is 200～300 purpose silica gel to the gained crude product with column chromatography, moving phase is the mixed solution of sherwood oil and acetone, sherwood oil: the volume ratio of acetone is 4: 1) separate, obtain compound 5.
6. compound 6 is synthetic
0.43g compound 5 (1mmol) is dissolved in dry N-N ' the dimethoxy methane amide, be cooled to 0 ℃ and drip 1.2g phosphorus oxychloride (1.4mmol), dropwising 5 ℃ of lower continuation of rear maintenance stirs half an hour, then be warming up to 70 ℃ and continue reaction 5 hours, cooling after reaction finishes, add the acid that generates in the saturated aqueous solution neutralization reaction of 20mL sodium bicarbonate, with 20mL extracted with diethyl ether 3 times, merge organic phase, organic phase is carried out drying with anhydrous magnesium sulfate, remove by filter siccative, (stationary phase is 200～300 purpose silica gel to the gained crude product through column chromatography, moving phase is the mixed solution of sherwood oil and acetone, sherwood oil: the volume ratio of acetone is 2: 1) separate, get pure compound 6.
7. compound 7 (TCP electron acceptor(EA)) is synthetic
Reference: Jang, S.H., J.Luo, et al., Pyrroline Chromophores for Electro-Optics, Chem.Mater., 2006,18 (13): 2982-2988.
8. compound 8 (the target chromophore molecule that contains the thiophene electronic bridge) is synthetic
0.5g compound 6 (1.1mmol) is dissolved in the 30mL ethanol with 0.2g (1.2mmol) compound 7 (TCP), be heated to 70 ℃ of reactions 1 hour, reaction is chilled to room temperature after finishing, remove by filter filtrate, (stationary phase is 200～300 purpose silica gel to remaining solid through column chromatography, moving phase is the mixed solution of sherwood oil and acetone, sherwood oil: the volume ratio of acetone is 3: 1) separate, can get compound 8 (the target chromophore molecule that contains the thiophene electronic bridge).
Embodiment 3.
The electrostrictive polymer optical thin film material preparation that contains chromophoric group ZFS that is used for the device center core layer material of communication field electrooptic modulator:
The chromophoric group ZFS that 0.02g embodiment 1 is prepared mixes with the unformed polycarbonate APC of 0.08g, adds the 1.2mL methylene bromide, in 40 ℃ of lower fully stirrings extremely fully dissolving in 12 hours; Then the tetrafluoroethylene membrane filter of gained solution through 0.22 μ m filtered, be spun in the ito glass substrate with 1200 rev/mins rotating speeds, vacuum-drying is 24 hours under the polymeric film normal temperature that obtains, and the gauge control of polymeric film is at 3～4 μ m.
Polymer thin-film material adopts the mode of corona polarizing to obtain electro-optical activity (reference: Singer, K.D., M.G.Kuzyk, et al.Electro-optic phase modulation and optical second-harmonic generation in corona-poled polymer films, Applied Physics Letters, 1988,53 (19): 1800-1802.), the polarization temperature is between 150～160 ℃, polarization time is 10～30 minutes, polarizing voltage is controlled at about 10～12kV, and the distance between needle point and the polymeric film is 1 centimetre.
Electro-optic coefficient (r
33) by simple reflex method (reference: Teng, C.C.and H.T.Man., Simple reflection technique for measuring the electro-optic coefficient of poled polymers, AIP., 1990) method is measured, and the maximum electro-optic coefficient that records is 35pm/V.
Claims (7)
1. a chromophore molecule that contains triptycene rigidity three-dimensional arrangement is characterized in that, the described chromophore molecule that contains triptycene rigidity three-dimensional arrangement has following formula:
Wherein:
B is electronic bridge, and structure is:
A is electron acceptor(EA), and structure is:
2. a synthetic method that contains the chromophore molecule of triptycene rigidity three-dimensional arrangement according to claim 1 is:
(1) N-phenylmaleimide and anthracene are dissolved in the dry dichloromethane solvent take the ratio of mol ratio as 1: 1, heated and stirred to reflux temperature carries out cycloaddition reaction; After reaction is finished, steam the part methylene chloride solvent, make the volume of solution be concentrated into 2/5 to 1/5 of gained liquor capacity after the reaction, remove by filter filtrate, obtain containing the reacting precursor of electron donor(ED) of the chromophore molecule of triptycene Three-dimensional Rigidity three-dimensional arrangement;
The reacting precursor of the electron donor(ED) of the chromophore molecule that (2) step (1) is obtained is dissolved in the dry dichloromethane solvent, drips reacting precursor molar ratio with the electron donor(ED) of chromophore molecule under the room temperature and be the diethyl ether solution of 2～3 tetrahydrochysene lithium aluminium; Stirring reaction is 6～12 hours under the room temperature, then be taken up in order of priority adding ethyl acetate and water with stopped reaction, remove by filter precipitation, the agent of filtrate drying is dry, remove by filter siccative, steam the electron donor(ED) part desolventize the chromophore molecule that obtains containing triptycene Three-dimensional Rigidity three-dimensional arrangement;
The electron donor(ED) of the chromophore molecule that contains triptycene Three-dimensional Rigidity three-dimensional arrangement that (3) step (2) is obtained is partially soluble in dry N-N ' the dimethoxy methane amide, be that 0～5 ℃ of lower molar ratio that drips with the electron donor(ED) part of the chromophore molecule that contains triptycene Three-dimensional Rigidity three-dimensional arrangement is 1.1～1.5 phosphorus oxychloride and stirs in temperature, dripping the complete rear maintenance temperature of phosphorus oxychloride is 0～5 ℃ of lower reaction 0.5～1 hour, and then be warming up to temperature be 60～70 ℃ the reaction 3～6 hours, stopped reaction, add the acid that generates in the aqueous solution neutralization reaction of sodium bicarbonate, filter and remove filtrate, crude product separates through column chromatography, obtains containing the reacting precursor of formyl radical;
(4) under the room temperature, the reacting precursor that contains formyl radical that step (3) is obtained and electron acceptor(EA) are tricyano furans or tricyano pyrroline according to mol ratio is that 1: 1.1～1.2 ratio is mixed and is dissolved in the methyl alcohol, be warming up to 60～70 ℃ of stirring reactions and filter removal filtrate after 1～2 hour, crude product separates through column chromatography, obtains containing the chromophore molecule that contains triptycene rigidity three-dimensional arrangement of carbon-carbon double bond electronic bridge;
Or
The reacting precursor that contains formyl radical that step (3) is obtained and bromo thiophene methyl triphenyl phosphine are that 1: 1～1.1 ratio is mixed in the anhydrous diethyl ether solvent according to mol ratio, and add the sodium hydride of 15～25 times of molar weights of the reacting precursor contain formyl radical, under being 20～50 ℃, temperature stirred 18～50 hours, reaction product is poured in the frozen water, separatory, the extracted with diethyl ether water, merge organic phase, carry out drying with siccative, remove by filter siccative, crude product separates with column chromatography, obtains containing the compound of thiophene electronic bridge;
The compound that gained is contained the thiophene electronic bridge is dissolved in dry N-N ' the dimethoxy methane amide, under temperature is 0～5 ℃, drip with the molar ratio that contains the compound of thiophene electronic bridge and be 1.1～1.5 phosphorus oxychloride and stir, dripping the complete rear maintenance temperature of phosphorus oxychloride is 0～5 ℃ of lower reaction 0.5～1 hour, and then be warming up to temperature be 60～70 ℃ the reaction 3～6 hours, cooling after reaction finishes, add the acid that generates in the aqueous solution neutralization reaction of sodium bicarbonate, use extracted with diethyl ether, merge organic phase, carry out drying with siccative, remove by filter siccative, crude product separates with column chromatography, obtains containing the reacting precursor of thiophene electronic bridge;
Be tricyano furans or tricyano pyrroline according to mol ratio with the reacting precursor that contains the thiophene electronic bridge that obtains and electron acceptor(EA) be that 1: 1.1～1.2 ratio is mixed and is dissolved in the ethanol, be warming up to 60～70 ℃ of stirring reactions and filter removal filtrate after 1～2 hour, crude product separates through column chromatography, obtains containing the chromophore molecule that contains triptycene rigidity three-dimensional arrangement of thiophene electronic bridge;
The described chromophore molecule that contains triptycene rigidity three-dimensional arrangement has following formula:
Wherein:
B is electronic bridge, and structure is:
A is electron acceptor(EA), and structure is:
3. synthetic method according to claim 1, it is characterized in that: the described time of carrying out cycloaddition reaction of step (1) is 24～48 hours.
4. synthetic method according to claim 1, it is characterized in that: the diethyl ether solution that drips reacting precursor molar ratio with the electron donor(ED) of chromophore molecule under the described room temperature of step (2) and be 2～3 tetrahydrochysene lithium aluminium, wherein, the volume ratio of ether and methylene dichloride is 1.5～2.5: 1.
5. application that contains the chromophore molecule of triptycene rigidity three-dimensional arrangement according to claim 1 is characterized in that: the described chromophore molecule of triptycene rigidity three-dimensional arrangement that contains is for the preparation of polymer as electro-optical material.
6. application according to claim 5, it is characterized in that: the described chromophore molecule of triptycene rigidity three-dimensional arrangement that contains is for the preparation of polymer as electro-optical material, that the polar polymer that obtains uses as the core material in the device of electrooptic modulator with the described chromophore molecule that contains triptycene rigidity three-dimensional arrangement and unformed polycarbonate or the polymethylmethacrylate preparation polar polymer that mixes.
7. application according to claim 6 is characterized in that: described doping is that to contain the chromophore molecule of triptycene rigidity three-dimensional arrangement and unformed polycarbonate or polymethylmethacrylate be 1: 1～10 to mix according to mass ratio.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115850187A (en) * | 2023-02-21 | 2023-03-28 | 季华实验室 | Organic electroluminescent material based on dibenzenesulfenimidazole derivative, preparation method and application thereof |
| US11634429B2 (en) | 2019-10-04 | 2023-04-25 | University Of Washington | Organic electro-optic chromophores |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63117013A (en) * | 1986-11-01 | 1988-05-21 | Chisso Corp | Novel polymeric substance |
| CN1274383A (en) * | 1997-10-10 | 2000-11-22 | 阿克西瓦有限公司 | Trypticene derivatives and their use in optoelectronic device, in particular as electroluminescent materials |
| US7307173B1 (en) * | 2004-02-19 | 2007-12-11 | University Of Washington | Pyrroline chromophores |
| US7425643B1 (en) * | 2004-01-26 | 2008-09-16 | University Of Washington | Electron acceptors for nonlinear optical chromophores |
| CN101497785A (en) * | 2008-01-28 | 2009-08-05 | 中国科学院理化技术研究所 | Organic second order non-linear optical chromophore group containing dendritic structured tricyano pyrroline receptor, synthesizing method and use thereof |
| US7601849B1 (en) * | 2001-08-02 | 2009-10-13 | University Of Washington | Nonlinear optical compounds and related macrostructures |
| CN101845040A (en) * | 2009-03-23 | 2010-09-29 | 中国科学院理化技术研究所 | Organic second-order non-linear optical chromophore with D-Pi-A structure and decorated by tree-like group, synthesizing method and application thereof |
| CN101845039A (en) * | 2009-03-23 | 2010-09-29 | 中国科学院理化技术研究所 | Second-order nonlinear optical chromophore with D-pai-A structure and synthetic method and use thereof |
-
2012
- 2012-04-19 CN CN201210117023.1A patent/CN103373990B/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63117013A (en) * | 1986-11-01 | 1988-05-21 | Chisso Corp | Novel polymeric substance |
| CN1274383A (en) * | 1997-10-10 | 2000-11-22 | 阿克西瓦有限公司 | Trypticene derivatives and their use in optoelectronic device, in particular as electroluminescent materials |
| US7601849B1 (en) * | 2001-08-02 | 2009-10-13 | University Of Washington | Nonlinear optical compounds and related macrostructures |
| US7425643B1 (en) * | 2004-01-26 | 2008-09-16 | University Of Washington | Electron acceptors for nonlinear optical chromophores |
| US7307173B1 (en) * | 2004-02-19 | 2007-12-11 | University Of Washington | Pyrroline chromophores |
| CN101497785A (en) * | 2008-01-28 | 2009-08-05 | 中国科学院理化技术研究所 | Organic second order non-linear optical chromophore group containing dendritic structured tricyano pyrroline receptor, synthesizing method and use thereof |
| CN101845040A (en) * | 2009-03-23 | 2010-09-29 | 中国科学院理化技术研究所 | Organic second-order non-linear optical chromophore with D-Pi-A structure and decorated by tree-like group, synthesizing method and application thereof |
| CN101845039A (en) * | 2009-03-23 | 2010-09-29 | 中国科学院理化技术研究所 | Second-order nonlinear optical chromophore with D-pai-A structure and synthetic method and use thereof |
Non-Patent Citations (2)
| Title |
|---|
| A. A. ABU-HASHEM 等: "Synthesis, Anti-inflammatory and Analgesic Evaluation of Certain New 3a,4,9,9a-Tetrahydro-4,9-benzenobenz[f]isoindole-1,3-diones", 《ARCH.PHARM.CHEM.LIFE SCI.》, vol. 344, 16 June 2011 (2011-06-16), pages 543 - 551 * |
| 陈传峰 等: "三蝶烯及其衍生物的合成与应用研究进展", 《科学通报》, vol. 52, no. 12, 30 June 2007 (2007-06-30), pages 1349 - 1361 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US11634429B2 (en) | 2019-10-04 | 2023-04-25 | University Of Washington | Organic electro-optic chromophores |
| CN115850187A (en) * | 2023-02-21 | 2023-03-28 | 季华实验室 | Organic electroluminescent material based on dibenzenesulfenimidazole derivative, preparation method and application thereof |
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