CN113480454A - Linear hydrogen bond type azobenzene crystal and preparation method and application thereof - Google Patents
Linear hydrogen bond type azobenzene crystal and preparation method and application thereof Download PDFInfo
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- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 30
- 239000007787 solid Substances 0.000 claims description 20
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
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- 238000001035 drying Methods 0.000 claims description 15
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- 239000012074 organic phase Substances 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- QPQKUYVSJWQSDY-CCEZHUSRSA-N 4-(phenylazo)aniline Chemical compound C1=CC(N)=CC=C1\N=N\C1=CC=CC=C1 QPQKUYVSJWQSDY-CCEZHUSRSA-N 0.000 claims description 12
- 238000004440 column chromatography Methods 0.000 claims description 12
- WSHHPNYAXLDUTG-UHFFFAOYSA-N n-(4-phenyldiazenylphenyl)acetamide Chemical compound C1=CC(NC(=O)C)=CC=C1N=NC1=CC=CC=C1 WSHHPNYAXLDUTG-UHFFFAOYSA-N 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- MMFZUKAAQGRXDU-PFONDFGASA-N Nc1ccc(cc1)[N+](\[O-])=N\c1ccccc1 Chemical compound Nc1ccc(cc1)[N+](\[O-])=N\c1ccccc1 MMFZUKAAQGRXDU-PFONDFGASA-N 0.000 claims description 11
- 239000003480 eluent Substances 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
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- 239000013067 intermediate product Substances 0.000 claims description 7
- 239000011368 organic material Substances 0.000 claims description 7
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- 239000011259 mixed solution Substances 0.000 claims description 6
- DMLAVOWQYNRWNQ-BUHFOSPRSA-N (E)-azobenzene Chemical compound C1=CC=CC=C1\N=N\C1=CC=CC=C1 DMLAVOWQYNRWNQ-BUHFOSPRSA-N 0.000 claims description 5
- 238000010992 reflux Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- HUDWXDLBWRHCKO-UHFFFAOYSA-N n'-phenylpyridine-4-carbohydrazide Chemical compound C=1C=NC=CC=1C(=O)NNC1=CC=CC=C1 HUDWXDLBWRHCKO-UHFFFAOYSA-N 0.000 claims description 2
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- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
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- 230000000052 comparative effect Effects 0.000 description 3
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- GAUZCKBSTZFWCT-UHFFFAOYSA-N azoxybenzene Chemical compound C=1C=CC=CC=1[N+]([O-])=NC1=CC=CC=C1 GAUZCKBSTZFWCT-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C291/00—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00
- C07C291/02—Compounds containing carbon and nitrogen and having functional groups not covered by groups C07C201/00 - C07C281/00 containing nitrogen-oxide bonds
- C07C291/08—Azoxy compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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Abstract
本发明公开了一种线性氢键型偶氮苯晶体及其制备方法和应用，晶体为(Z)‑2‑(4‑氨基苯基)‑1‑苯基二氮烯‑2‑氧化物，分子结构呈现出反式构型，相邻分子之间通过线性的N‑H…O线性氢键作用相互联接，形成无限延伸的一维氢键作用链，使得该化合物具备极性，并具有极强的中红外二阶非线性效应。晶体通过室温挥发结晶的方式得到，该材料的倍频系数是商业KDP的7~8倍，并且具备良好的热稳定性，在激光倍频转换、电光调制器、Q开关以及高速摄影用的快门等元器件领域有着潜在的应用价值。
The invention discloses a linear hydrogen bond type azobenzene crystal and a preparation method and application thereof, wherein the crystal is ( Z )-2-(4-aminophenyl)-1-phenyldiazene-2-oxide, The molecular structure exhibits a trans configuration, and adjacent molecules are connected to each other through linear N-H…O linear hydrogen bonds to form an infinitely extending one-dimensional hydrogen bond chain, which makes the compound polar and extremely polar. Strong mid-infrared second-order nonlinear effects. The crystal is obtained by volatilizing crystallization at room temperature. The frequency doubling coefficient of this material is 7~8 times that of commercial KDP, and it has good thermal stability. It is used in laser frequency doubling conversion, electro-optic modulator, Q switch and shutter for high-speed photography. It has potential application value in the field of components and so on.
Description
Technical Field
The invention belongs to an organic nonlinear optical material, and particularly relates to a linear hydrogen bond type azobenzene second-order nonlinear optical material and a preparation method thereof.
Background
The nonlinear optical effect results from the strong coherent light interaction of the laser light with the medium. When laser light propagates in a medium with a non-zero second-order polarizability, optical frequency doubling, sum frequency, difference frequency, optical parametric oscillation and other effects can be generated. The second-order nonlinear optical effect of the crystal can be used for preparing nonlinear optical components such as a laser frequency converter, a second harmonic generator, an optical parametric oscillator and the like, and has important application value in the high-tech fields such as optical information processing, high-speed optical communication, optical storage, electronic instruments and the like. Nonlinear optical materials can be divided into two categories according to chemical compositions, namely inorganic nonlinear optical materials and organic nonlinear optical materials. Compared with inorganic nonlinear optical materials, organic nonlinear optical materials have incomparable advantages of large nonlinear optical coefficient, fast nonlinear response, high damage threshold, low cost, easy processing, flexibility and the like, and inorganic crystals attract extensive attention of scientific researchers.
Among a plurality of organic nonlinear optical materials, azobenzene organic compounds have good photosensitivity, nonlinear optical characteristics, good thermal stability and easy film forming characteristics, and show potential application prospects in the fields of optical devices, optical information storage, biological materials and the like, and become one of research hotspots in the field in recent years. In general, the macroscopic doubling factor χ of a crystal(2)Is the vector sum of the microscopic doubling factors beta of all the molecules making up this crystal. The design concept of the traditional azobenzene second-order nonlinear material mainly comprises the following two points: (1) electron pushing groups and electron pulling groups are respectively introduced into two ends of azobenzene to form intramolecular charge transfer, and the microscopic frequency doubling coefficient beta of the molecules is improved; (2) the azobenzene molecules containing chiral centers are utilized to form polymers, so that second-order nonlinearity is macroscopically expressed. However, both of these methods have certain drawbacks. For the former, the random arrangement of molecules in the crystal may cause dipoles to cancel each other, eventually leading to a macroscopic frequency multiplication coefficient χ(2)Tends towards 0; in the latter case, the crystallinity of the polymer material is poor, and the macroscopic frequency doubling coefficient is often low, which greatly limits the application of the material.
Disclosure of Invention
The purpose of the invention is as follows: the invention aims to provide a linear azobenzene crystal which enables molecules to be directionally arranged under the action of hydrogen bonds; the second object of the present invention is to provide a process for producing the above-mentioned linear hydrogen bond-type azobenzene-based crystal; the third purpose of the invention is to provide the application of the linear hydrogen bond type azobenzene crystal as a second-order nonlinear optical material.
The technical scheme is as follows: the invention discloses a linear hydrogen bond type azobenzene crystal, which is characterized in that: the crystal is (Z) -2- (4-aminophenyl) -1-phenylDiazene-2-oxide of formula C12H11N3O, belonging to the orthorhombic system, and having a space group of Pca21Cell parameter of
α＝β＝γ＝90°、Z＝4、
Containing a chain of hydrogen bonding interactions along the crystallographic c-axis.
Furthermore, crystal molecules are in trans-azobenzene conformation, and adjacent crystal molecules are connected through N-H … O hydrogen bond action to form a one-dimensional hydrogen bond action chain.
The invention also provides a preparation method of the linear hydrogen bond type azobenzene crystal, which is characterized by comprising the following steps:
(1) dissolving 4-aminoazobenzene in acetic anhydride, stirring at room temperature until a solid appears, then adding ethyl acetate to dissolve the solid, separating out an organic phase, washing the organic phase with a saturated sodium bicarbonate aqueous solution, then adding anhydrous sodium sulfate, standing, filtering the organic phase, and spin-drying to obtain an orange solid mixture;
(2) performing column chromatography separation on the orange solid mixture obtained in the step (1) to separate an intermediate product 4-acetamido azobenzene;
(3) dissolving the intermediate product 4-acetamido azobenzene obtained in the step (2) in a mixed solution of glacial acetic acid and acetic anhydride, and then adding H2O2Reacting, when the color of the solution is changed from orange to yellow, putting the reaction solution into ice water for cooling, generating a large amount of yellow milky suspended matters, filtering and drying to obtain yellow solid;
(4) dissolving the yellow solid obtained in the step (3) in ethanol, adding NaOH aqueous solution, refluxing the reaction solution, placing the reaction solution in an ice-water bath for cooling, adding cold water into the reaction solution to generate a large amount of yellow milky suspended matters, filtering and drying to obtain a yellow crude product;
(5) performing column chromatography separation on the yellow crude product obtained in the step (4) to obtain a product (Z) -2- (4-aminophenyl) -1-phenyldiazene-2-oxide;
(6) dissolving the product of the step (5) in a mixed solvent of dichloromethane and petroleum ether, and slowly volatilizing the solvent to obtain yellow flaky crystals.
Further, in the step (1), 20-30 mmol of 4-aminoazobenzene is added to 30-40 mL of acetic anhydride.
Further, in the step (3), 30-40 mol of 4-acetamido azobenzene is added into each 120-140 mL of the mixed solution; wherein the volume ratio of glacial acetic acid to acetic anhydride in the mixed solution is 10-13: 3-5; mixing the solution with H2O2The volume ratio of (A) to (B) is 13-18: 3-6; wherein H2O2The mass percentage concentration of (B) is 25-35 wt%, preferably 30 wt%.
Further, in the step (3), the reaction temperature is 40-50 ℃, and the reaction time is 6-8 hours.
Further, the eluent used in the column chromatography separation in the step (2) and the step (5) is a mixed solvent of dichloromethane and methanol; in the step (2), the volume ratio of the dichloromethane to the petroleum ether is 10-15: 1; in the step (5), the volume ratio of dichloromethane to petroleum ether is 3-5: 1.
further, in the step (6), the volume ratio of the dichloromethane to the petroleum ether is 3-5: 1; the volatilization temperature is 20-30 ℃.
The invention further protects the application of the linear hydrogen bond type azobenzene crystal as a second-order nonlinear optical organic material. The second-order nonlinear optical organic material is mainly used for preparing laser frequency doubling conversion, an electro-optic modulator, a Q-switch and a shutter component for high-speed photography.
The structural unit diagram of the linear hydrogen bond type azobenzene crystal prepared by the invention is shown in figure 1, wherein, for a single crystal molecule in trans-azobenzene conformation, the molecule contains-NO-N-bond connection, so that O atom becomes a hydrogen bond receptor, and in the process of stacking crystal molecules, substituted-NH on benzene ring2N in (b) has a hydrogen atom as a hydrogen bond donor, and is linked to O in-NO ═ N-by linear N-H … O hydrogen bonding. With the infinite extension of hydrogen bonds, adjacent molecules are stacked into a zigzag structure by intermolecular interaction. As the molecules are directionally arranged under the action of the hydrogen bonds by introducing the groups of the hydrogen bonds into the molecules, and the N-O bonds point to the same side, the vector sum of the microscopic frequency doubling coefficients beta of all the molecules has a maximum value in the direction, and the compound has strong polarity and endows the prepared crystal with good second-order nonlinear optical properties.
The preparation principle of the invention is as follows: firstly, NH with strong electron-pushing capability is introduced on one side of benzene ring of azobenzene2The groups transfer charges in azobenzene molecules, and improve the microscopic frequency doubling coefficient beta of the molecules. Secondly, introducing a hydrogen bond acceptor through an N ═ N double bond in azoxybenzene so as to be connected with-NH2The H atoms on the N atoms form linear N-H … O strong hydrogen bonding, and finally the prepared crystal obtains good second-order nonlinear optical properties.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: the linear hydrogen bond azobenzene second-order nonlinear optical organic material (Z) -2- (4-aminophenyl) -1-phenyldiazene-2-oxide prepared by the invention shows good mid-infrared second-order nonlinear effect, and the frequency multiplication coefficient chi of the linear hydrogen bond azobenzene second-order nonlinear optical organic material(2)The KDP is 7-8 times of that of commercial KDP, and has potential application value in the field of components and parts such as laser frequency doubling conversion, electro-optic modulators, Q-switches and shutters for high-speed photography. The product has the characteristics of simple synthesis, cheap and easily obtained raw materials, environmental friendliness, high stability and the like, and is suitable for large-scale industrial production.
Drawings
FIG. 1 is a structural view of a linear hydrogen bond type azobenzene crystal of the present invention;
FIG. 2 is a diffraction pattern of a linear hydrogen bond type azobenzene crystal powder prepared in example 1;
FIG. 3 shows frequency multiplication coefficients χ of linear hydrogen bond type azobenzene crystal and commercial KDP(2)Intensity contrast map of (a);
FIG. 4 is a comparison of thermal stability test plots for linear hydrogen bond type azobenzene crystals and commercial KDP;
FIG. 5 is a crystal structure diagram of 4-aminoazobenzene in comparative example 1;
FIG. 6 is a second order nonlinear multiplication factor χ for 4-aminoazobenzene and commercial KDP prepared in comparative example 1(2)Intensity contrast map of
Detailed Description
The technical solution of the present invention is further described in detail with reference to the accompanying drawings and examples.
Example 1
(1) 25mmol of 4-aminoazobenzene are dissolved in 35mL of acetic anhydride and stirred at room temperature until a solid appears, then ethyl acetate is added to dissolve the solid, the organic phase is separated off and saturated NaHCO is used3The organic phase was washed with an aqueous solution, followed by addition of anhydrous Na2SO4Standing for 30min, filtering the organic phase, and spin-drying to obtain an orange solid mixture;
(2) and (3) carrying out column chromatography separation on the obtained orange solid mixture, wherein an eluent is a mixture of 13: 1, and separating an intermediate product, namely 4-acetamido azobenzene;
(3) 40mmol of the intermediate obtained 4-acetamidoazobenzene were dissolved in 100mL of glacial acetic acid and 30mL of acetic anhydride, and 40mL of 30% strength H were added2O2Stirring the reaction solution in an oil bath kettle at the temperature of 50 ℃ for 4 hours at constant temperature, gradually changing the color of the solution from orange to yellow, then placing the reaction solution in ice water for cooling, generating a large amount of yellow milky suspended matters, filtering and drying to obtain yellow solid;
(4) dissolving the obtained yellow solid in ethanol, adding a concentrated NaOH aqueous solution, refluxing the reaction solution for 2h, then placing the reaction solution in an ice-water bath for cooling, adding cold water into the reaction solution to generate a large amount of yellow milky suspended matters, filtering and drying to obtain a yellow crude product;
(5) and (3) carrying out column chromatography separation on the obtained yellow crude product, wherein an eluent is a mixture of an eluent and a solvent in a volume ratio of 3: 1, and separating a final product (Z) -2- (4-aminophenyl) -1-phenyldiazene-2-oxide;
(6) the final product was dissolved in a volume ratio of 3: 1 at 25 ℃, stirring in a 100mL beaker until the solvent is uniformly dissolved and is slowly volatilized at room temperature, and precipitating yellow flaky crystals after about 1-2 days.
Selecting the size of 0.20 × 0.20 × 0.20mm3The crystals of (2) were used for single crystal structure analysis, and single crystal Diffraction data were collected on a Rigaku Oxford Diffraction,2020 diffractometer, and the crystal structure data of the resulting compounds are shown in Table 1.
TABLE 1 Main crystallographic data of the compound (Z) -2- (4-aminophenyl) -1-phenyldiazene-2-oxide
[a]R1＝Σ||Fo|-|Fc||/|Fo|.[b]wR2＝[Σw(Fo 2-Fc 2)2]/Σw(Fo 2)2]1/2.[c]Maximum and minimum residual electron density.
The crystal structure of the obtained yellow plate-like crystals was analyzed at 293K, and it was found to be in a trans-azobenzene conformation. Using an orthogonal polar crystal system, space group Pca21，
α＝β＝γ＝90°，
The Z value is 4. During the molecular stacking process of the crystal, hydrogen bonds between adjacent molecules are formed through N-H … OThe interactions form a one-dimensional chain along the crystallographic c-axis. Due to the macroscopic frequency multiplication coefficient chi of the crystal(2)Is the vector sum of microscopic frequency multiplication coefficients beta of all molecules forming the crystal, so that the linear hydrogen bond type azobenzene compound has such high second-order nonlinear coefficient chi(2)7-8 times the commercial KDP in intensity.
Referring to fig. 2, the characteristic peaks 2 θ are 10.2 °, 13.2 °, 16.8 °, 19.0 °, 19.7 °, 21 °, 22 °, 23.6 °, 26 °, 26.3 °, 27.2 °, 27.8 °, 30.98 °, and 31.7 °, which indicates that the obtained powder diffraction experimental data of the yellow flaky block crystal completely coincided with the simulated data, indicating that the purity of the prepared compound is high.
The yellow patch crystals (Z) -2- (4-aminophenyl) -1-phenyldiazene-2-oxide obtained were compared in terms of properties with commercial KDP. Firstly, grinding the prepared yellow block crystal into powder with the particle size of about 200-300 mu m, then taking about 3-5 mg of powder sample to be clamped in a transparent glass sheet with the size of 1cm multiplied by 1cm, and then placing the glass sheet on a laser light path, wherein the Nd: YAG pulse laser generates 1064nm fundamental frequency light as light source, which is transmitted through a sample clamped by glass, and the generated signal is displayed on an oscilloscope through a photomultiplier tube. Similarly, KDP crystal as reference was ground to a powder of about 200-300 μm size and tested in the same experimental conditions. Referring to FIG. 3, the macroscopic doubling factor χ of (Z) -2- (4-aminophenyl) -1-phenyldiazene-2-oxide with commercial KDP(2)Intensity comparison, χ of product(2)The KDP is 14-15 times higher than that of the commercial KDP; also, see FIG. 4, χ of product(2)Along with the stability test of the temperature, the sample is gradually melted when the temperature reaches 410K-420K, namely chi(2)Then it falls to 0.
(Z) -2- (4-aminophenyl) -1-phenyldiazene-2-oxide is capable of exhibiting such a strong macroscopic frequency doubling factor χ(2)And high thermodynamic temperature properties, all thanks to the strong hydrogen bonding interactions of N-H … O formed when the compound crystallizes. The N-H … O hydrogen bond action not only makes the molecules orderly arranged along the same direction in the stacking process, but also promotes the macroscopic frequency doubling coefficient chi(2)Presenting a maximum value; and the molecules are combined more tightly, so that the thermal stability of the compound is greatly improved.
Example 2
(1) 30mmol of 4-aminoazobenzene are dissolved in 40mL of acetic anhydride and stirred at room temperature until a solid appears, then ethyl acetate is added to dissolve the solid, the organic phase is separated off and saturated NaHCO is used3The organic phase was washed with an aqueous solution, followed by addition of anhydrous Na2SO4Standing for 30min, filtering the organic phase, and spin-drying to obtain an orange solid mixture;
(2) and (3) carrying out column chromatography separation on the obtained orange solid mixture, wherein an eluent is a mixture of 15: 1, and separating an intermediate product, namely 4-acetamido azobenzene;
(3) 35mmol of the intermediate obtained 4-acetamidoazobenzene were dissolved in 110mL of glacial acetic acid and 40mL of acetic anhydride, and 60mL of 30% strength H were added2O2Stirring the reaction solution in an oil bath kettle at 40 ℃ for 5 hours at constant temperature, gradually changing the color of the solution from orange to yellow, then placing the reaction solution in ice water for cooling, generating a large amount of yellow milky suspended matters, filtering and drying to obtain yellow solid;
(4) dissolving the obtained yellow solid in ethanol, adding a concentrated NaOH aqueous solution, refluxing the reaction solution for 2h, then placing the reaction solution in an ice-water bath for cooling, adding cold water into the reaction solution to generate a large amount of yellow milky suspended matters, filtering and drying to obtain a yellow crude product;
(5) and (3) carrying out column chromatography separation on the obtained yellow crude product, wherein an eluent is a mixture of an eluent and a solvent in a volume ratio of 4: 1, and separating a final product (Z) -2- (4-aminophenyl) -1-phenyldiazene-2-oxide;
(6) the final product was dissolved in a volume ratio of 4: 1 at the temperature of 20 ℃, stirring in a 100mL beaker until the solvent is uniformly dissolved, slowly volatilizing in a room-temperature environment, and precipitating yellow flaky crystals after about 1-2 days.
Example 3
(1) 20mmol of 4-aminoazobenzene are dissolved in 30mL of acetic anhydride and stirred at room temperature until a solid appears, then ethyl acetate is added to dissolve the solid, the organic phase is separated off and saturated NaHCO is used3The organic phase was washed with an aqueous solution, followed by addition of anhydrous Na2SO4Standing for 30min, filtering the organic phase, and spin-drying to obtain an orange solid mixture;
(2) and (3) carrying out column chromatography separation on the obtained orange solid mixture, wherein an eluent is a mixture of 10: 1, and separating an intermediate product, namely 4-acetamido azobenzene;
(3) the resulting intermediate, 30mmol of 4-acetamidoazobenzene, was dissolved in 130mL of glacial acetic acid and 50mL of acetic anhydride, followed by the addition of 50mL of 30% strength H2O2Stirring the reaction solution in an oil bath kettle at the temperature of 45 ℃ for 8 hours at constant temperature, gradually changing the color of the solution from orange to yellow, then placing the reaction solution in ice water for cooling, generating a large amount of yellow milky suspended matters, filtering and drying to obtain yellow solid;
(4) dissolving the obtained yellow solid in ethanol, adding a concentrated NaOH aqueous solution, refluxing the reaction solution for 2h, then placing the reaction solution in an ice-water bath for cooling, adding cold water into the reaction solution to generate a large amount of yellow milky suspended matters, filtering and drying to obtain a yellow crude product;
(5) and (3) carrying out column chromatography separation on the obtained yellow crude product, wherein an eluent is a mixture of an eluent and a solvent in a volume ratio of 5: 1, and separating a final product (Z) -2- (4-aminophenyl) -1-phenyldiazene-2-oxide;
(6) the final product was dissolved in a volume ratio of 5: 1 at 30 ℃, stirring in a 100mL beaker until the solvent is uniformly dissolved and is slowly volatilized at room temperature, and precipitating yellow flaky crystals after about 1-2 days.
Comparative example 1
Directly selecting 4-aminoazobenzene, dissolving in absolute ethyl alcohol, stirring in a 100ml beaker until the mixture is uniformly dissolved and clear, slowly volatilizing in a room temperature environment, and precipitating orange yellow strip crystals after about 1-2 days.
Selecting the size of 0.20 × 0.20 × 0.20mm3The crystals of (2) were used for single crystal structure analysis, and single crystal Diffraction data were collected on a Rigaku Oxford Diffraction,2020 diffractometer, and the crystal structure data of the resulting compounds are shown in Table 2.
TABLE 2 Main crystallographic data of the compound 4-aminoazobenzene
The obtained orange yellow stripe crystal was analyzed for its crystal structure at 293K, see fig. 5, and found to be also in trans-azobenzene conformation, but the crystal did not form significant hydrogen bond interactions during molecular stacking. By using a monoclinic polar crystal system, space group Pn,
β＝98.369(6)°，
the Z value is 2. During the molecular stacking process, the crystal does not form obvious hydrogen bond interaction.
Subjecting it to second-order nonlinear coefficient χ(2)And (6) testing. Similarly, according to the above preparation method, 4-aminoazobenzene crystals were ground into powder having a particle size of about 200 to 300 μm, then about 3 to 5mg of the powder sample was sandwiched between transparent glass plates having a size of 1cm × 1cm, and the glass plates were placed on a laser light path, and experiment was carried out using a Nd: YAG pulse laser as a light source to generate 1064nm fundamental frequency light to transmit through the sample sandwiched by the glass, and the generated signal was displayed on an oscilloscope via a photomultiplier. Referring to FIG. 6, the macroscopic second-order nonlinear frequency doubling factor χ of the 4-aminoazobenzene compound(2)About 1.3-1.4, which is only 0.7-0.8 times of that of commercial KDP, and is far lower than the linear hydrogen bond azobenzene second-order nonlinear optical organic material in the embodiment 1. The fact that the molecules are directionally arranged under the action of hydrogen bonds by introducing the groups of the hydrogen bonds into the molecules is proved to be the key point for endowing the linear hydrogen bond type azobenzene crystal prepared by the invention with good second-order nonlinear optical properties.
Claims (10)
1. A linear hydrogen bond type azobenzene crystal characterized in that: the crystal is (Z) -2- (4-aminophenyl) -1-phenyldiazene-2-oxide, and the molecular formula is C12H11N3O, belonging to the orthorhombic system, and having a space group of Pca21Cell parameter of
α＝β＝γ＝90°、Z＝4、
Containing a chain of hydrogen bonding interactions along the crystallographic c-axis.
2. The linear hydrogen bond-type azobenzene crystal according to claim 1, wherein: the crystal molecules are in trans-azobenzene conformation, and adjacent crystal molecules are connected through N-H … O hydrogen bond action to form a one-dimensional hydrogen bond action chain.
3. The method for producing a linear hydrogen bond-type azobenzene crystal according to claim 1 or 2, comprising the steps of:
(1) dissolving 4-aminoazobenzene in acetic anhydride, stirring at room temperature until a solid appears, then adding ethyl acetate to dissolve the solid, separating out an organic phase, washing the organic phase with a saturated sodium bicarbonate aqueous solution, then adding anhydrous sodium sulfate, standing, filtering the organic phase, and spin-drying to obtain an orange solid mixture;
(2) performing column chromatography separation on the orange solid mixture obtained in the step (1) to separate an intermediate product 4-acetamido azobenzene;
(3) dissolving the intermediate product 4-acetamido azobenzene obtained in the step (2) in a mixed solution of glacial acetic acid and acetic anhydride, and then adding H2O2Reacting, when the color of the solution is changed from orange to yellow, putting the reaction solution into ice water for cooling, generating a large amount of yellow milky suspended matters, filtering and drying to obtain yellow solid;
(4) dissolving the yellow solid obtained in the step (3) in ethanol, adding NaOH aqueous solution, refluxing the reaction solution, placing the reaction solution in an ice-water bath for cooling, adding cold water into the reaction solution to generate a large amount of yellow milky suspended matters, filtering and drying to obtain a yellow crude product;
(5) performing column chromatography separation on the yellow crude product obtained in the step (4) to obtain a product (Z) -2- (4-aminophenyl) -1-phenyldiazene-2-oxide;
(6) dissolving the product of the step (5) in a mixed solvent of dichloromethane and petroleum ether, and slowly volatilizing the solvent to obtain yellow flaky crystals.
4. The method for producing a linear hydrogen bond-type azobenzene crystal according to claim 3, characterized in that: in the step (1), 20-30 mmol of 4-aminoazobenzene is added to every 30-40 mL of acetic anhydride.
5. The method for producing a linear hydrogen bond-type azobenzene crystal according to claim 3, characterized in that: in the step (3), 30-40 mol of 4-acetamido azobenzene is added into every 120-140 mL of the mixed solution; wherein the volume ratio of glacial acetic acid to acetic anhydride in the mixed solution is 10-13: 3-5; mixing the solution with H2O2The volume ratio of (A) to (B) is 13-18: 3-6; wherein H2O2The mass percentage concentration of the component (A) is 25-35 wt%.
6. The method for producing a linear hydrogen bond-type azobenzene crystal according to claim 3, characterized in that: in the step (3), the reaction temperature is 40-50 ℃, and the reaction time is 6-8 h.
7. The method for producing a linear hydrogen bond-type azobenzene crystal according to claim 3, characterized in that: the eluent adopted in the column chromatography separation in the step (2) and the step (5) is a mixed solvent of dichloromethane and methanol; in the step (2), the volume ratio of the dichloromethane to the petroleum ether is 10-15: 1; in the step (5), the volume ratio of dichloromethane to petroleum ether is 3-5: 1.
8. the method for producing a linear hydrogen bond-type azobenzene crystal according to claim 3, characterized in that: in the step (6), the volume ratio of dichloromethane to petroleum ether is 3-5: 1; the volatilization temperature is 20-30 ℃.
9. Use of the linear hydrogen bond-type azobenzene crystal according to claim 1 as a second-order nonlinear optical organic material.
10. Use according to claim 9, characterized in that: the second-order nonlinear optical organic material is mainly used for preparing laser frequency doubling conversion, electro-optic modulators, Q-switches and shutter components for high-speed photography.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US5075043A (en) * | 1988-11-21 | 1991-12-24 | Eastman Kodak Company | Optical article containing a linear condensation polymer exhibiting a high level of second order polarization susceptibility |
| CN108424377A (en) * | 2018-04-19 | 2018-08-21 | 温州大学 | A kind of synthetic method of asymmetric oxidation azobenzene compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5075043A (en) * | 1988-11-21 | 1991-12-24 | Eastman Kodak Company | Optical article containing a linear condensation polymer exhibiting a high level of second order polarization susceptibility |
| CN108424377A (en) * | 2018-04-19 | 2018-08-21 | 温州大学 | A kind of synthetic method of asymmetric oxidation azobenzene compound |
Non-Patent Citations (2)
| Title |
|---|
| DOMANSKI, ANDRZEJ ET AL.: ""Two trans-4-aminoazoxybenzenes"", 《ACTA CRYSTALLOGRAPHICA, SECTION C: CRYSTAL STRUCTURE COMMUNICATIONS》 * |
| EJSMONT, KRZYSZTOF ET AL.: ""Orthorhombic polymorphs of two trans-4-aminoazoxybenzenes"", 《ACTA CRYSTALLOGRAPHICA, SECTION C: CRYSTAL STRUCTURE COMMUNICATIONS》 * |
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