CN1258764A - Tetragonal conical compound as non-linear optical material and crystal growth - Google Patents
Tetragonal conical compound as non-linear optical material and crystal growth Download PDFInfo
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- CN1258764A CN1258764A CN 99116465 CN99116465A CN1258764A CN 1258764 A CN1258764 A CN 1258764A CN 99116465 CN99116465 CN 99116465 CN 99116465 A CN99116465 A CN 99116465A CN 1258764 A CN1258764 A CN 1258764A
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Abstract
The compounds have a general formula of LML'2, where L is pyridine and its derivative, urea and its derivative or thiourea and its derivative; M is Zn or Cd; and L' is acac or its derivative. The compounds are complete transparent in visible light range and has high optical non-linearity and good physical and chemical properties. Relatively large monocrystal of the compounds may be produced, so that the compounds may be used as non-linear optical material.
Description
The invention relates to a novel tetragonal pyramid complex, a preparation method thereof and a crystal growth method, belonging to the chemical field of complexes and the field of optical materials.
Nonlinear optical effects originate from the interaction of the laser light with the medium. When laser light propagates in a medium with a non-zero second-order polarizability, nonlinear optical effects such as frequency doubling, sum frequency, difference frequency, parametric amplification and the like can be generated. By using the nonlinear optical effect of the crystal, nonlinear optical devices such as a second harmonic generator, a frequency converter, an optical parametric oscillator and the like can be manufactured.
Common nonlinear optical crystals in the visible light region are mainly inorganic ferroelectric crystals, such as potassium dihydrogen phosphate (KDP) and lithium niobate (LiNbO)3) Potassium titanyl phosphate (KTP), and the like. The advantages of these inorganic crystals are that sufficiently large crystals can be grown, and the comprehensive physical and chemical properties (such as optical uniformity, stability and the like) are good. However, the nonlinear optical coefficient of inorganic materials is not high enough, and it is generally difficult to use for frequency doubling of low-power laser.
The organic nonlinear optical material has developed rapidly in recent 20 years, and the greatest advantage of the organic nonlinear optical material is that the nonlinear optical coefficient of the organic material is large, and can be hundreds or even thousands of times of that of the inorganic material, and some organic crystals also have high laser damage threshold. However, organic compounds are difficult to grow into large-size and high-quality single crystals, and the mechanical strength is not high, which affects the practicability of the organic compounds.
The main application direction of the organic nonlinear optical crystal material is to use the organic nonlinear optical crystal material as a frequency doubling material in a visible light region, and to use the organic nonlinear optical crystal material as an Optical Parametric Oscillator (OPO) in a visible or infrared band, which is described in the first-stage 'Laser Focus World' special document published in 3, 15, 1998, and the organic nonlinear optical crystal materialThe material is suitable for being used as OPO, and the performance is far superior to that of lithium niobate LiNbO3。
The non-linear optical material used in visible light band must show strong non-linear optical effect and at the same time, it is completely transparent in visible light region, which is one of the contradictions, in general, the color of the compound with strong non-linear optical effect is also dark, there is another contradiction, organic molecules with large β value (microscopic second order polarizability) often have large ground state molecular dipole moment, the electrostatic interaction often leads to the formation of central symmetrical molecular arrangement and crystal space group, thus leading β value to cancel each other out and unable to show macroscopic non-linear optical effect, therefore, it is one of themain attack directions of current organic non-linear optical material research to find new material which is completely transparent in visible light region and has strong macroscopic non-linear optical effect.
The complex connects the organic ligand and the metal atom through a coordination bond, and has the characteristics of both inorganic matters and organic matters. By selecting proper ligand, metal and spatial configuration, on one hand, the crystal structure with non-central symmetry is formed with greater opportunity, and on the other hand, the contradiction between the effect and the color can be considered at the same time. In addition, many complexes have good thermal stability, chemical stability and other physical and chemical properties, and are expected to become a practical nonlinear optical material.
The invention aims to provide a novel tetragonal pyramid complex, a preparation method thereof and a crystal growth preparation method thereof. The materials should be completely transparent in the visible light region, have high optical nonlinearity and good physicochemical properties, and can be used as nonlinear optical materials.
The technical scheme adopted for realizing the above purpose of the invention is as follows:
the general formula of the novel tetragonal pyramid type complex in the invention is LML'2Wherein the ligand L can be pyridine or derivatives thereof, urea or derivatives thereof, and thiourea or derivatives thereof; the metal M is zinc or cadmium; the ligand L' is acetylacetone (acac) or a derivative thereof.
The synthesis of the complex adopts a two-step method; .
In the freshly prepared M (OH)2Adding L' into acetone suspension, heating and refluxing, gradually cleaning solution, filtering, and cooling filtrate to obtain colorless needle Crystal (CH)3)2COML′2. Then, equivalent amounts of ligands L and (CH)3)2COML′2Reacting in acetone to obtain a large amount of white precipitate, and filtering to obtain the corresponding complex.
Selecting proper solvent, measuring the solubility of the complex, and adopting a solution method for growing a single crystal:
weighing LML'2Loading into a Schlenk tube, adding a mixed solvent of acetone and acetylacetone, heating for dissolving, and adding a selected small seed crystal with complete shape and no obvious defects. Keeping the temperature for 5-10 minutes under the condition that the temperature is higher than the saturation temperature by 1-4 ℃, and then cooling to room temperature by adopting a gradual cooling method to obtain LML'2The single crystal of (1).
The following are the chemical reaction formulas for preparing some of the tetragonal pyramid complexes described in the present invention:
(1)
(2)
(3)
(4)
(5)
therefore, the penta-coordination complex is a novel tetragonal pyramid complex, has higher probability of forming a non-centrosymmetric crystal structure, is transparent in a visible light region, can change organic molecules without frequency doubling effect into complexes with frequency doubling effect, can solve the contradiction between color and effect in organic nonlinear optical materials, and can also greatly improve the physical and chemical properties of organic matters.
Compared with the background art, the method has the beneficial effects that:
the novel tetragonal pyramid complex prepared by the invention has the following characteristics:
1. most compounds have a second order frequency doubling (SHG) effect, with the largest reaching 10 times KDP (kurtz powder test);
2. the compounds are completely transparent in a visible light area, and the maximum absorption wavelength of the compounds in ethanol is about 280 nm;
3. the probability of forming a non-centrosymmetric crystal structure is high, about 80%;
4. the thermal stability is good, and the melting points of the two are all above 100 ℃;
5. the chemical stability is good, and the paint is stable to air and water;
6. a proper solvent is selected, and a single crystal with better quality can be grown by a solution method.
The technical solution of the present invention is further described with reference to the following specific examples:
example 1: c5H5N Zn(acac)2Preparation of
10g of zinc dichloride and 3g of sodium hydroxide are reacted in water to form a white zinc hydroxide precipitate. Mixing with 100ml acetone to obtain suspension, adding acetylacetone 50ml, heating under reflux, electromagnetically stirring, gradually cleaning, reacting for 1 hr, filtering, removing a little insoluble substance, standing the filtrate at room temperature, and cooling to obtain colorless needle crystals(CH3)2CO Zn(acac)2. Dissolving the colorless needle crystal in 50ml acetone, adding 6ml pyridine, stirring, standing, cooling, precipitating colorless crystal, filtering, washing with acetone, and drying to obtain colorless crystal C5H5N Zn(acac)2. Example 2: (phNH) (NH)2)C＝S Zn(acac)2(abbreviated as PZDA) production
Weighing 10g of ZnCl2And 3g of NaOH are respectively dissolved in two beakers by water, the two solutions are combined and stirred, a large amount of white precipitate is generated, the solution is filtered, washed by water and acetone and dried. Reacting the resulting Zn (OH)2Is loaded into one250ml round bottom flask, 100ml acetone and 50ml acetylacetone are weighed in, stirred and refluxed for 1 hour, Zn (OH)2All dissolved. Stopping heating, adding 5.5g phenylthiourea after the solution stops boiling, stirring to dissolve phenylthiourea quickly, standing for cooling, precipitating a large amount of colorless crystals, filtering, washing with acetone, and drying to obtain colorless crystals (phNH) (NH)2)C＝SZn(acac)2(abbreviated as PZDA). Example 3: growth of PZDA single crystals
Weighing 1.5g of PZDA, filling into a Schlenk tube, adding 50ml of mixed solvent of acetone and acetylacetone (2: 1), heating for dissolving, placing into a water tank with the temperature of about 51 ℃, and adding selected small seed crystals with complete shapes and no obvious defects. Because the temperature is higher than the saturation temperature and the compound is dissolved slowly, the temperature is kept constant for a little time at the temperature, and the method is favorable for dissolving a small amount of impurities and tiny defects on the surface. Keeping the temperature at 51 deg.C for 10 min, cooling at 2.6 deg.C/day for ten days to obtain a product with a size of 18 × 16× 15mm3The single crystal of (1).
The second-order frequency doubling effect of the complex is 10 times KDP by adopting a Kurtz powder method. Example 4: c5H5NCd(acac)2Preparation of
13.5g of cadmium dichloride and 3g of sodium hydroxide are reacted in water to prepare a fresh cadmium hydroxide precipitate. Mixing with 100ml acetone to form suspension, adding acetylacetone 50ml, heating under reflux, electromagnetically stirring, gradually cleaning solution, adding 6ml pyridine after cadmium hydroxide is completely dissolved, stirring, standing, cooling, precipitating colorless crystal, filtering, washing with acetone, and drying to obtain colorless crystal C5H5N Cd(acac)2. Example 5: (phNH) (NH)2)C＝S Cd(acac)2Preparation of
13.5g of CdCl2And 3g NaOH in water to make fresh Cd (OH)2Precipitating, dissolving in 100ml acetone and 50ml acetylacetone, adding 5.5g phenylthiourea, stirring, standing for cooling to separate colorless crystal, filtering, washing with acetone, and drying to obtain colorless crystal (phNH) (NH)2)C＝SCd(acac)2。
Claims (4)
1. A novel tetragonal pyramid type complex with a general formula of LML'2Wherein the ligand L is pyridine or derivatives thereof, urea or derivatives thereof, or thiourea or derivatives thereof; the metal M is zinc or cadmium; the ligand L' is acetylacetone or its derivative.
2. Preparation of tetragonal pyramid-type complex LML 'of claim 1'2The method of (1), characterized by: to freshly prepared M (OH)2Adding ligand L' into acetone solution, heating and refluxing to clear, filtering, and cooling to obtain (CH)3)2COML′2Crystals of the ligand L and (CH) in equivalent amounts3)2COML′2Reacting in acetone, and collecting white precipitate to obtain LML'2。
3. Preparation of LML'2A method of single crystal, characterized by: prepared from LML'2Filling the mixture into a Schlenk tube, adding a mixed solvent of acetone and acac, heating for dissolving, adding corresponding seed crystals, keeping the temperature at the saturation temperature of 1-4 ℃ for 5-10 minutes, and cooling to room temperature by adopting a gradual cooling method to obtain LML'2And (3) single crystal.
4.LML′2Single crystals are used as nonlinear optical materials or devices.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114195833A (en) * | 2021-12-27 | 2022-03-18 | 郑州轻工业大学 | Crystalline molecular base material generated by chiral mononuclear nickel third-order harmonic and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114195833A (en) * | 2021-12-27 | 2022-03-18 | 郑州轻工业大学 | Crystalline molecular base material generated by chiral mononuclear nickel third-order harmonic and preparation method thereof |
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