CN1850788A - D-pi-A structure nonlinear optical chromophore, and its synthesizing method - Google Patents
D-pi-A structure nonlinear optical chromophore, and its synthesizing method Download PDFInfo
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- CN1850788A CN1850788A CN 200610051653 CN200610051653A CN1850788A CN 1850788 A CN1850788 A CN 1850788A CN 200610051653 CN200610051653 CN 200610051653 CN 200610051653 A CN200610051653 A CN 200610051653A CN 1850788 A CN1850788 A CN 1850788A
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Abstract
This invention discloses D- pi-A structure nonlinear optics chromophore and ts synthesizing method. Its structure general formula is shown as (1), and R is fluorin, chlorine or bromine and other halogen atoms. Nitroaniline compound contains halogen atoms is react with nitrolys-sulfuric acid to generate diazo salt, then it is coupled reacted with 2, 5-dimethyl phenol to generate the species chromophore compound. Its synthesis technique is simple, yield is high, the material is easy to get, and reaction condition is wild. This kind of compound has higher second order nonlinear optics capability and excellent light permeability at visible light wave band, it can be used to blue green wave band laser double frequency field.
Description
Technical field
The present invention relates to the non-linear optical chromophore and the synthetic method thereof of D-pi-A structure.
Background technology
Along with development of times, people are more and more higher to the requirement of information transmission, storage, exchange and processing.Traditional electronic information type of transmission is because its inherent defective has all restricted the widespread use of electronic information in Future Society at aspects such as speed, capacity, space compatible and information accuracy of detection.In order to overcome the bottleneck effect of electronics, collection, storage and the processing of adopting the alternative electronics of photon to carry out data have become the inevitable development trend of information science engineering from now on.For the development of photon technology, nonlinear optics is indispensable crucial subject.Four during the last ten years, and nonlinear optics has progressively developed into an independently subject branch, in fields such as laser freuqency doubling, mixing, parameter amplification, optical communication and storages extremely important application arranged all.
Short wavelength's blue laser is a HIGH-DENSITY OPTICAL STORAGE, digital video technology, and the indispensable light sources in field such as color laser demonstration and laser medicine, countries in the world are just starting the research boom of solid-state blue laser light source.At present, the technology of near-infrared band semiconductor laser is very ripe, by the nonlinear optics frequency-doubled effect near-infrared laser is carried out frequency-doubled conversion, the effective way thereby the wavelength spread of realization all solid state laser then be can yet be regarded as.At the characteristics of present semiconductor laser, laser freuqency doubling requires non-linear double-frequency material must have good light transmission at bluish-green wave band, and this will ask the maximum absorption band λ of chromophore molecule
MaxWill be away from operation wavelength, though the chromophore of more existing high non-linearity optical properties has bigger β value at present, absorption peak all about 500nm, use by the frequency multiplication that at all can not be used for GaAs based semiconductor laser device mostly.
Generally speaking, for the chromophore of D-π-A structure, give, acceptor intensity is big more, helps the conjugation attitude that system forms charge transfer more, thereby enlarge the flow range of πDian Zi, make molecule intramolecular charge transfer of easier generation and help increasing the β value of molecule under outer field action.But increase is simply given, the intensity of acceptor can make the maximum absorption wavelength red shift, cause the transparency of molecule to descend, promptly so-called " non-linear-light transmission contradiction ", this just needs to pass through, and searching is given, the incompatible reduction of best group " non-linear-light transmission contradiction " of acceptor intensity.So design, the synthetic nlo molecule that had not only had higher non-linear optical property but also had a good transparency still have bigger challenge.
Summary of the invention
The object of the present invention is to provide the non-linear optical chromophore and the synthetic method thereof of D-pi-A structure.This compounds not only synthesis technique is simple, and productive rate is higher, and raw material is easy to get, the reaction conditions gentleness, and can be used as the novel non-linearity optical material in field practical applications such as optical communication, laser freuqency doubling, data-storings.
The non-linear optical chromophore of D-pi-A structure provided by the invention, its general structure is suc as formula (1)
Formula (1)
R is halogen atoms such as fluorine, chlorine or bromine in the formula.
The synthetic method of above-mentioned non-linear optical chromophore, its step is as follows:
1) acid of adding 100-5000ml in 1 mole N-methyl-p-nitroaniline compound stirs into pasty state, slowly drips the nitrosyl-sulfuric acid of 1-1.5 mole then, 0-5 ℃ of following diazotization reaction;
2) after diazotization reaction finishes, add 1-1.5 mole 2,5-xylenol and 500-5000ml volume ratio are 2: 1 the methyl alcohol and the mixing solutions of water, 0-10 ℃ of coupled reaction, regulate the pH value to 7-8 with alkaline solution, continue reaction at least 0.5 hour;
3) filter and wash the head product that obtains, the mixture recrystallization twice of water and organic solvent gets non-linear optical chromophore.
Said N-methyl-p-nitroaniline compound is 2-fluoro-4-N-methyl-p-nitroaniline, 2-chloro-4-N-methyl-p-nitroaniline or 2-bromo-4-N-methyl-p-nitroaniline in the above-mentioned synthetic method; Said acid is hydrochloric acid, sulfuric acid or glacial acetic acid; Said alkaline solution is ammoniacal liquor, sodium hydroxide solution or sodium carbonate solution; Said organic solvent is ethanol, acetone or tetrahydrofuran (THF).
Beneficial effect of the present invention is:
1. non-linear optical chromophore of the present invention not only has the higher non-linearity optical property, and has the good transparency at visible light wave range, is expected to obtain practical application in the fields such as laser freuqency doubling of bluish-green wave band.
2. the non-linear optical chromophore synthesis technique of D-π of the present invention-A structure-type is simple, and productive rate is higher, and raw material is easy to get the reaction conditions gentleness.
Embodiment
Embodiment 1:
R is the chlorine atom, non-linear optical chromophore 2,5-dimethyl-4-(2 '-chloro-4 '-the nitro-azo base) synthetic route of phenol is as follows:
Synthetic method is: the 1.38g Sodium Nitrite slowly joins in the vitriol oil of 20ml 98% in batches, and temperature is controlled at below 20 ℃, stirs it is dissolved fully, is cooled to 0 ℃ again, obtains nitrosyl-sulfuric acid.In 3.45g (20mmol) 2-chloro-4-N-methyl-p-nitroaniline, add the 10ml vitriol oil again, stir into pasty state, inwardly slowly drip the 20mmol nitrosyl-sulfuric acid, 0 ℃ the reaction 1 hour after, add 2.44g (20mmol) 2 again, the mixing solutions of the methyl alcohol of 5-xylenol and 10ml and water (volume ratio of methyl alcohol and water is 2/1), 0 ℃ was reacted 1 hour, regulated the pH value with ammoniacal liquor and continued to react 2 hours to 7-8.After the standing over night, suction filtration, and washing obtains head product.Water and ethanol mixed solvent recrystallization twice obtain orange-red compound again, productive rate 53%.
196 ℃ of fusing points.
Nucleus magnetic resonance:
1H-NMR (500 MHz, DMSO-d
6, ppm): 1 0.64 (s, OH, 1H), 8.46 (d, ArH, 1H), 8.26 (m, ArH, 1H), 7.76 (d, ArH, 1H), 7.56 (s, ArH, 1H), 6.83 (s, ArH, 1H), 3.34 (s, CH
3, 3H), 2.13 (s, CH
3, 3H).
Ultimate analysis: theoretical value C
14H
12ClN
3O
3(305.7): C, 55.00; H, 3.96; N, 13.74; Measured value: C, 54.96; H, 3.91; N, 13.59.
The maximum absorption wavelength of chromophore in the present embodiment in tetrahydrofuran (THF) is 417nm, makes the d behind the material
33Be 14.3pm/V.Show that this chromophore has higher second-order nonlinear optical property and in the good light transmission of visible light wave range
Embodiment 2:
R is the chlorine atom, chromophore 2,5-dimethyl-4-(2 '-chloro-4 '-the nitro-azo base) synthetic method of phenol: the 1.38g Sodium Nitrite slowly joins in the vitriol oil of 20ml98% in batches, temperature is controlled at below 20 ℃, stirring is dissolved it fully, is cooled to 0 ℃ again, obtains nitrosyl-sulfuric acid.In 3.45g (20mmol) 2-chloro-4-N-methyl-p-nitroaniline, add the 2ml glacial acetic acid again, stir into pasty state, inwardly slowly drip the nitrosyl-sulfuric acid of 20mmol, 0 ℃ the reaction 1 hour after, add 3.66g (30mmol) 2 again, the mixing solutions of the methyl alcohol of 5-xylenol and 100ml and water (volume ratio of methyl alcohol and water is 2/1) 0 ℃ of reaction 1 hour, is regulated the pH value with sodium carbonate solution and is continued to react 2 hours to 7-8.After the standing over night, suction filtration, and washing obtains head product.The mixed solvent recrystallization twice of water and acetone obtains required non-linear optical chromophore again.
Embodiment 3:
R is a bromine atoms, non-linear optical chromophore 2,5-dimethyl-4-(2 '-bromo-4 '-the nitro-azo base) synthetic route of phenol is as follows:
Synthetic method is: the 0.14g Sodium Nitrite slowly joins in the vitriol oil of 2ml98% in batches, and temperature is controlled at below 20 ℃, stirs it is dissolved fully, is cooled to 0 ℃ again, obtains nitrosyl-sulfuric acid.In 0.44g (2mmol) 2-bromo-4-N-methyl-p-nitroaniline, add the 10ml concentrated hydrochloric acid again, stir into pasty state, inwardly slowly drip the 2mmol nitrosyl-sulfuric acid, 0 ℃ of reaction is after 1 hour, add 0.24g (2mmol) 2 again, the mixing solutions of the methyl alcohol of 5-xylenol and 6ml and water (volume ratio of methyl alcohol and water is 2/1), 0 ℃ was reacted 1 hour, regulated the pH value with sodium hydroxide solution and continued to react 2 hours to 7-8.After the standing over night, suction filtration, and washing obtains head product.Water and ethanol mixed solvent recrystallization twice promptly get required non-linear optical chromophore again.
Embodiment 4:
R is a fluorine atom, non-linear optical chromophore 2,5-dimethyl-4-(2 '-fluoro-4 '-the nitro-azo base) synthetic method of phenol is: the 0.27g Sodium Nitrite slowly joins in the vitriol oil of 4ml98% in batches, temperature is controlled at below 20 ℃, stirring is dissolved it fully, be cooled to 0 ℃ again, obtain nitrosyl-sulfuric acid.In 4mmol2-fluoro-4-N-methyl-p-nitroaniline, add the 15ml concentrated hydrochloric acid again, stir into pasty state, inwardly slowly drip the 4mmol nitrosyl-sulfuric acid, 0 ℃ of reaction is after 1 hour, add 0.49g (4mmol) 2 again, the mixing solutions of the methyl alcohol of 5-xylenol and 12ml and water (volume ratio of methyl alcohol and water is 2/1), 0 ℃ was reacted 1 hour, regulated the pH value with sodium hydroxide solution and continued to react 2 hours to 7-8.After the standing over night, suction filtration, and washing obtains head product.Water and ethanol mixed solvent recrystallization twice promptly get required non-linear optical chromophore again.
Claims (6)
1. the non-linear optical chromophore of D-pi-A structure, its general structure is suc as formula (1)
Formula (1)
R is fluorine, chlorine or bromine in the formula.
2. the synthetic method of non-linear optical chromophore according to claim 1 is characterized in that:
1) acid of adding 100-5000ml in 1 mole N-methyl-p-nitroaniline compound stirs into pasty state, slowly drips the nitrosyl-sulfuric acid of 1-1.5 mole then, 0-5 ℃ of following diazotization reaction;
2) after diazotization reaction finishes, add 1-1.5 mole 2,5-xylenol and 500-5000ml volume ratio are 2: 1 the methyl alcohol and the mixing solutions of water, 0-10 ℃ of coupled reaction, regulate the pH value to 7-8 with alkaline solution, continue reaction at least 0.5 hour;
3) filter and wash the head product that obtains, the mixture recrystallization twice of water and organic solvent gets non-linear optical chromophore.
3. according to the synthetic method of right 2 described non-linear optical chromophores, it is characterized in that said N-methyl-p-nitroaniline compound is 2-fluoro-4-N-methyl-p-nitroaniline, 2-chloro-4-N-methyl-p-nitroaniline or 2-bromo-4-N-methyl-p-nitroaniline.
4. according to the synthetic method of right 2 described non-linear optical chromophores, it is characterized in that said acid is hydrochloric acid, sulfuric acid or glacial acetic acid.
5. according to the synthetic method of right 2 described non-linear optical chromophores, it is characterized in that said alkaline solution is ammoniacal liquor, sodium hydroxide solution or sodium carbonate solution.
6. according to the synthetic method of right 2 described non-linear optical chromophores, it is characterized in that said organic solvent is ethanol, acetone or tetrahydrofuran (THF).
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102053448A (en) * | 2009-10-28 | 2011-05-11 | 中国科学院福建物质结构研究所 | Nitroaniline chiral non-linear optical material |
| CN103969879A (en) * | 2013-01-25 | 2014-08-06 | 北京京东方光电科技有限公司 | Display substrate and display device |
-
2006
- 2006-05-26 CN CN 200610051653 patent/CN1850788A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102053448A (en) * | 2009-10-28 | 2011-05-11 | 中国科学院福建物质结构研究所 | Nitroaniline chiral non-linear optical material |
| CN103969879A (en) * | 2013-01-25 | 2014-08-06 | 北京京东方光电科技有限公司 | Display substrate and display device |
| CN103969879B (en) * | 2013-01-25 | 2016-12-28 | 北京京东方光电科技有限公司 | Display base plate and display device |
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