A piperidine-based zinc-based organic-inorganic hybrid crystal and a method for preparing and using the same

Abstract

The application discloses a kind of piperidine-based zinc-based organic-inorganic hybrid crystal and its preparation method and application, crystal is (4-chloro-1-methylpiperidinium-1-ol) 2ZnBr4, crystallize in chiral space group P21 in monoclinic system, present typical zero-dimensional packing structure, crystal is obtained by the way of room temperature volatilization crystallization, exhibit certain intensity mid-infrared second-order nonlinear optical effect, its frequency doubling coefficient is 0.29 times of commercial potassium dihydrogen phosphate (KDP) crystal, with simple preparation method and good phase purity, in laser frequency converter, electro-optic modulator, electro-optic deflector and related fields have potential application value.

Description

TECHNICAL FIELD

[0001] The present application relates to an organic-inorganic hybrid crystal, in particular to a piperidine-based zinc-based organic-inorganic hybrid crystal, and to the preparation and application of the above hybrid crystal. BACKGROUND

[0002] Functional materials refer to a class of materials with dielectric, piezoelectric, ferroelectric, pyroelectric, nonlinear optical and other rich properties, which are involved in information storage, energy conversion, force-sensitive sensing, intelligent switching and other high-tech fields, such as infrared detection, sonar systems, ignition devices, laser frequency converters, optical parametric oscillators and other practical application scenarios. The inorganic materials in the prior art have high energy consumption and complex preparation process, high toxicity, and do not meet the mechanical flexibility required in specific applications, so researchers need to seek alternatives to overcome these shortcomings. As one of the feasible solutions, polyvinylidene fluoride (PVDF) and odd-numbered nylon exhibit strong piezoelectric, pyroelectric and other properties, good structural flexibility, and convenient film preparation process, but they are criticized for poor thermal stability and low crystallinity, which limits further development. To solve the difficulties faced by pure inorganic materials and polymer materials, organic-inorganic hybrid crystal materials have been successfully explored to develop new flexible devices, portable wearable devices, biomimetic materials, and biocompatible materials.

[0003] As an important physical property in functional materials, nonlinear optics refers to the effects of optical frequency multiplication, sum frequency, difference frequency and optical parametric oscillation when laser propagates in a medium with non-zero second-order polarizability. Materials with this property can be used to prepare laser frequency converters, electro-optic modulators, electro-optic deflectors and other components, and play an extremely important role in high-tech fields such as optical information processing, high-speed optical communication, optical information storage, and electronic instruments.

[0004] Currently, organic-inorganic hybrid crystals with nonlinear optical effects have the advantages of light weight, rich and designable chemical structure, and easy film preparation. However, the construction of existing second-order nonlinear optical materials is often based on molecular-based ferroelectrics, and the basic ideas are "spherical-like non-spherical theory", "introduction of chiral molecules" or "hydrogen-fluorine substitution"; however, whether it is molecular modification or introduction of chiral molecules, the above preparation methods require complex experiments and high prices to achieve, which greatly limits the application of organic-inorganic hybrid materials. SUMMARY

[0005] Invention purposes: The purpose of the present application is to provide a piperidine-based zinc-based organic-inorganic hybrid crystal with strong mid-infrared second-order nonlinear optical effect, the second purpose is to provide a preparation method of the above-mentioned piperidine-based zinc-based organic-inorganic hybrid crystal, and the third purpose is to provide the application of the above-mentioned piperidine-based zinc-based organic-inorganic hybrid crystal as a second-order nonlinear optical material.

[0006] Technical scheme: The piperidine-based zinc-based organic-inorganic hybrid crystal of the present application is (4-chloro-1-methylpiperidin-1-ium) 2ZnBr4, and its chemical formula is C 12 H 26 Br4Cl2N2Zn, which belongs to a monoclinic system, a space group is P21, and a unit cell parameter is Alpha = gamma = 90 degrees, beta = 93.065 (4), Z = 2,

[0007] Preferably, the organic cation is 4-chloro-1-methylpiperidin-1-ium, which is dispersed in ZnBr4 2- Octahedron around, the overall structure is a zero-dimensional type of accumulation.

[0008] The preparation method of the above-mentioned piperidine-based zinc-based organic-inorganic hybrid crystal comprises the following steps:

[0009] (1) 4-chloro-1-methylpiperidine is added dropwise into water, and a mixed solution A is obtained by stirring;

[0010] (2) Zinc bromide is added to the mixed solution A, and a mixed solution B is obtained by stirring;

[0011] (3) Hydrobromic acid aqueous solution is added to the mixed solution B, reaction is carried out, and solution C is obtained by stirring until it is clear;

[0012] (4) Solution C is evaporated at room temperature to obtain colorless transparent block crystals.

[0013] Preferably, in step (1), 5-8 mmol of 4-chloro-1-methylpiperidine is added to 100 mL of water, and further preferably 5 mmol of 4-chloro-1-methylpiperidine is added to 100 mL of water.

[0014] Preferably, in step (2), 5-8 mmol of zinc bromide is added to 100 mL of the mixed solution A, and further preferably 5 mmol of zinc bromide is added to 100 mL of the mixed solution A.

[0015] Preferably, in step (2), the molar ratio of 4-chloro-1-methylpiperidine to zinc bromide in the mixed solution B is 1:1-2, and further preferably the molar ratio of 4-chloro-1-methylpiperidine to zinc bromide in the mixed solution B is 1:1.

[0016] Preferably, in step (3), 10-15 mL of hydrobromic acid aqueous solution is added to every 100 mL of mixed solution B, and the hydrobromic acid in the hydrobromic acid aqueous solution accounts for 45-48% of the total mass of the solution.

[0017] Preferably, in step (4), the evaporation temperature of solution C is 20-30°C.

[0018] The above-mentioned application of piperidine-based zinc-based organic-inorganic crystals as second-order nonlinear optical organic-inorganic hybrid materials.

[0019] Preferably, the second-order nonlinear optical organic-inorganic hybrid material is mainly used in components such as laser frequency converters, electro-optic modulators, and electro-optic deflectors.

[0020] Invention principle: The (4-chloro-1-methylpiperidine-1-onium)2ZnBr4 of the present invention crystallizes in the chiral space group P21 of the monoclinic crystal system, exhibiting a typical zero-dimensional stacked structure. The crystal is obtained by room temperature volatilization crystallization and exhibits a certain intensity of mid-infrared second-order nonlinear optical effect.

[0021] 4-Chloro-1-methylpiperidine-1-onium intercalates in tetrahedral ZnBr4 2- Between the two, under the weak interaction between them, a zero-dimensional stacked structure is finally formed, with symmetric elements of E and i, belonging to point group 2 (C2). When the amine is protonated, it needs to combine with corresponding negatively charged clusters, ions, etc. to achieve charge conservation. The interaction between the two causes the crystal to crystallize in the chiral space group P21, and its second-order nonlinear optical polarizability is non-zero, thus exhibiting second-order nonlinear optical properties.

[0022] Beneficial effects: Compared with the prior art, the present invention has the following significant advantages: (1) The hybrid crystal (4-chloro-1-methylpiperidin-1-onium)2ZnBr4 of the present invention exhibits good mid-infrared second-order nonlinear effect, and its χ (2) It is 0.29 times that of commercial potassium dihydrogen phosphate crystals and has potential application value in components such as laser frequency converters, electro-optic modulators, and electro-optic deflectors; (2) The 4-chloro-1-methylpiperidine and zinc bromide used in the preparation method are inexpensive, readily available, environmentally friendly and non-toxic, and the preparation method is simple and requires a short time. Attached Figure Description

[0023] Figure 1 This is a crystal structure diagram of (4-chloro-1-methylpiperidine-1-onium)2ZnBr4 of the present invention;

[0024] Figure 2 This is the crystal asymmetric unit of (4-chloro-1-methylpiperidine-1-onium)2ZnBr4 of the present invention;

[0025] Figure 3 The powder X-ray diffraction and simulation diagram of (4-chloro-1-methylpiperidine-1-onium)2ZnBr4 of this invention are shown below.

[0026] Figure 4 The overtone coefficient χ of (4-chloro-1-methylpiperidin-1-onium)2ZnBr4 and potassium dihydrogen phosphate crystals in this invention is... (2) Intensity comparison chart. Detailed Implementation

[0027] The technical solution of the present invention will be further described below with reference to the accompanying drawings and embodiments.

[0028] Example 1

[0029] (1) Add 5 mmol of 4-chloro-1-methylpiperidine dropwise to 100 mL of deionized water and stir thoroughly;

[0030] (2) Add 5 mmol of zinc bromide to the mixed liquid in an equimolar ratio with 4-chloro-1-methylpiperidine, and stir thoroughly;

[0031] (3) Add 15 mL of 48% hydrobromic acid to the mixed liquid and stir thoroughly until clear;

[0032] (4) The clear solution was evaporated at room temperature (30°C) to obtain colorless and transparent blocky crystals (4-chloro-1-methylpiperidine-1-onium)2ZnBr4.

[0033] Select a size of 0.20×0.20×0.20mm. 3 Crystals of approximately 1000-2000 mm were used for single-crystal structure analysis. Single-crystal diffraction data were collected on a Bruker APEX-IICCD diffractometer. The crystal structure data of the obtained compounds are shown in Table 1.

[0034] Table 1. Main crystallographic data of compound (4-chloro-1-methylpiperidin-1-onium)2ZnBr4

[0035]

[0036]

[0037] [a] R1=Σ||F o |-|F c || / |F o | [b] wR2=[Σw(F o 2 -F c 2 ) 2 ] / Σw(F o2 ) 2 ] 1 / 2.[c] Maximum and minimum residual electron densities.

[0038] The obtained colorless and transparent bulk crystals have the chemical formula C at 223 K. 12 H 26 Br4Cl2N2Zn, the crystal adopts the monoclinic crystal system, space group P21, and cell parameters are as follows: α=γ=90°, β=93.065(4), Z=2,

[0039] like Figure 1 In terms of the stacked structure, the entire crystal adopts a zero-dimensional stacking pattern, an inorganic tetrahedron (ZnBr4). 2- It cleverly fills the entire structure with 4-chloro-1-methylpiperidine-1-onium through intermolecular forces. For example... Figure 2 The basic structural unit of a crystal is an inorganic tetrahedron (ZnBr4). 2- It is composed of a 4-chloro-1-methylpiperidine-1-onium organic cation.

[0040] Example 2

[0041] Diffraction experiments were performed on the colorless and transparent bulk crystal powder obtained in Example 1.

[0042] like Figure 3 As shown, the characteristic peaks 2θ are 11°, 11.6°, 12.5°, 13.7°, 18°, 19.2°, 19.9°, 20.9°, 21.6°, 23.3°, 24.5°, 25°, 25.6°, 26.4°, 26.9°, 27.6°, 29.1°, 29.9°, and 35.2°, indicating that the powder diffraction experimental data of the obtained colorless and transparent bulk crystals are in perfect agreement with the simulated data, demonstrating the high purity of the prepared compound.

[0043] Example 3

[0044] The performance of the colorless and transparent blocky (4-chloro-1-methylpiperidine-1-onium)2ZnBr4 prepared in Example 1 was compared with that of commercial KDP.

[0045] First, the prepared colorless and transparent bulk crystals were ground into powder with a particle size of approximately 200–300 μm. Then, approximately 3–5 mg of the powder sample was sandwiched in a transparent glass slide measuring 1 cm × 1 cm. This glass slide was then placed in the optical path of a laser. An Nd:YAG pulsed laser was used as the light source to generate 1064 nm fundamental frequency light, which was transmitted through the sample sandwiched in the glass. The generated signal was then displayed on an oscilloscope via a photomultiplier tube. Similarly, a reference KDP crystal was ground into powder with a particle size of approximately 200–300 μm, and comparative tests were conducted under the same experimental conditions.

[0046] like Figure 4 As shown, the macroscopic overtone coefficient χ of (4-chloro-1-methylpiperidin-1-onium)₂ZnBr₄ with commercial KDP is... (2) The intensity comparison is 0.29 times that of commercial KDP.

Claims

1. A zinc-based organic-inorganic hybrid crystal based on piperidine, characterized in that, The crystal is (4-chloro-1-methylpiperidin-1-onium)2ZnBr4, with the chemical formula C. 12 H 26 Br4Cl2N2Zn belongs to the monoclinic crystal system, space group P21, and its unit cell parameters are... α=γ=90°, β=93.065(4), Z=2, 2. The zinc-based organic-inorganic hybrid crystal based on piperidine according to claim 1, characterized in that, The organic cation is 4-chloro-1-methylpiperidin-1-onium, which is dispersed in ZnBr4. 2- Around the octahedron, the overall structure is a zero-dimensional stack.

3. A method for preparing the zinc-based organic-inorganic hybrid crystal based on piperidine as described in claim 1, characterized in that, Includes the following steps: (1) Add 4-chloro-1-methylpiperidine dropwise to water and stir to obtain mixed solution A; (2) Add zinc bromide to the mixed liquid A and stir to obtain mixed solution B; (3) Add hydrobromic acid aqueous solution to mixed solution B, react and stir until clear to obtain solution C; (4) Evaporate solution C at room temperature to obtain colorless and transparent blocky crystals.

4. The manufacturing method according to claim 3, characterized in that, In step (1), 5 to 8 mmol of 4-chloro-1-methylpiperidine is added to every 100 mL of water.

5. The manufacturing method according to claim 3, characterized in that, In step (2), 5 to 8 mmol of zinc bromide is added to every 100 mL of mixed solution A.

6. The manufacturing method according to claim 3, characterized in that, In step (2), the molar ratio of 4-chloro-1-methylpiperidine to zinc bromide in mixed solution B is 1:1 to 2.

7. The manufacturing method according to claim 3, characterized in that, In step (3), 10-15 mL of hydrobromic acid aqueous solution is added to every 100 mL of mixed solution B, and the hydrobromic acid in the hydrobromic acid aqueous solution accounts for 45-48% of the total mass of the solution.

8. The manufacturing method according to claim 3, characterized in that, In step (4), the temperature at which solution C evaporates is 20–30 °C.

9. The application of the piperidine-based zinc-based organic-inorganic crystal of claim 1 as a second-order nonlinear optical organic-inorganic hybrid material.

10. The application according to claim 9, characterized in that, The second-order nonlinear optical organic-inorganic hybrid material is mainly used in laser frequency converters, electro-optic modulators, or electro-optic deflectors.

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