CN115947712A - Crown ether regulation and control non-core organic amine salt material and preparation method thereof - Google Patents
Crown ether regulation and control non-core organic amine salt material and preparation method thereof Download PDFInfo
- Publication number
- CN115947712A CN115947712A CN202211590465.8A CN202211590465A CN115947712A CN 115947712 A CN115947712 A CN 115947712A CN 202211590465 A CN202211590465 A CN 202211590465A CN 115947712 A CN115947712 A CN 115947712A
- Authority
- CN
- China
- Prior art keywords
- crown ether
- organic amine
- amine salt
- betaine
- salt material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 28
- -1 amine salt Chemical class 0.000 title claims abstract description 27
- 150000003983 crown ethers Chemical class 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 8
- KWIUHFFTVRNATP-UHFFFAOYSA-N Betaine Natural products C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000013078 crystal Substances 0.000 claims abstract description 27
- 229960003237 betaine Drugs 0.000 claims abstract description 24
- 230000003287 optical effect Effects 0.000 claims abstract description 23
- 229960003403 betaine hydrochloride Drugs 0.000 claims abstract description 15
- HOPSCVCBEOCPJZ-UHFFFAOYSA-N carboxymethyl(trimethyl)azanium;chloride Chemical compound [Cl-].C[N+](C)(C)CC(O)=O HOPSCVCBEOCPJZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 229910001504 inorganic chloride Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 28
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- XEZNGIUYQVAUSS-UHFFFAOYSA-N 18-crown-6 Chemical compound C1COCCOCCOCCOCCOCCO1 XEZNGIUYQVAUSS-UHFFFAOYSA-N 0.000 claims description 9
- 239000012153 distilled water Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 230000000747 cardiac effect Effects 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000012984 biological imaging Methods 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract 1
- 229940125782 compound 2 Drugs 0.000 description 9
- 229940125904 compound 1 Drugs 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011521 glass Substances 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000001427 coherent effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000002447 crystallographic data Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000009022 nonlinear effect Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004467 single crystal X-ray diffraction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a crown ether controlled noncardial organic amine salt material and a preparation method thereof, wherein the crystal is betaine hydrochloride with a molecular formula of C 5 H 12 NO 2 Cl, which belongs to the monoclinic system, crystallized in polar space groupsCmThe molecules are mutually connected in the a-axis direction through O-H … Cl hydrogen bonds formed between betaine cations and inorganic chloride ions, so that the compound has polarity and good second-order nonlinear optical characteristics; the preparation method is simple to operate, short in time and low in cost, can be induced to generate the noncentral crystal material with nonlinear optics only by adding the crown ether, and has good stability at room temperature. The method has potential application value in the fields of photoelectric switches, laser frequency doubling conversion, biological imaging and high-speed photographic components.
Description
Technical Field
The invention relates to an organic amine salt material and a preparation method thereof, in particular to a crown ether regulation and control non-cardiac organic amine salt material and a preparation method thereof.
Background
The solid-state nonlinear optical (NLO) effect is a phenomenon of nonlinear relationship between optical medium response and field strength under strong coherent light stimulation. The solid nonlinear optical material can perform nonlinear response on an applied optical field, can generate optical frequency doubling, sum frequency, difference frequency and optical parametric oscillation equivalence when laser is transmitted in a medium with nonzero second-order polarizability, and can be applied to high-tech emerging fields such as conductors, biological imaging, photoelectric switches, digital processing and the like. Compared with inorganic nonlinear optical materials, the organic amine salt nonlinear optical material has the incomparable advantages of fast nonlinear response, simple structure, low cost, easy processing, flexibility, environment friendliness and the like, and inorganic crystals attract extensive attention of researchers. Structurally, a necessary condition for generating second-order nonlinear optics is to ensure that the crystal is crystallized in a non-centrosymmetric space group. Therefore, how to controllably adjust the organic amine salt generating the non-centrosymmetric space structure is very important. Although regulation of noncardial crystals has been reported in previous studies, crown ethers do not report regulation of noncardial organic amine salts. The crown ether is a common chemical, can efficiently regulate and control the crystal structure of the betaine hydrochloride from a centrosymmetric structure to a non-centrosymmetric structure, and has second-order nonlinear optical response. Therefore, the search for the non-cardiac crystal with SHG response generated by controllable regulation has great scientific significance and application value, and simultaneously has the challenge of greater difficulty.
Disclosure of Invention
The purpose of the invention is as follows: the invention provides a non-core organic amine salt material which has the advantages of second-order nonlinear optical property, environmental friendliness, simple and easily obtained method and better stability in crown ether solvent regulation; the invention also aims to provide a preparation method of the crown ether regulation and control non-cardiac organic amine salt material.
The technical scheme is as follows: the crown ether regulated non-core organic amine salt material is betaine hydrochloride with a non-core structure, and the molecular formula of the material is as follows: c 5 H 12 NO 2 Cl, the molecules are connected with each other in the a-axis direction through O-H … Cl hydrogen bonds formed between betaine cations and inorganic chloride ions.
Further, the crown ether controlled noncardial organic amine salt material has a crystal structure, belongs to a monoclinic system, is crystallized in a polar space group Cm, and has a unit cell parameter of
α＝γ＝90 ° 、β＝111.25(2) ° 、Z＝2、/>
The invention also provides a preparation method of the second-order nonlinear optical material for regulating and controlling betaine chloride by crown ether, which comprises the following steps:
(1) Dissolving betaine in distilled water, stirring at room temperature to dissolve the betaine completely to obtain colorless transparent solution;
(2) Dropwise adding hydrochloric acid into the colorless transparent solution obtained in the step (1) to ensure that the hydrochloric acid is fully protonated;
(3) Adding the solution obtained in the step (2) into 18-crown-6, and continuously stirring to obtain a colorless transparent solution;
(4) And (4) slowly volatilizing the colorless transparent solution obtained in the step (3) at room temperature to obtain colorless transparent blocky crystals with good quality.
Further, in the step (1), the concentration of the betaine aqueous solution is 0.5-1mmol mL -1 5-10mmol of betaine is dissolved in 10mL of distilled water.
Further, in the step (2), the volume ratio of the added hydrochloric acid to the colorless transparent solution is 0.5-1:1. further, in the step (3), the molar ratio of the 18-crown-6 to the betaine is 0.5-1.5:1.
further, in the step (4), the volatilization temperature is 20-40 ℃.
The second-order nonlinear optical betaine hydrochloride compound obtained by crown ether regulation can be applied to second-order nonlinear optical materials.
Has the advantages that: compared with the prior art, the invention has the following remarkable advantages: the betaine hydrochloride second-order nonlinear optical organic material shows a good second-order nonlinear effect, a noncentral crystal structure can be controllably synthesized through crown ether, the appearance of second-order nonlinear optical response is regulated, and the product has the characteristics of simple structure, simple synthesis method, 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 crystal structure diagram of Compound 1, which is the central structure of betaine hydrochloride;
FIG. 2 is a crystal structure diagram of betaine hydrochloride non-cardiac structure Compound 2;
fig. 3 is a second-order nonlinear SHG intensity plot for compound 2.
Detailed Description
The technical scheme of the invention is further explained by combining the attached drawings.
Comparative example
Dissolving 10mmol of betaine in 20mL of distilled water at normal temperature, stirring to fully dissolve the betaine to obtain a colorless transparent solution, dropwise adding 5mL of hydrochloric acid, stirring for 30min to obtain a colorless transparent solution, standing slowly at room temperature of 30 ℃ to obtain a colorless transparent crystal, namely the betaine hydrochloride compound 1 with the central structure.
Example 1
At normal temperature, 10mmol of betaine is dissolved in 20mL of distilled water, stirred to be fully dissolved to obtain a colorless transparent solution, 5mL of hydrochloric acid is dropwise added, 10mmol of 18-crown ether-6 is added, the mixture is stirred for 30min to obtain a colorless transparent solution, and the colorless transparent solution is slowly stood at room temperature of 30 ℃ to obtain a colorless transparent crystal, namely the betaine hydrochloride compound 2 with a non-heart structure and second-order nonlinear optical properties.
Example 2
At normal temperature, 15mmol of betaine is dissolved in 20mL of distilled water, the mixture is stirred to be fully dissolved to obtain a colorless transparent solution, 10mL of hydrochloric acid is dropwise added, 10mmol of 18-crown ether-6 is added, the mixture is stirred for 30min to obtain a colorless transparent solution, and the colorless transparent solution is kept stand at room temperature slowly and 25 ℃ to obtain a colorless transparent crystal, namely the betaine hydrochloride compound 2 with a non-heart structure and second-order nonlinear optical properties.
Example 3
At normal temperature, 5mmol of betaine is dissolved in 10mL of distilled water, stirring is carried out to fully dissolve the betaine to obtain colorless transparent solution, 8mL of hydrochloric acid is dropwise added, 5mmol of 18-crown ether-6 is added, stirring is carried out for 30min to obtain colorless transparent solution, and the colorless transparent solution is slowly stood at room temperature of 40 ℃ to obtain colorless transparent crystals, namely the betaine hydrochloride compound 2 with the non-heart structure and the second-order nonlinear optical property.
Example 4
At normal temperature, 10mmol of betaine is dissolved in 10mL of distilled water, the mixture is stirred to be fully dissolved to obtain colorless transparent solution, 10mL of hydrochloric acid is dropwise added, 15mmol of 18-crown ether-6 is added, the mixture is stirred for 30min to obtain colorless transparent solution, and the colorless transparent solution is kept stand at room temperature slowly and 35 ℃ to obtain colorless transparent crystals, namely the betaine hydrochloride compound 2 with the non-heart structure and the second-order nonlinear optical property.
The colorless transparent crystals prepared in comparative example and example 1 were each subjected to single crystal structure analysis, and a single crystal of an appropriate size was taken under a microscope and Mo K α rays (λ =) monochromatized with graphite were used under room temperature conditions
) The single crystal X-ray diffraction structures were characterized on a Rigaku Saturn 724diffractometer single crystal diffractometer and the results of the crystallographic parameters for compounds 1 and 2 are given in table 1. The unit cell parameters are determined by a least square method, the data structure analysis is respectively completed by using Olex2 software, and all non-hydrogen atoms are anisotropically refined by a full matrix least square method.
TABLE 1 Main crystallographic data for betaine hydrochloride of the Compound
[a] R 1 ＝Σ||F o |-|F c ||/|F o |. [b] wR 2 ＝[Σw(F o 2 -F c 2 ) 2 ]/Σw(F o 2 ) 2 ] 1/2 .
The betaine chloride compound 1 with a central structure is generated in a solution without adding crown ether, and the molecular formula is C 5 H 12 NO 2 Cl, space group of crystal is P2 1 C, unit cell parameter of
α＝γ＝90 ° 、β＝96.702(4) ° 、Z＝4、/>
The compound 2 of betaine chloride with non-heart structure is obtained by adding and regulating 18-crown ether-6, and the molecular formula is C 5 H 12 NO 2 Cl, a crystal space group Cm and cell parameters->
α＝γ＝90 ° 、β＝111.25(2) ° 、Z＝2、/>
As shown in FIG. 1, the central structure of Compound 1 is that betaine organic cation and chloride ion are connected by hydrogen bond.
As shown in FIG. 2, the noncardial structure of Compound 2 is that the betaine organic cation and chloride ion are linked along the a-axis via hydrogen bonding.
The prepared colorless transparent bulk crystal was ground into a powder having a particle size of about 200 μm, and then a sample of about 5mg of the powder was placed in two transparent glass sheets having a size of 1cm × 1cm, and thereafter the glass sheets were placed on a laser light path, and an 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. As shown in fig. 3, the SHG signal intensity response of compound 2 with a noncardial structure is shown, indicating that the betaine hydrochloride with a noncardial structure has good second-order nonlinear optical properties. And the compound 1 is a central structure and has no second-order nonlinear optical response.
Claims (8)
1. A crown ether regulation and control non-core organic amine salt material is characterized in that: the material is betaine hydrochloride with a noncardial structure, and the molecular formula is as follows: c 5 H 12 NO 2 Cl, the molecules are connected with each other in the a-axis direction through O-H … Cl hydrogen bonds formed between betaine cations and inorganic chloride ions.
2. The crown ether regulated non-cardiac organic amine salt material of claim 1, characterized in that: the material has a crystal structure belonging to a monoclinic system, is crystallized in a polar space group Cm and has a unit cell parameter of
α＝γ＝90、β＝111.25(2)、Z＝2、
3. A method for preparing the crown ether controlled noncardiac organic amine salt material as claimed in claim 1, which is characterized in that: the method comprises the following steps:
(1) Dissolving betaine in distilled water, stirring at room temperature to dissolve the betaine completely to obtain colorless transparent solution;
(2) Dropwise adding hydrochloric acid into the colorless transparent solution to ensure that the solution is fully protonated;
(3) Adding the solution obtained in the step (2) into 18-crown-6, and continuously stirring to obtain a colorless transparent solution;
(4) And (4) slowly volatilizing the colorless transparent solution obtained in the step (3) at room temperature to obtain colorless transparent blocky crystals.
4. The method for preparing the crown ether controlled noncardiac organic amine salt material according to claim 3, wherein the crown ether controlled noncardiac organic amine salt material comprises the following steps: the concentration of the betaine aqueous solution in the step (1) is 0.5-1mmol mL -1 。
5. The method for preparing the crown ether controlled noncardiac organic amine salt material according to claim 3, wherein the crown ether controlled noncardiac organic amine salt material comprises the following steps: the volume ratio of the added hydrochloric acid to the colorless transparent solution in the step (2) is 0.5-1:1.
6. the method for preparing the crown ether controlled noncardiac organic amine salt material as claimed in claim 3, wherein the method comprises the following steps: the mol ratio of the dosage of the 18-crown ether-6 to the betaine in the step (3) is 0.5-1.5:1.
7. the method for producing a noncardiac crystal according to claim 3, wherein: the volatilization temperature in the step (4) is 20-40 ℃.
8. Use of the crown ether-controlled noncardial organic amine salt material of any one of claims 1-2 as a second order nonlinear optical material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211590465.8A CN115947712B (en) | 2022-12-12 | 2022-12-12 | Crown ether regulated non-core organic amine salt material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211590465.8A CN115947712B (en) | 2022-12-12 | 2022-12-12 | Crown ether regulated non-core organic amine salt material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115947712A true CN115947712A (en) | 2023-04-11 |
| CN115947712B CN115947712B (en) | 2024-03-26 |
Family
ID=87288634
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211590465.8A Active CN115947712B (en) | 2022-12-12 | 2022-12-12 | Crown ether regulated non-core organic amine salt material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115947712B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255118A (en) * | 2008-03-20 | 2008-09-03 | 山西新立源生物科技有限公司 | Method for preparing beet alkali hydrochlorate |
| US20120129967A1 (en) * | 2009-07-30 | 2012-05-24 | Michael Veith | Method For Producing Thin Films And The Application Thereof |
| CN107305776A (en) * | 2016-04-18 | 2017-10-31 | 中国科学院化学研究所 | A kind of information recording method and information transmitting methods using photonic crystal as carrier |
| CN112321441A (en) * | 2020-10-14 | 2021-02-05 | 天津大学 | Evaporative crystallization method for increasing thickness of anhydrous betaine flaky crystal |
| CN112521292A (en) * | 2020-12-18 | 2021-03-19 | 深圳市萱嘉生物科技有限公司 | Eutectic crystal of betaine and organic acid and preparation method and application thereof |
-
2022
- 2022-12-12 CN CN202211590465.8A patent/CN115947712B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101255118A (en) * | 2008-03-20 | 2008-09-03 | 山西新立源生物科技有限公司 | Method for preparing beet alkali hydrochlorate |
| US20120129967A1 (en) * | 2009-07-30 | 2012-05-24 | Michael Veith | Method For Producing Thin Films And The Application Thereof |
| CN107305776A (en) * | 2016-04-18 | 2017-10-31 | 中国科学院化学研究所 | A kind of information recording method and information transmitting methods using photonic crystal as carrier |
| CN112321441A (en) * | 2020-10-14 | 2021-02-05 | 天津大学 | Evaporative crystallization method for increasing thickness of anhydrous betaine flaky crystal |
| CN112521292A (en) * | 2020-12-18 | 2021-03-19 | 深圳市萱嘉生物科技有限公司 | Eutectic crystal of betaine and organic acid and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115947712B (en) | 2024-03-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Tran et al. | Deep ultraviolet nonlinear optical materials | |
| Zhao et al. | Beryllium-free Rb3Al3B3O10F with reinforced interlayer bonding as a deep-ultraviolet nonlinear optical crystal | |
| Goel et al. | Enhanced optical, NLO, dielectric and thermal properties of novel sodium hydrogen phthalate single crystals doped with zinc | |
| Gonsago et al. | Crystal structure, optical and thermal studies of a new organic nonlinear optical material: L-Histidinium maleate 1.5-hydrate | |
| Yi et al. | Recent advances on the synthesis of Sb (III)-based inorganic ultraviolet nonlinear optical materials | |
| Liu et al. | Rb3B11P2O23: Materials design of a new chemically benign deep-ultraviolet nonlinear optical material | |
| CN113872037A (en) | Nonlinear frequency doubling equipment, chiral perovskite material and preparation method and application thereof | |
| Huang et al. | “Removing Center”─ An Effective Structure Design Strategy for Nonlinear Optical Crystals | |
| Liu et al. | One-side capping in two-dimensional WO3-type materials leading to strong second-harmonic response | |
| Zhao et al. | A2 (TeO) P2O7 (A= K, Rb, Cs): Three new tellurite-pyrophosphates with large birefringence | |
| CN1958883A (en) | Crystal of barium tellurium aluminate, preparation method and application | |
| Phillips et al. | Inclusion tuning of nonlinear optical materials: KTP isomorphs | |
| Wensheng et al. | SHG from centrosymmetric supermolecular crystal | |
| Li et al. | A UV non-hydrogen pure selenite nonlinear optical material for achieving balanced properties through framework-optimized structural transformation | |
| CN115947712B (en) | Crown ether regulated non-core organic amine salt material and preparation method thereof | |
| WO2016011994A1 (en) | Crystalline metal cyanurate compounds, method for producing said compounds, and use of said compounds | |
| CN1076054C (en) | Non-linear optical crystal Ba2Be2B2O7 | |
| US10858756B2 (en) | Nonlinear optical crystal fluorine boron beryllium salt and its preparation process and use | |
| Vasantha et al. | The structural, thermal and optical characterizations of a new nonlinear optical material | |
| CN113480454B (en) | Linear hydrogen bond type azobenzene crystal and preparation method and application thereof | |
| Tang et al. | Na4 [B6O9 (OH) 3](H2O) Cl: A Deep-Ultraviolet Transparent Nonlinear Optical Borate Chloride with {[B6O9 (OH) 3] 3–}∞ Chains | |
| CN110306240A (en) | Potassiumiodate sodium nonlinear optical crystal and its preparation method and application | |
| Parvathy et al. | Experimental and theoretical approach of novel third-order nonlinear optical single crystal: benzamide 5-chloro-2-hydroxybenzoic acid | |
| Wu et al. | Second-order nonlinear optical property of the ultraviolet transparent alkali metal-rare earth metal carbonate Na3Y (CO3) 3.3 H2O | |
| CN113912091B (en) | Cs 3 C 6 N 9 ·H 2 O compound, cs 3 C 6 N 9 ·H 2 O-nonlinear optical crystal and its preparation method and use |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |