CN106957437B - Second-order nonlinear optical switch material based on reversible structure phase change and preparation method thereof - Google Patents

Second-order nonlinear optical switch material based on reversible structure phase change and preparation method thereof Download PDF

Info

Publication number
CN106957437B
CN106957437B CN201710153515.9A CN201710153515A CN106957437B CN 106957437 B CN106957437 B CN 106957437B CN 201710153515 A CN201710153515 A CN 201710153515A CN 106957437 B CN106957437 B CN 106957437B
Authority
CN
China
Prior art keywords
cadmium
coordination polymer
thiocyanate
nonlinear optical
order nonlinear
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.)
Active
Application number
CN201710153515.9A
Other languages
Chinese (zh)
Other versions
CN106957437A (en
Inventor
杜恣毅
张世勇
谢永荣
卢莹冰
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Gannan Normal University
Original Assignee
Gannan Normal University
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Gannan Normal University filed Critical Gannan Normal University
Priority to CN201710153515.9A priority Critical patent/CN106957437B/en
Publication of CN106957437A publication Critical patent/CN106957437A/en
Application granted granted Critical
Publication of CN106957437B publication Critical patent/CN106957437B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/54—Organic compounds
    • C30B29/58—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
    • C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)

Abstract

A cadmium thiocyanate coordination polymer and a preparation method thereof, the cadmium thiocyanate coordination polymer has a chemical formula of (C)5H14N)[Cd(SCN)3]Wherein "(C)5H14N) "is the protonated N, N-dimethylisopropylammonium cation. The compound crystallizes in an orthorhombic system at room temperature with a space group Cmc21Unit cell parameter of
Figure DDA0002449052910000011
Figure DDA0002449052910000012
α - β -gamma-90 deg. and Z-4 deg. the cadmium thiocyanic acid coordination polymer is prepared by using cadmium sulfate 8/3 hydrate, N-dimethyl isopropylamine, potassium thiocyanate and dilute sulfuric acid as raw material, and has good second-order nonlinear optical property, its powder frequency doubling effect strength at room temp. is about 2 times that of potassium dihydrogen phosphate (KDP) which is a second-order nonlinear optical material with extensive commercial application, when its temp. is raised to about 50 deg.C, it can produce solid-state structure phase change to result in disappearance of frequency-doubled signal, and can be used as solid-state nonlinear optical switch materialSufficient material source, easy operation, low production cost, higher yield, good reproducibility and high purity, and is suitable for the requirement of expanded production.

Description

Second-order nonlinear optical switch material based on reversible structure phase change and preparation method thereof
Technical Field
The invention relates to a cadmium thiocyanate coordination polymer with an optical frequency doubling effect 'switching' function and a preparation method thereof, belonging to the field of inorganic chemistry and also belonging to the field of material science and the field of optics.
Background
Nonlinear optical effects originate from the interaction of the laser light with a specific medium. When laser light propagates in a medium with a non-zero second-order polarizability, nonlinear optical effects such as frequency doubling, sum frequency, difference frequency, parametric oscillation and amplification can be generated. By using the second-order nonlinear optical effect of the crystal, nonlinear optical devices such as a second harmonic generator, a frequency converter, an optical parametric oscillator and the like can be manufactured.
The second-order nonlinear optical switching material refers to a class of materials capable of realizing the switching function of second-order nonlinear optical behaviors, and is concerned due to the fact that the materials have important application values in the fields of modern laser technology, photoelectric communication, optical information processing, data storage and the like. Currently, finding second-order nonlinear optical switching materials capable of achieving reversible, large contrast is a hotspot and frontier of material science research. Since the second-order nonlinear optical effect can be generated only by nonlinear polarization of the non-centrosymmetric structure, the solid-state structure phase change which can be reversibly converted between the centrosymmetric structure and the non-centrosymmetric structure is an important strategy for realizing the second-order nonlinear optical switching material with high switching ratio.
Disclosure of Invention
The invention aims to provide a cadmium thiocyanate coordination polymer and a preparation method thereof, and the cadmium thiocyanate coordination polymer can be used as a potential second-order nonlinear optical switching material.
The invention takes protonated N, N-dimethyl isopropylamine as an organic cation template agent, and synthesizes the cadmium thiocyanate coordination polymer with obvious frequency doubling effect at room temperature through the coordination of inorganic cadmium ions and thiocyanate radicals. The cadmium thiocyanate coordination polymer material disappears by frequency doubling effect when heated to about 50 ℃, so that the cadmium thiocyanate coordination polymer material can be used as a second-order nonlinear optical switch material. The method is realized by the following steps:
a cadmium thiocyanate coordination polymer with the chemical formula (C)5H14N)[Cd(SCN)3]Wherein "(C)5H14N) "is the protonated N, N-dimethylisopropylammonium cation. The compound crystallizes in an orthorhombic system at room temperature with a space group Cmc21Unit cell parameter of
Figure GDA0002449052900000011
α＝β＝γ＝90°，Z＝4。
The preparation method of the cadmium thiocyanate coordination polymer comprises the following steps: putting cadmium sulfate 8/3 hydrate and N, N-dimethyl isopropylamine in equal molar ratio into a small beaker, adding a proper amount of distilled water, and stirring until the mixture is dissolved; adding 3 times of molar ratio of potassium thiocyanate solid into the solution to generate white precipitate, slowly dripping dilute sulfuric acid under stirring until the solution becomes clear, and then standing at room temperature; and (3) precipitating a colorless rod-shaped crystal from the solution after several hours, namely the cadmium thiocyanate coordination polymer crystal.
The specific reaction formula of the preparation method is as follows: 6KSCN +2CdSO4·8/3H2O+2(i-PrNMe2)+H2SO4→2(i-PrNHMe2)[Cd(SCN)3]+3K2SO4。
The concentration of the dilute sulfuric acid is about 1 mmol/g.
The crystal structure of the cadmium thiocyanate coordination polymer is determined by an X-ray single crystal diffractometer test (shown in figure 1), and the crystal precipitated in the solution is a pure-phase compound (shown in figure 2) by the X-ray powder diffractometer test.
When the cadmium thiocyanate coordination polymer is heated to about 50 ℃, the frequency doubling signal disappears (as shown in figure 3) due to solid-state structural phase change, so that the cadmium thiocyanate coordination polymer can be used as a solid-state second-order nonlinear optical switching material.
The invention has the beneficial effects that: 1. the obtained cadmium thiocyanate coordination polymer has good second-order nonlinear optical characteristics, and the strength of the powder frequency doubling effect is about 2 times of that of second-order nonlinear optical material potassium dihydrogen phosphate (KDP for short) which is widely used commercially; when the material is heated to about 50 ℃, the frequency doubling signal disappears due to the solid-state structural phase change, so that the material can be used as a potential solid-state second-order nonlinear optical switching material.
2. The preparation method is simple, the raw material source is sufficient, the operation is easy, the production cost is low, the yield of the cadmium thiocyanate coordination polymer is high, the reproducibility is good, the purity is high, and the requirements of expanded production are met.
Drawings
FIG. 1 is a molecular structural diagram of a cadmium thiocyanate coordination polymer according to the present invention;
FIG. 2 is an X-ray diffraction pattern of in situ temperature change powder of a cadmium thiocyanate coordination polymer in accordance with the present invention;
FIG. 3 is a diagram showing the second-order nonlinear optical effect of the cadmium thiocyanate coordination polymer of the present invention as a function of temperature.
Detailed Description
Cadmium thiocyanate coordination polymer (C) in the invention5H14N)[Cd(SCN)3]The synthesis of (2):
(C5H14N)[Cd(SCN)3]is obtained by adopting a conventional solution method, and has the specific reaction formula: 6KSCN +2CdSO4·8/3H2O+2(i-PrNMe2)+H2SO4→2(i-PrNHMe2)[Cd(SCN)3]+3K2SO4。
The specific operation steps are as follows: cadmium sulfate 8/3 hydrate and N, N-dimethyl isopropylamine in equal molar ratio are put into a small beaker, and a proper amount of distilled water is added and stirred until being dissolved. Adding potassium thiocyanate solid with the molar ratio of 3 times into the solution to generate white precipitate, slowly dropping dilute sulfuric acid with the concentration of 1mmol/g under stirring until the solution becomes clear, and then standing at room temperature. Colorless rod-shaped crystals are precipitated from the solution after several hours, namely the cadmium thiocyanate coordination polymer crystals, and the yield is about 80 percent. The crystal structure of the coordination polymer (shown in FIG. 1) was determined by X-ray single crystal diffractometry, and the crystallographic data thereof are shown in the following table.
Figure GDA0002449052900000031
In addition, the X-ray powder diffractometer tests show that the crystals precipitated in the solution are pure phase compounds, and structural phase transition occurs when the temperature is heated to a certain degree (as shown in fig. 2).
The crystal structure parameters of the cadmium thiocyanate coordination polymer at room temperature are as follows: orthorhombic, space group Cmc21Unit cell parameter of
Figure GDA0002449052900000032
α - β -gamma-90 deg. and Z-4 deg. it is proved by second-order nonlinear optical test that the coordination polymer has good second-order nonlinear optical property, the strength of its powder frequency doubling effect is about 2 times of that of potassium dihydrogen phosphate (KDP) which is a second-order nonlinear optical material widely used in commercial application, when it is heated to 50 deg.C, the frequency doubling signal disappears due to solid-state structure phase change, so it can be used as good potential second-order nonlinear optical switch material.

Claims (3)

1. A cadmium thiocyanate coordination polymer with the chemical formula (C)5H14N)[Cd(SCN)3]Wherein "(C)5H14N) "is a protonated N, N-dimethylisopropylammonium cation that crystallizes in an orthorhombic system at room temperature with a space group ofCmc21Unit cell parameter ofa=9.3607(1)Å，b=14.6857(2)Å，c=10.6812(1)Å，α=β=γ=90º，Z=4。
2. The method for preparing the cadmium thiocyanate coordination polymer according to claim 1, comprising the steps of: putting cadmium sulfate 8/3 hydrate and N, N-dimethyl isopropylamine in equal molar ratio into a small beaker, adding a proper amount of distilled water, and stirring until the mixture is dissolved; adding 3 times of molar ratio of potassium thiocyanate solid into the solution to generate white precipitate, slowly dripping dilute sulfuric acid under stirring until the solution becomes clear, and then standing at room temperature; and (3) precipitating a colorless rod-shaped crystal from the solution after several hours, namely the cadmium thiocyanate coordination polymer crystal.
3. Use of a cadmium thiocyanate coordination polymer according to claim 1, characterized in that: the cadmium thiocyanate coordination polymer is used as a second-order nonlinear optical material when the temperature is lower than 50 ℃ and a switching material capable of generating second-order nonlinear optical signal disappearance when the temperature rises to about 50 ℃.
CN201710153515.9A 2017-03-15 2017-03-15 Second-order nonlinear optical switch material based on reversible structure phase change and preparation method thereof Active CN106957437B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710153515.9A CN106957437B (en) 2017-03-15 2017-03-15 Second-order nonlinear optical switch material based on reversible structure phase change and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710153515.9A CN106957437B (en) 2017-03-15 2017-03-15 Second-order nonlinear optical switch material based on reversible structure phase change and preparation method thereof

Publications (2)

Publication Number Publication Date
CN106957437A CN106957437A (en) 2017-07-18
CN106957437B true CN106957437B (en) 2020-06-09

Family

ID=59470106

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710153515.9A Active CN106957437B (en) 2017-03-15 2017-03-15 Second-order nonlinear optical switch material based on reversible structure phase change and preparation method thereof

Country Status (1)

Country Link
CN (1) CN106957437B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108593563A (en) * 2018-05-15 2018-09-28 中国科学院福建物质结构研究所 Optical material test method and optic analytical instrument used
CN111286783B (en) * 2020-03-06 2021-04-20 北京师范大学 Nonlinear optical crystal, nonlinear optical switch, and preparation method and use method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4447335A (en) * 1981-03-31 1984-05-08 Argus Chemical Corporation Process for the preparation of thin films of cadmium sulfide and precursor solutions of cadmium ammonia thiocyanate complex useful therein
CN105646549A (en) * 2016-01-13 2016-06-08 山西大学 Double-terminal-group pyridine copper complex and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4447335A (en) * 1981-03-31 1984-05-08 Argus Chemical Corporation Process for the preparation of thin films of cadmium sulfide and precursor solutions of cadmium ammonia thiocyanate complex useful therein
CN105646549A (en) * 2016-01-13 2016-06-08 山西大学 Double-terminal-group pyridine copper complex and preparation method thereof

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
Crystal growth and characterization of a novel inorganic–organic hybrid NLO crystal: (NH4)[Cd(NCS)3]•C12H24O6;V. Ramesh等;《Applied Physics B》;20130510;第113卷(第1期);第99-106页 *
The Syntheses and the X-Ray Crystal Structure of Tetramethylammonium Tetrakis- and Tris(thiocyanato)cadmates(II), [(CH3)4N]2[Cd(SCN)4] and [(CH3)4N][Cd(SCN)3];Kuniyasu Yasumitsu;《Bulletin of the Chemical Society of Japan 》;19870131;第60卷(第1期);第179-183页 *
Wide Spectral Range Nonlinear Optical Crystals of One-Dimensional Coordination Solids [Et4N][Cd(SCN)3] and [Et4N][Cd(SeCN)3] and the General Design Criteria for [R4N][Cd(XCN)3] (Where R ) Alkyl and X ) S, Se, Te) as NLO Crystals;Hong Zhang等;《Inorganic Chemistry》;20000412;第39卷(第9期);第1868-1873页 *
阳离子导向的硫氰酸镉的合成、结构及性质研究;贾红丽;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20140915(第9期);第B014-79页 *

Also Published As

Publication number Publication date
CN106957437A (en) 2017-07-18

Similar Documents

Publication Publication Date Title
Zhang et al. Functional materials design via structural regulation originated from ions introduction: A study case in cesium iodate system
Guo et al. A Series of New Infrared NLO Semiconductors, ZnY6Si2S14, Al x Dy3 (Si y Al1− y) S7, and Al0. 33Sm3SiS7
Aggarwal et al. Bulk crystal growth and characterization of semiorganic nonlinear optical materials
Shi et al. A2Bi2 (SeO3) 3F2 (A= K and Rb): excellent mid-infrared nonlinear optical materials with both strong SHG responses and large band gaps
CN109023502B (en) Compound cerium fluoroiodate, cerium fluoroiodate nonlinear optical crystal, preparation method and application
CN106957437B (en) Second-order nonlinear optical switch material based on reversible structure phase change and preparation method thereof
Boopathi et al. Investigation on growth, structural, optical, thermal, dielectric and mechanical properties of organic L-prolinium trichloroacetate single crystals
Muralidharan et al. Growth and characterization of L-arginine acetate single crystals: a new NLO material
Shanmugavadivu et al. Crystal growth, thermal and optical studies of nonlinear optical material: Glycine potassium sulphate
CN101921196B (en) Organic amine phosphate nonlinear optical crystal [C6H9N3O2][HPO4]
Bai et al. [C (NH2) 3] 2Zn (CO3) 2: A Guanidinium-Templated Ultraviolet Nonlinear Optical Material
WO2019119513A1 (en) Non-linear optical crystal monoflurophospate
Raghavan et al. Studies on the growth, structural, optical, thermal and electrical properties of nonlinear optical cadmium mercury thiocyanate glycol monomethyl ether single crystal
JP5653130B2 (en) Method for producing bis (fluorosulfonyl) imide
Xie et al. A new method for the preparation of a [Sn 2 (H 2 PO 2) 3] Br SHG-active polar crystal via surfactant-induced strategy
CN101560218B (en) Organometallic complex of nonlinear optical and ferroelectric material, synthesis and application thereof
Wang et al. Growth and properties of UV nonlinear optical crystal ZnCd (SCN) 4
KR20190061478A (en) Method for producing lithium fluorosulfonylimide and lithium fluorosulfonylimide produced by the same
Jesudurai et al. Synthesis, growth and characterization of new borate-mixed crystals of type (NH4) 1− xKxB5O8
CN111850695B (en) Fluorinated lutetium selenite frequency doubling crystal and preparation and application thereof
Devi et al. Investigations on the effect of transition metals on the growth and characterization of sodium acid phthalate single crystals
Singh et al. Growth and characterization of new nonlinear optical thiourea l-alanine acetate single crystal
CN102516276B (en) Tartaric acid terbium ferroelectric functional material and preparation method thereof
CN113667457B (en) Ferroelectric material with second harmonic effect and preparation method thereof
CN102191548B (en) Nonlinear optical and ferroelectric crystals dimethylammonium germanium tetraborate and preparation method and application thereof

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