阅读说明：本技术 p-甲基苯磺酸[4-(4-二乙基氨苯乙烯基)甲基吡啶]水合物、制备方法及应用 (P-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine ] hydrate, preparation method and application ) 是由 孙志华 刘艺 郭吴倩 罗军华 于 2020-12-28 设计创作，主要内容包括：本发明涉及p-甲基苯磺酸[4-(4-二乙基氨苯乙烯基)甲基吡啶]水合物、制备方法及应用。该化合物的化学分子式为C-(25)H-(32)N-2O-4,组成为C-(18)H-(23)N-2·CH-3C-6H-4SO-3·H-2O,属于三斜晶系,空间群为P-1,晶胞参数为a＝7.9587(3),b＝9.6568(4),α＝92.889(4)°,β＝98.665(4)°,γ＝101.321(4)°,Z＝2和本发明的化合物主要表现为明显的饱和吸收特性,且其制备过程具有反应条件温和、合成路线简单和原料易得等优点,作为非线性饱和吸收材料在激光脉冲压缩、光学双稳态器件等方面具有潜在的实施价值。(The invention relates to p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine]Hydrate, preparation method and application. The chemical formula of the compound is C 25 H 32 N 2 O 4 With the composition C 18 H 23 N 2 ·CH 3 C 6 H 4 SO 3 ·H 2 O belongs to a triclinic system, the space group is P-1, the unit cell parameters are a-7.9587 (3), b-9.6568 (4), a is 92.889(4) °, β is 98.665(4) °, γ is 101.321(4) °, Z is 2 and the compound mainly has obvious saturation absorption characteristics, and the preparation process has the advantages of mild reaction conditions, simple synthetic route, easily obtained raw materials and the like, and has potential implementation values in the aspects of laser pulse compression, optical bistable devices and the like as a nonlinear saturation absorption material.)

P-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine]Hydrate of the sameCharacterized in that the p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine]The chemical formula of the hydrate is C₂₅H₃₂N₂O₄With the composition C₁₈H₂₃N₂·CH₃C₆H₄SO₃·H₂O belongs to a triclinic system, the space group is P-1, the unit cell parameters are a-7.9587 (3), b-9.6568 (4),a is 92.889(4) °, β is 98.665(4) °, γ is 101.321(4) °, Z is 2 and

2. a process for preparing p-toluenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine ] hydrate according to claim 1, comprising the steps of:

(1) at room temperature, mixing a stoichiometric ratio of 1: 1: dissolving 4-diethylaminobenzaldehyde, methyl iodide and 4-methylpyridine of 1 in absolute methanol, heating to 65-75 ℃, adding 5-10ml of piperidine, carrying out reflux reaction for 24-48h until the color of the solution gradually changes from light yellow to dark red, cooling, crystallizing, filtering and drying to obtain an iodinated 4- (4-diethylaminostyryl) methylpyridine salt;

(2) dissolving p-methyl benzene sulfonic acid sodium salt and the iodized 4- (4-diethylaminostyryl) picoline salt obtained in the step (1) in a mixed solution of water and methanol according to a stoichiometric ratio of 1:1, and reacting for 24-48h to obtain p-methyl benzene sulfonic acid [4- (4-diethylaminostyryl) picoline ] hydrate; the volume ratio of water to methanol in the mixed solution of water and methanol is 1: 1-5.

Use of p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) picoline ] hydrate in a laser pulse compressor, characterized in that: the laser pulse compressor comprising p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine ] hydrate according to claim 1.

Use of p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine ] hydrate in an optically bistable device, characterized in that: the optically bistable device comprises p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine ] hydrate according to claim 1.

5. Laser pulse compressor, its characterized in that: the laser pulse compressor comprises p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine ] hydrate.

6. An optical bistable device, characterized by: the optical bistable device comprises p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine ] hydrate.

Technical Field

The invention belongs to the field of functional materials, and particularly relates to a p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine ] hydrate, and a preparation method and application thereof.

Background

Modern society develops rapidly towards high information quantity and high-speed information exchange, and the requirements on information acquisition, processing, transmission, storage, display and the like are higher and higher. The current optical fiber communication technology and communication system have been developed rapidly, but there still exist a lot of electronic devices for signal switching and processing in the related equipment, and these devices often have the disadvantages of clock skew, severe crosstalk, high loss, slow response rate, etc., and become a potential bottleneck for further improving the optical information storage and carrying capability. Optical elements designed based on third-order nonlinear optical materials (e.g., all-optical switches, optical calculators, optical cross-connects, and phase complex conjugates) are expected to play an important role in the next-generation information communication industry, and are expected to be strong candidates for solving the above-mentioned problems. Therefore, the third-order nonlinear optical material has a wide application prospect in the fields of optical information processing, optical calculation, optical communication, optical amplitude limiting and the like, and is widely concerned by people.

Currently, the research objects of the third-order nonlinear optical effect mainly focus on inorganic materials, organic materials, metal-organic complexes and the like. Nonlinear optical effects originate from inorganic materials, which have large electric polarizability and are practically used in many fields. Generally, the nonlinear effect of inorganic materials originates from the electronic properties of the materials, and the nonlinear optical coefficients thereof are closely related to the electronic structure; the response mechanism is mainly lattice distortion and resonance absorption, so that the response time of the optical device is generally longer, and the obvious defects exist in the process of developing the optical technology to ultra-high speed and ultra-high capacity. Meanwhile, the inorganic material also has the characteristics of more complicated preparation process, less selectable types, single device type and the like. In contrast, the nonlinear response of organic molecular materials arises from the interaction of delocalized pi-electrons with photons, the off-resonance time of the electrons being much in the order of fs, a process involving photon absorption and depending on the excited state lifetime, the recovery time for multiphoton annihilation being in the order of ps. Therefore, the organic material has the advantages of larger nonlinear optical coefficient, wide light transmission range, short response time, easy molecular tailoring and modification, good processing performance and the like. In recent years, organic materials having a three-order nonlinear optical effect are gradually emphasized by people, and materials with excellent performance are gradually developed, such as polythiophene, azo compounds, phthalocyanine porphyrin compounds, organic thioketone, ferrocene derivative polymers and other materials with a larger pi electron conjugated system, fullerene, high molecular polymers, atom cluster compounds and the like.

For organic third-order nonlinear molecular materials, a large pi electron conjugated structure with an intramolecular charge transfer system is an important structural factor influencing nonlinear performance, and the conjugated structure is also a main characteristic of organic dye molecules. Under the action of strong laser, the geometric relaxation of molecules originates from the instantaneous change of excited state pi electron density, i.e. the great correction of wave function, and the change of the whole molecule excited state pi electron is the key to cause nonlinear optical polarization. The organic dye molecule generally has a larger pi-electron conjugated system, the electron delocalization effect and the non-simple harmonic effect of electrons are obvious, and the photoinduced excitation easily increases the transition dipole moment in the molecule so as to present a more obvious third-order nonlinear optical effect. Therefore, a novel organic molecular material with excellent third-order nonlinear optical effect can be designed by using the structural model of the organic color body.

Disclosure of Invention

The invention aims to provide p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) picoline ] hydrate, a preparation method of the p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) picoline ] hydrate, and application of the p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) picoline ] hydrate in laser pulse compressors and optical bistable devices.

Scheme I)

The p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine of the present invention]The chemical formula of the hydrate is C₂₅H₃₂N₂O₄With the composition C₁₈H₂₃N₂·CH₃C₆H₄SO₃·H₂O belongs to a triclinic system, the space group is P-1, the unit cell parameters are a-7.9587 (3), b-9.6568 (4),a is 92.889(4) °, β is 98.665(4) °, γ is 101.321(4) °, Z is 2 and

scheme two)

The preparation method of the p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine ] hydrate comprises the following steps:

(1) at room temperature, mixing a stoichiometric ratio of 1: 1: dissolving 4-diethylaminobenzaldehyde, methyl iodide and 4-methylpyridine of 1 in absolute methanol, heating to 65-75 ℃, adding 5-10ml of piperidine, carrying out reflux reaction for 24-48h until the color of the solution gradually changes from light yellow to dark red, cooling, crystallizing, filtering and drying to obtain an iodinated 4- (4-diethylaminostyryl) methylpyridine salt;

(2) dissolving p-methyl benzene sulfonic acid sodium salt and 4- (4-diethylaminostyryl) picolinate iodide obtained in the step (1) in a mixed solution of water and methanol according to a stoichiometric ratio of 1:1, and reacting for 24-48hh to obtain p-methyl benzene sulfonic acid [4- (4-diethylaminostyryl) picoline ] hydrate; the volume ratio of water to methanol in the mixed solution of water and methanol is 1: 1-5.

Scheme three)

Use of p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) picoline ] hydrate in a laser pulse compressor comprising the p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) picoline ] hydrate.

Use of p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) picoline ] hydrate in an optically bistable device comprising said p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) picoline ] hydrate.

Scheme four)

A laser pulse compressor comprising said p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) picoline ] hydrate.

An optically bistable device, said optically bistable device comprising said p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine ] hydrate.

The organic three-order nonlinear optical molecular material provided by the invention is p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine]The hydrate has a stronger pi electron conjugated system in the molecular structure of the compound. The crystal structure is tested by X-single crystal diffraction, and the result shows that the chemical formula is C₂₅H₃₂N₂O₄Ion composition of C₁₈H₂₃N₂ ⁺·CH₃C₆H₄SO₃ ^-·H₂And O. The crystal is crystallized in a triclinic system under the condition of methanol at room temperature, the space group is P-1, the unit cell parameters are a-7.9587 (3), b-9.6568 (4),a is 92.889(4) °, β is 98.665(4) °, γ is 101.321(4) °, Z is 2 and

compared with the prior art, the invention has the following beneficial effects: the invention provides p-toluenesulfonic acid [4- (4-diethylaminostyryl) picoline ] hydrate, which mainly shows obvious saturated absorption characteristics. In addition, the preparation process of the compound has the advantages of mild reaction conditions, simple synthetic route, easily obtained raw materials and the like, and has potential implementation value in the aspects of laser pulse compression, optical bistable devices and the like as a nonlinear saturated absorption material.

Drawings

FIG. 1 is a molecular structural diagram of p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine ] hydrate according to the present invention.

FIG. 2 is a crystal structure packing diagram of p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine ] hydrate according to the present invention.

FIG. 3 is a Z-scan open pore curve of an acetonitrile solution of p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine ] hydrate according to the present invention.

FIG. 4 is a Z-scan closed/open cell curve of an acetonitrile solution of p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine ] hydrate of the present invention.

Detailed Description

The invention is further described with reference to the following figures and detailed description.

Example 1

The preparation method of the p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine ] hydrate comprises the following steps:

(1) at room temperature, mixing a stoichiometric ratio of 1: 1: dissolving 4-diethylaminobenzaldehyde, methyl iodide and 4-methylpyridine of 1 in absolute methanol, heating to 65 ℃, adding 5ml of piperidine, refluxing for 24 hours until the color of the solution gradually changes from light yellow to dark red, cooling, crystallizing, filtering and drying to obtain 4- (4-diethylaminostyryl) methylpyridine iodide;

(2) dissolving the sodium p-methylbenzenesulfonate and the 4- (4-diethylaminostyryl) methylpyridine iodide obtained in the step (1) in a mixed solution of water and methanol in a stoichiometric ratio of 1:1, and reacting for 24 hours to obtain the p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine ] hydrate; the volume ratio of water to methanol in the mixed solution of water and methanol is 1: 1.

the p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine ] obtained above was reacted with a carboxylic acid]The hydrate is tested for the crystal structure by X-single crystal diffraction, and the result shows that the chemical formula of the hydrate is C₂₅H₃₂N₂O₄Ion composition of C₁₈H₂₃N₂ ⁺·CH₃C₆H₄SO₃ ^-·H₂And O. The crystal is crystallized in a triclinic system under the condition of methanol at room temperature, the space group is P-1, the unit cell parameters are a-7.9587 (3), b-9.6568 (4),a is 92.889(4) °, β is 98.665(4) °, γ is 101.321(4) °, Z is 2 and

example 2

The preparation method of the p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine ] hydrate comprises the following steps:

(1) at room temperature, mixing a stoichiometric ratio of 1: 1: dissolving 4-diethylaminobenzaldehyde, methyl iodide and 4-methylpyridine of 1 in anhydrous methanol, heating to 75 ℃, adding 10ml of piperidine, refluxing for 48 hours until the color of the solution gradually changes from light yellow to dark red, cooling, crystallizing, filtering and drying to obtain 4- (4-diethylaminostyryl) methylpyridine iodide;

(2) dissolving p-methyl benzene sulfonic acid sodium salt and the iodized 4- (4-diethylaminostyryl) picolinate obtained in the step (1) in a mixed solution of water and methanol according to a stoichiometric ratio of 1:1, and reacting for 48 hours to obtain p-methyl benzene sulfonic acid [4- (4-diethylaminostyryl) picoline ] hydrate; the volume ratio of water to methanol in the mixed solution of water and methanol is 1: 5.

p-methylbenzenesulfonic acid obtained above is reacted with a catalyst[4- (4-diethylaminostyryl) methylpyridine]The hydrate is tested for the crystal structure by X-single crystal diffraction, and the result shows that the chemical formula of the hydrate is C₂₅H₃₂N₂O₄Ion composition of C₁₈H₂₃N₂ ⁺·CH₃C₆H₄SO₃ ^-·H₂And O. The crystal is crystallized in a triclinic system under the condition of methanol at room temperature, the space group is P-1, the unit cell parameters are a-7.9587 (3), b-9.6568 (4),a is 92.889(4) °, β is 98.665(4) °, γ is 101.321(4) °, Z is 2 and

example 3

The preparation method of the p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine ] hydrate comprises the following steps:

(1) at room temperature, mixing a stoichiometric ratio of 1: 1: dissolving 4-diethylaminobenzaldehyde, methyl iodide and 4-methylpyridine of 1 in anhydrous methanol, heating to 70 ℃, adding 8ml of piperidine, refluxing for 36 hours until the color of the solution gradually changes from light yellow to dark red, cooling, crystallizing, filtering and drying to obtain 4- (4-diethylaminostyryl) methylpyridine iodide;

(2) dissolving the sodium p-methylbenzenesulfonate and the 4- (4-diethylaminostyryl) methylpyridine iodide obtained in the step (1) in a mixed solution of water and methanol in a stoichiometric ratio of 1:1, and reacting for 36 hours to obtain the p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine ] hydrate; the volume ratio of water to methanol in the mixed solution of water and methanol is 1: 35.

the p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine ] obtained above was reacted with a carboxylic acid]The hydrate is tested for the crystal structure by X-single crystal diffraction, and the result shows that the chemical formula of the hydrate is C₂₅H₃₂N₂O₄Ion composition of C₁₈H₂₃N₂ ⁺·CH₃C₆H₄SO₃ ^-·H₂And O. The crystal is crystallized in a triclinic system under the condition of methanol at room temperature, the space group is P-1, the unit cell parameters are a-7.9587 (3), b-9.6568 (4),a is 92.889(4) °, β is 98.665(4) °, γ is 101.321(4) °, Z is 2 and

third-order nonlinear optical properties of p-toluenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine ] hydrate:

by Z-scan at a concentration of 2X 10^－5Testing p-methylbenzenesulfonic acid [4- (4-diethylaminostyryl) methylpyridine in mol/L acetonitrile solution]Third order nonlinear optical properties of hydrates. The open cell curve was used to study the nonlinear absorption effect of the material (see fig. 3), and the closed/open cell curve was used to study the nonlinear refraction effect (see fig. 4). The light source is mode-locked Nd: YAG laser with wavelength of 532nm, pulse width of 40ps and repetition frequency of 10Hz after frequency doubling by KTP crystal. The sample was moved in the direction of the optical axis (z-axis) during the test with a beam waist radius of about 39 μm and a corresponding rayleigh length of 4.5 mm.

The test result shows that: the nonlinear absorption coefficient of the sample is a negative value, and the curve after normalization processing has a peak first and a valley second and shows a self-defocusing property. Fitting and calculating the curve by utilizing normalization processing to obtain the nonlinear refractive index n of the sample₂＝1.2×10^-19m²W, nonlinear absorption coefficient beta-2.4 x 10^-12m/W, third order non-linear polarizability x⁽³⁾＝3.9×10^{- 13}esu and molecular second order hyperpolarizability ═ 3.5X 10^-31esu (esu). The material has potential application value in laser pulse compression, optical bistable devices and the like as a nonlinear saturated absorption material.