CN101619497B - Non-linear optical crystal N-methyl-1,3-propane-diammonium aluminum pentaborate, preparation method and application thereof - Google Patents
Non-linear optical crystal N-methyl-1,3-propane-diammonium aluminum pentaborate, preparation method and application thereof Download PDFInfo
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- CN101619497B CN101619497B CN 200810071334 CN200810071334A CN101619497B CN 101619497 B CN101619497 B CN 101619497B CN 200810071334 CN200810071334 CN 200810071334 CN 200810071334 A CN200810071334 A CN 200810071334A CN 101619497 B CN101619497 B CN 101619497B
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Abstract
The invention relates to non-linear optical crystal N-methyl-1,3-propane-diammonium aluminum pentaborate, a preparation method and application thereof. The non-linear optical crystal N-methyl-1,3-propane-diammonium aluminum pentaborate has a chemical formula of Al(B4O9)(BO).NH3CH2CH2CH2NH3; and the chemical formula has molecular weight of 317.18, belongs to a monoclinic system with a space group of Cc, single cell parameters: a is equal to 10.933 (7), b is equal to 8.297 (5), c is equal to 13.317(8)*, alpha and gamma are equal to 90 degrees, beta is equal to 97.919 (8) degrees, V is equal to 1196.5 (1)*<3>, and Z is equal to 4. The non-linear optical crystal N-methyl-1,3-propane-diammonium aluminum pentaborate is prepared by a water (agent) method, has excellent non-linear optical property, and the powder coefficient of the non-linear optical crystal N-methyl-1,3-propane-diammonium aluminum pentaborate is two times of KDP, which corresponds to LBO.
Description
Technical field
The present invention relates to a kind of nonlinear optical material 1,3-propane-diammonium five aluminum borates (chemical formula: [Al (B
4O
9) (BO)] NH
3CH
2CH
2CH
2NH
3) preparation and application.
Background technology
(Nonlinear Optics is a frontier of contemporary optics NLO) to nonlinear optics, is the research response of material and science of the nonlinear relationship that field intensity presents under the high light effect.In numerous non-linear optical effects, frequency-doubled effect (SHG) be the most noticeable also be the non-linear effect of studying at most.Has the optical material of non-linear effect in modern science and technology, particularly in some civilian and military high-tech areas, for example photoelectricity communication, optical information storage, unicircuit, photoswitch, light slicer, color laser printing, blinding laser weapons, the ocean locating fish etc. have a series of important application.
Studies show that borate compound compares the non-centrosymmetrical structure of the easier formation of compound of other type, but not the structure of the heart is the precondition that produces non-linear optical effect.Therefore, for a long time, the borate crystal of nonlinear optics is people's research focus always.The nonlinear optics borate crystal of practical application comprises LiB at present
3O
5(LBO), β-BaB
2O
4(BBO), BiB
3O
6(BIBO) etc.Though these nonlinear optical materials are widely used in all trades and professions, yet different fields is also different to the requirement of nonlinear optical material, therefore can not have single nonlinear optical material optimization to be applied to all fields.This has just proposed requirement to the diversity of nonlinear optical material, so that can the specific nonlinear optical material of optimized selection in specific field.So be necessary to continue to seek and develop new nonlinear optical material.We are by adopting the AlO of chirality
4The poly-boron anion bunch coordinated groups of group and the non-heart is dressed up the strategy of the non-heart or chiral structure, thereby has obtained the novel non-linearity optical material of superior performance.
Summary of the invention
The objective of the invention is to prepare a kind of non-linear optic crystal 1,3-propane-diammonium five aluminum borates (chemical formula: [Al (B
4O
9) (BO)] NH
3CH
2CH
2CH
2NH
3), its technical scheme is as follows:
We select aluminum isopropylate (Al (i-PrO)
3), boric acid (H
3BO
3), 1,3-propylene diamine (C
3H
10N
2) make raw material, its mol ratio is 1: 13: 4, adopts water and pyridine to make mixed solvent, the chirality AlO that utilizes aluminum isopropylate to be hydrolyzed into
4The collaborative assembling of the non-the heart-yin ion cluster that group and boric acid aggregate into, and with 1 of diprotonization, 3-propylene diamine positively charged ion is made counter ion, obtains the crystalline material of 1,3-propane-diammonium, five aluminum borates under hydrothermal condition.
We record the single crystal structure of this compound, and its structural parameter are as follows:
Chemical formula is [Al (B
4O
9) (BO)] NH
3CH
2CH
2CH
2NH
3, molecular weight is 317.18, belongs to oblique system, spacer Cc, cell parameter are a=10.933 (7), and b=8.297 (5),
α=γ=90 °, β=97.919 (8) °,
Z=4.
The structure of 1,3-propane-diammonium, five aluminum borates is by AlO
4, B
4O
9, BO
3Be connected to a compound AlB by being total to the summit
5O
13Bunch unit, each AlB
5O
13Bunch unit is identical with on every side six bunch links to each other and forms and have 10 yuan of rings and 9 yuan of rings and intersect the tridimensional network in duct, 1 of diprotonization, and the 3-propylene diamine is filled in 10 membered ring channels as counter cation.
The nonlinear optics measurement shows that 1,3-propane-diammonium, five aluminum borates have good non-linear optical property, the very strong 532nm green glow of output under the 1064nm laser radiation, and its powder SHG coefficient is 2.1 times of KDP, and is suitable with LBO.
Provided by the invention 1,3-propane-diammonium five aluminum borates are the crystal that grow by water (agent) process for thermosynthesizing.Material preparation method of the present invention has that technology is simple, productive rate is high and advantage such as good reproducibility.The advantage of this material is not to be soluble in general solvent, and heat decomposition temperature point high (can be stabilized to 360 ℃ in the air atmosphere), photoabsorption is low, transparency range is big.
The prepared nonlinear optical material of this invention can be applicable to laser frequency conversion, Electro-optical Modulation, light and sells off high-tech areas such as information processing.
Embodiment
1, the preparation of compound
At first Al (i-PrO)
3(204mg) and H
3BO
3Mixture (804mg) joins 1.0mL water (H is housed
2O) and in the tetrafluoroethylene reactor of 3.0mL pyridine (pyridine) mixing solutions, use magnetic stirrer.After the question response thing dissolves fully, stop to stir.In mixing solutions, add 1 of 0.3mL, and the 3-propylene diamine (1,3-diaminopropane), make Al in the reactor (i-PrO)
3/ H
3BO
3/ 1,3-diaminopropane/pyridine/H
2The mol ratio of O is 1/6/15/37/56, and the tetrafluoroethylene reactor is packed into seals in the stainless steel high-pressure reactor then, 170 ℃ down reaction obtained water white needle-like crystal in 7 days.
2, performance test
We to obtain 1,3-propane-diammonium five aluminum borates carry out optical performance test, its second order nonlinear optical effect is about 2.1 times of KDP.
Claims (3)
1. non-linear optic crystal 1,3-propane-diammonium five aluminum borates is characterized in that: this crystal-chemical formula is [Al (B
4O
9) (BO)] NH
3CH
2CH
2CH
2NH
3, molecular weight is: 317.18, belong to oblique system, and spacer Cc (No.9), cell parameter are a=10.933 (7), b=8.297 (5),
α=γ=90 °, β=97.919 (8) °,
Z=4.
2. a claim 1 is described 1, and the preparation method of 3-propane-diammonium five aluminum borates adopts Hydrothermal Preparation, comprises the steps: reactant A l (I-PrO)
3, H
3BO
3, the mol ratio of 1,3-propylene diamine is 1: 13: 4, adopts water and pyridine to make mixed solvent, and temperature of reaction is 170 ℃, and the reaction times is 7 days.
3. 1 of a claim 1, the purposes of 3-propane-diammonium five aluminum borates is characterized in that: this crystal is used for photoelectricity communication, optical information storage, unicircuit, photoswitch, light slicer, color laser printing, blinding laser weapons, the ocean locating fish.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810071334 CN101619497B (en) | 2008-07-03 | 2008-07-03 | Non-linear optical crystal N-methyl-1,3-propane-diammonium aluminum pentaborate, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200810071334 CN101619497B (en) | 2008-07-03 | 2008-07-03 | Non-linear optical crystal N-methyl-1,3-propane-diammonium aluminum pentaborate, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101619497A CN101619497A (en) | 2010-01-06 |
| CN101619497B true CN101619497B (en) | 2013-08-14 |
Family
ID=41512903
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200810071334 Expired - Fee Related CN101619497B (en) | 2008-07-03 | 2008-07-03 | Non-linear optical crystal N-methyl-1,3-propane-diammonium aluminum pentaborate, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101619497B (en) |
-
2008
- 2008-07-03 CN CN 200810071334 patent/CN101619497B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| A novel open-framework aluminoborate with intersecting three dimensional helical channels;GuoMing Wang;《Inorganic Chemistry Communication》;20080522;第47卷(第12期);5039-5041 * |
| GuoMing Wang.A novel open-framework aluminoborate with intersecting three dimensional helical channels.《Inorganic Chemistry Communication》.2008,第47卷(第12期),5039-5041. |
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| Publication number | Publication date |
|---|---|
| CN101619497A (en) | 2010-01-06 |
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