CN102053448A - Nitroaniline chiral non-linear optical material - Google Patents
Nitroaniline chiral non-linear optical material Download PDFInfo
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- CN102053448A CN102053448A CN2009101127066A CN200910112706A CN102053448A CN 102053448 A CN102053448 A CN 102053448A CN 2009101127066 A CN2009101127066 A CN 2009101127066A CN 200910112706 A CN200910112706 A CN 200910112706A CN 102053448 A CN102053448 A CN 102053448A
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- nitroaniline
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- nitrobenzyl
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Abstract
The invention discloses a new nitroaniline chiral non-linear optical crystal material. The new nitroaniline chiral non-linear optical crystal material is (S)-N-(4-nitrobenzyl)-glutamic acid and is prepared by performing condensation on natural chiral amino acid serving as a raw material and nitrobenzaldehyde. Transition metal complexes [NiL2(4,4'-bpy)(H2O)2]n and {[CdL2(4,4'-bpy)].2H2O}n of the chiral compound are prepared, wherein L is chiral ligand (S)-N-(4-nitrobenzyl)-glutamic acid. The metal complexes are prepared by performing hydro-thermal synthesis on the chiral ligand, metals such as nickel carbonate, cadmium carbonate and the like and 4,4'-bipyridyl in aqueous solution. A chiral group of the compound guarantees the existence of a non-heart space group required by a second-order non-linear optical crystal material. A preparation method of the new nitroaniline chiral non-linear optical crystal material is simple, low in cost and stable in properties. The obtained compound crystal has high second-order non-linear optical properties and can be widely and prospectively applied in the fields of high and new technology such as optical communication, optical information processing, optical storage and the like.
Description
[technical field]
The present invention relates to a kind of nitrobenzene amine chirality non-linear optical crystal material, belong to inorganic and organic field, also belong to the optical material field.
[background technology]
Nonlinear optics is a new subject that grows up after laser occurs, and has obtained important progress in many new research fields in recent decades, and has brought the remarkable economical effect.Nonlinear optical material is mainly used in the conversion of frequency of light wave, with open up new LASER Light Source and control, light signals such as switch, amplification, storage handle.Can make various optical device thus, be widely used in various fields such as optical communication, optical information processing, optical storage and processing and medical treatment.
The research of early stage nonlinear optical material mainly concentrates on inorganic crystal material, has much to have obtained practical application.For example KDP, BBO, LiNbO3 etc.But the nonlinear optical coefficients of inorganic crystal material are low, light injury threshold is low, and it is very difficult further to find out the gem-quality crystal that can produce big nonlinear effect.And organic compound has nonlinear optical coefficients height, optical damage threshold height, response soon, particularly can carry out advantages such as MOLECULE DESIGN as requested, makes it become the new focus of nonlinear optical material research.Studying maximum organic non linear optical materials has: the nitroaniline derivant, and the compound that vinyl connects, hydrazone system and schiff bases system, pyridine derivate, and the arone based compound etc.Yet organic molecule or its complex compound because intermolecular electrostatic interaction may generate centrosymmetric crystal space group, cause crystal forfeiture nonlinear effect when forming crystal.And its structure of control is comparatively difficult in the crystal incubation.Introducing chiral atom in molecule is a method of effectively avoiding producing symcenter.
Amino acid is the natural chirality storehouse of wide material sources, and amino acid whose crystal itself also has certain non-linear optical active, and therefore, it is the method that effectively obtains higher order hyperpolarizability β that amino acid is used in nonlinear optical material.At present the correlative study majority of report concentrates on amino acid whose inorganic salts crystal and amino acid other nonlinear optical material that mixes in the world, obtains the also less report of research of new nonlinear optical material by design synthesizing amino acid derivative.
[summary of the invention]
The object of the present invention is to provide a kind of nitroaniline quasi-nonlinear optical crystal material that contains chiral center.
The chirality nonlinear optical material of the present invention's preparation is (S)-N-(4-nitrobenzyl)-glutamic acid, and its structure is as follows:
In this compound, the amido that electrical nitro and power supply property are inhaled in the contraposition of phenyl ring respectively replaces, and has formed an A-π-D electron donor-acceptor structure.Analyze theoretically, the conjugated system with A-π-D structure often has non-linear optical active preferably.Simultaneously, adjacent with amido asymmetric carbon atom has guaranteed that compound can not form intentionally space group in crystallization process.
The present invention has simultaneously also prepared the cadmium and the nickel metal complex crystal of this compound, and its chemical formula is respectively [Ni L
2(4,4 '-bpy) (H
2O)
2]
n{ [CdL
2(4,4 '-bpy)] 2H
2O}n, wherein L is chiral ligand (S)-N-(4-nitrobenzyl)-glutamic acid.Cadmium complex belongs to monoclinic system, P2
1Space group, crystal unit cell parameter are a=11.759 (7), b=8.819 (5), c=18.246 (11), V=1835.4 (18), Z=2; Nickel complex belongs to monoclinic system, and C2 space group, crystal unit cell parameter are a=15.444 (11), b=11.308 (7), c=10.076 (7), V=1706 (2), Z=2.With organic compound and metal complex, can improve the thermal stability and the mechanical stability of material, further improve the performance of material.
The chirality nonlinear optical material of the present invention's preparation is to utilize natural chiral amino acid to be raw material, forms with the nitrobenzaldehyde condensation.Its complex be will be synthetic chipal compounds and metals such as nickelous carbonate, cadmium carbonate, and 4,4 '-dipyridine synthesizes by hydro-thermal method in aqueous solution.
The concrete synthetic method of chirality nonlinear optical material (S) N-(4-the nitrobenzyl)-glutamic acid of the present invention's preparation is: L-glutamic acid is dissolved in the sodium hydrate aqueous solution of doubling dose, then drip the ethanolic solution of paranitrobenzaldehyde, the mol ratio of paranitrobenzaldehyde and glutamic acid is 1: 1.After dropwising, add sodium borohydride reduction at low temperatures, stirred for several hour makes and to react completely, and dripping hydrochloric acid adjust pH to acidity is separated out product at low temperatures then, and suction filtration, washing solid, vacuum drying obtain the higher chiral product of purity.
The synthetic method of the chiral metal complex of the present invention's preparation is:
With synthetic chiral ligand and slaine, 4,4 '-dipyridine stirs in aqueous solution, L/M/4, the mol ratio of 4 '-bpy is 1: 1: 1, reactant liquor is heated to 100-120 ℃, sustained response 12-24 hour, then slowly reduce to room temperature, suction filtration obtains the product crystal
The chirality nonlinear optical crystal of the present invention preparation has that preparation is easy, with low cost, product purity is high, to air-stable, not deliquescence, Heat stability is good, characteristics such as higher frequency-doubled effect are arranged, be expected to be used widely at high-technology fields such as optical communication, optical information processing, optical storages.
[description of drawings]
The structural representation of Fig. 1 (S) N-(4-nitrobenzyl)-glutamic acid
The crystal structure accumulation graph of Fig. 2 cadmium complex
The crystal structure accumulation graph of Fig. 3 nickel complex
[embodiment]
Below in conjunction with accompanying drawing embodiments of the invention are elaborated.Present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1:
Chiral ligand (S)-N-(4-nitrobenzyl)-glutamic acid synthetic: will (S)-glutamic acid (14.7g, 0.1mol) be dissolved in 2M NaOH aqueous solution (0.2mol, 100mL) in, dropping 4-nitrobenzaldehyde (15.1g, methyl alcohol 0.1mol) (50mL) solution.After dripping off this mixed liquor is chilled to below 5 ℃ with ice bath, adds NaBH in batches
4(1.2g 0.03mol), and makes reacting liquid temperature remain on 0-5 ℃.After adding reactant liquor is risen to room temperature and continue to stir 1.5h.(3.02g, methyl alcohol 0.02mol) (10mL) solution then adds NaBH to drip the 4-nitrobenzaldehyde once more
4(0.24g 6mmol), continues to stir 0.5h, 0-5 ℃ of following dripping hydrochloric acid, transfers pH to 3.Have a large amount of faint yellow solids to separate out this moment.Suction filtration with frozen water washing solid, then is placed on solid 50 ℃ of dry a few hours in the vacuum drying chamber.Obtain 24g (85.1%) (S)-N-(4-nitrobenzyl)-glutamic acid.Ultimate analysis theoretical value (experiment value) %:C, 51.06 (50.99); H, 5.00 (4.96); N, 9.93 (9.96).Infrared spectrum (KBr, cm
-1): 3505.73 (m); 1712.54 (s); 1614.73 (s); 1528.56 (s); 1351.18 (s); 1270.61 (m); 1234.72 (w); 859.24 (m).Nucleus magnetic hydrogen spectrum: δ 8.176-8.219 (m, 2H, H-arom); 7.500-7.522 (m, 2H, H-arom); 4.645-4.882 (m, 1H ,-CH); 4.039-4.066 (m, 2H ,-CH
2); 2.499-2.517 (m, 2H ,-CH
2); 2.310-2.402 (m, 2H ,-CH2); 1.978-2.031 (m, 1H ,-NH).
Embodiment 2:
Synthesizing of cadmium complex: part (S)-N-(4-nitrobenzyl)-glutamic acid (0.25mmol) and cadmium carbonate (0.25mmol), 4,4 '-dipyridine (0.25mmol), and 5mL water is stirred to evenly, enclose volume and be in the stainless steel cauldron of teflon lined of 25mL and be heated to 100 ℃, sustained response 1 day is then reduced to room temperature with the speed of 1.6 ℃/h.Obtain yellow column crystal 43.6mg (21.0%).Ultimate analysis theoretical value (experiment value) %:C, 49.26 (49.18); H, 3.89 (3.54); N, 10.14 (10.07).Infrared spectrum (KBr, cm
-1): 3421.34 (m), 1677.45 (s), 1659.26 (s), 1591.70 (s), 1519.79 (s), 1448.35 (w), 1414.63 (m), 1347.46 (s), 1297.32 (w), 1218.68 (w), 814.28 (m), 708.26 (m), 627.58 (m).
Embodiment 3:
Synthesizing of nickel complex: part (S)-N-(4-nitrobenzyl)-glutamic acid (0.25mmol) and nickelous carbonate (0.25mmol), 4,4 '-dipyridine (0.25mmol), and 5mL water is stirred to evenly, enclose volume and be in the stainless steel cauldron of teflon lined of 25mL and be heated to 120 ℃, sustained response 12h then reduces to room temperature with the speed of 2 ℃/h.Obtain green column crystal 56.5mg (29.1%).Ultimate analysis theoretical value (experiment value) %:C, 52.67 (52.48); H, 4.16 (4.29); N, 10.84 (10.80).Infrared spectrum (KBr, cm
-1): 3314.65 (m), 1669.52 (s), 1608.17 (s), 1516.30 (m), 1418.05 (m), 1401.41 (m), 1343.35 (s), 1305.34 (m), 732.62 (w).
Embodiment 4:
Powder frequency-doubled effect test: the gained crystalline material is contained in the sample cell, sample cell is placed on the laser optical path, using the Nd:YAG pulsed laser to produce wavelength as light source is that the fundamental frequency light of 1064 nanometers is injected sample cell, as standard specimen, signal is shown on the oscillograph through photomultiplier with the KDP monocrystal of about 200 mm particle sizes.
The gained compound is measured through x-ray crystal structure, and its crystal structure is seen Fig. 2-3.
Claims (2)
1. nitrobenzene amine chirality second-order non-linear optical materials, it is characterized in that: this material is (S)-N-(4-nitrobenzyl)-glutamic acid, and structural formula is:
2. the metal complex of the described chirality second-order non-linear optical materials of claim 1, it is characterized in that: chemical formula is respectively [NiL
2(4,4 '-bpy) (H
2O)
2]
n{ [CdL
2(4,4 '-bpy)] 2H
2O}
n, wherein L is chiral ligand (S)-N-(4-nitrobenzyl)-glutamic acid; The cadmium complex crystal belongs to monoclinic system, P2
1Space group, cell parameter are a=11.759 (7), b=8.819 (5), c=18.246 (11), V=1835.4 (18), Z=2; The nickel complex crystal belongs to monoclinic system, the C2 space group, and cell parameter is a=15.444 (11), b=11.308 (7), c=10.076 (7), V=1706 (2), Z=2.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727624A (en) * | 2018-04-20 | 2018-11-02 | 苏州科技大学 | A kind of preparation method and applications of self-assembled nanometer composite high-molecular functional material |
| CN114775062A (en) * | 2022-06-24 | 2022-07-22 | 季华实验室 | Nonlinear optical crystal, preparation method thereof and nonlinear optical device |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030187052A1 (en) * | 2002-03-20 | 2003-10-02 | George W. Muller | (+)-2-[1-(3-Ethoxy-4-methoxyphenyl)-2-methylsulfonylethyl]-4-acetylaminoisoindoline-1,3-dione: methods of using and compositions thereof |
| CN1850788A (en) * | 2006-05-26 | 2006-10-25 | 浙江大学 | D-pi-A structure nonlinear optical chromophore, and its synthesizing method |
| US20070267606A1 (en) * | 2006-05-16 | 2007-11-22 | Diyun Huang | Low Loss Electro-Optic Polymers Composites |
-
2009
- 2009-10-28 CN CN2009101127066A patent/CN102053448A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030187052A1 (en) * | 2002-03-20 | 2003-10-02 | George W. Muller | (+)-2-[1-(3-Ethoxy-4-methoxyphenyl)-2-methylsulfonylethyl]-4-acetylaminoisoindoline-1,3-dione: methods of using and compositions thereof |
| US20070267606A1 (en) * | 2006-05-16 | 2007-11-22 | Diyun Huang | Low Loss Electro-Optic Polymers Composites |
| CN1850788A (en) * | 2006-05-26 | 2006-10-25 | 浙江大学 | D-pi-A structure nonlinear optical chromophore, and its synthesizing method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108727624A (en) * | 2018-04-20 | 2018-11-02 | 苏州科技大学 | A kind of preparation method and applications of self-assembled nanometer composite high-molecular functional material |
| CN114775062A (en) * | 2022-06-24 | 2022-07-22 | 季华实验室 | Nonlinear optical crystal, preparation method thereof and nonlinear optical device |
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Application publication date: 20110511 |