CN102191550B - Nonlinear optical crystals cadmium diethyldithiocarbamate aluminum hexaborate and preparation method and application thereof - Google Patents
Nonlinear optical crystals cadmium diethyldithiocarbamate aluminum hexaborate and preparation method and application thereof Download PDFInfo
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- CN102191550B CN102191550B CN201010116297.XA CN201010116297A CN102191550B CN 102191550 B CN102191550 B CN 102191550B CN 201010116297 A CN201010116297 A CN 201010116297A CN 102191550 B CN102191550 B CN 102191550B
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- Prior art keywords
- aluminum
- cadmium
- diethylenetriamine
- hexaborate
- nonlinear optical
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Abstract
The invention relates to nonlinear optical crystals cadmium diethyldithiocarbamate aluminum hexaborate, a preparation method and application thereof. A chemical formula of the crystals is [Cd(dien)2][AlB6O11(OH)]; the molecular weight is 603.61; the crystals belong to a monoclinic system; the space group is Pc; and unit cell parameters are that: a= 9.4602(19), b= 10.765(2), c=13.816(4)Angstrom, alpha=gamma= 90 degrees, beta= 129.657(19) degrees, V=1083.2(4)Angstrom<3>, and Z= 2. The cadmium diethyldithiocarbamate aluminum hexaborate is prepared by a hydro(solvo)thermal method. The cadmium diethyldithiocarbamate aluminum hexaborate has certain nonlinear optical properties; and the powder second harmonic generation (SHG) coefficient of the cadmium diethyldithiocarbamate aluminum hexaborate is 1.7 times that of potassium dihydrogen phosphate (KDP).
Description
Technical field
The present invention relates to a kind of nonlinear optical material diethylenetriamine and close cadmium six aluminum borate (chemical formula: [Cd (dien)
2] [AlB
6o
11(OH) Synthesis and applications]).
Background technology
Nonlinear optics (Nonlinear Optics, NLO) is a frontier of contemporary optics, is the science of research nonlinear relationship that the response of material and field intensity present under high light effect.In numerous non-linear optical effects, frequency-doubled effect (SHG) is the most noticeable is also the non-linear effect studying at most.There is the optical material of non-linear effect in modern science and technology, particularly in some civilian and military high-tech areas, such as photoelectric communication, optical information storage, unicircuit, photoswitch, optical limiter, color laser printing, the ocean locating fish etc., have a series of important application.
For a long time, the borate crystal of nonlinear optics is the study hotspot of people 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.Although these nonlinear optical materials are widely used in all trades and professions, but different fields is also different to the requirement of nonlinear optical material, and single nonlinear optical material therefore can not be had optimization can be applied to all fields.This just proposes 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 find 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 dresses up the strategy of the non-heart or chiral structure, thus obtains the novel non-linearity optical material of superior performance.
Summary of the invention
The object of the invention is to prepare a kind of non-linear optic crystal diethylenetriamine and close cadmium six aluminum borate (chemical formula: [Cd (dien)
2] [AlB
6o
11(OH)]), its technical scheme is as follows:
We select CdAc
24H
2o (nickel acetate), Al (i-PrO)
3(aluminum isopropylate), H
3bO
3(boric acid) is raw material, and its mol ratio is 0.6:1:5.6, under diethylenetriamine (dien) existence condition, adopts water and pyridine to make mixed solvent, at 180 DEG C, utilizes the chirality AlO that aluminum isopropylate is hydrolyzed into
4the non-the heart-yin ion cluster that group and boric acid aggregate into is collaborative assembles, and makes counter ion with diethylenetriamine conjunction cadmium coordination cation, obtains the crystalline material that diethylenetriamine closes cadmium six aluminum borate under water (agent) heat condition.
We record the single crystal structure of this compound, and its structural parameter are as follows:
Chemical formula is [Cd (dien)
2] [AlB
6o
11(OH)], molecular weight is: 603.61, and belong to oblique system, spacer Pc, cell parameter is a=9.4602 (19), b=10.765 (2),
α=γ=90 °, β=129.657 (19) °,
z=2.
Close in the structure of cadmium six aluminum borate at diethylenetriamine, AlO
4, B
6o
11(OH) be connected to by being total to summit the spacious skeleton structure of three-dimensional that has 7-/9-/11-/13-membered ring channel, coordination cation is filled in 13-membered ring channel as counter ion.Nonlinear optics measurement shows, diethylenetriamine closes cadmium six aluminum borate and has good non-linear optical property, and under 1064nm laser radiation, export very strong 532nm green glow, its powder SHG coefficient is 1.7 times of KDP.Expection has certain using value in high-tech areas such as laser frequency conversion, Electro-optical Modulation, Preset grating information processings.
It is the crystal grown by water (agent) process for thermosynthesizing that diethylenetriamine provided by the invention closes cadmium six aluminum borate.Material preparation method of the present invention has that technique is simple, productive rate is high and the advantage such as reproducible.The advantage of this material is not soluble in general solvent.This crystal is used for the fields such as photoelectric communication, optical information storage, unicircuit, photoswitch, optical limiter, color laser printing, the ocean locating fish, laser frequency conversion, Electro-optical Modulation, Preset grating information processing.
Embodiment
1, the preparation of compound
0.6mmol CdAc
24H
2o, 1.0mmol Al (i-PrO)
3, 5.6mmol H
3bO
3mixture in add 3mL pyridine and 2mL water, 0.7mL diethylenetriamine (dien) is added after Keep agitation agglutination, this mixture is transferred in the stainless steel cauldron of 23mL inner liner polytetrafluoroethylene lining, react 11 days in the baking oven of 180 DEG C, naturally cool to room temperature, suction filtration, distilled water wash, air drying, obtains clear crystal.
2, performance test
We close cadmium six aluminum borate to diethylenetriamine and carry out optical performance test, and its second order nonlinear optical effect is about 1.7 times of KDP.
Claims (3)
1. non-linear optic crystal diethylenetriamine closes cadmium six aluminum borate, is characterised in that: its chemical formula is [Cd (dien)
2] [AlB
6o
11(OH)], molecular weight is: 603.61, and belong to oblique system, spacer Pc, cell parameter is a=9.4602 (19), b=10.765 (2),
α=γ=90 °, β=129.657 (19) °,
z=2.
2. the diethylenetriamine of claim 1 closes a preparation method for cadmium six aluminum borate, adopts the hot legal system of water solvent standby, it is characterized in that: adopt CdAc
24H
2o or Cd (OH)
2, Al (i-PrO)
3, H
3bO
3be raw material with diethylenetriamine, react in the mixed solvent of pyridine and water, temperature of reaction is 180 DEG C.
3. the diethylenetriamine described in claim 1 closes a potential use for cadmium six aluminum borate, it is characterized in that: this crystal is used for photoelectric communication, optical information storage, unicircuit, photoswitch, optical limiter, color laser printing, the ocean locating fish, laser frequency conversion, Electro-optical Modulation, Preset grating field of information processing.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010116297.XA CN102191550B (en) | 2010-03-02 | 2010-03-02 | Nonlinear optical crystals cadmium diethyldithiocarbamate aluminum hexaborate and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201010116297.XA CN102191550B (en) | 2010-03-02 | 2010-03-02 | Nonlinear optical crystals cadmium diethyldithiocarbamate aluminum hexaborate and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102191550A CN102191550A (en) | 2011-09-21 |
| CN102191550B true CN102191550B (en) | 2015-05-13 |
Family
ID=44600388
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201010116297.XA Expired - Fee Related CN102191550B (en) | 2010-03-02 | 2010-03-02 | Nonlinear optical crystals cadmium diethyldithiocarbamate aluminum hexaborate and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102191550B (en) |
-
2010
- 2010-03-02 CN CN201010116297.XA patent/CN102191550B/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| A new layered aluminoborate [Zn(dien)2][{Al(OH)}{B5O9F}] templated by transition metal complexes;Jian Zhou et al.;《CrystEngComm》;20090821;第11卷;第2597-2600页 * |
| A Series of Open-Framework Aluminoborates Templated by Transition-Metal Complexes;Jian Zhou et al.;《Chemistry A European Journal》;20100322;第16卷;第4852-4863页 * |
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| Publication number | Publication date |
|---|---|
| CN102191550A (en) | 2011-09-21 |
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