CN114195833A - Crystalline molecular base material generated by chiral mononuclear nickel third-order harmonic and preparation method thereof - Google Patents
Crystalline molecular base material generated by chiral mononuclear nickel third-order harmonic and preparation method thereof Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 196
- 239000000463 material Substances 0.000 title claims abstract description 83
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 34
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000012360 testing method Methods 0.000 claims abstract description 23
- 239000013078 crystal Substances 0.000 claims abstract description 19
- 238000003756 stirring Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000000706 filtrate Substances 0.000 claims abstract description 9
- 239000013110 organic ligand Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 5
- -1 hexafluoroacetylacetone anion Chemical class 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 44
- QAMFBRUWYYMMGJ-UHFFFAOYSA-N hexafluoroacetylacetone Chemical compound FC(F)(F)C(=O)CC(=O)C(F)(F)F QAMFBRUWYYMMGJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 8
- 230000008569 process Effects 0.000 abstract description 4
- 239000008204 material by function Substances 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 description 14
- 239000003446 ligand Substances 0.000 description 9
- 230000004044 response Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- 229910052681 coesite Inorganic materials 0.000 description 5
- 229910052906 cristobalite Inorganic materials 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 229910052682 stishovite Inorganic materials 0.000 description 5
- 229910052905 tridymite Inorganic materials 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000002983 circular dichroism Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001228 spectrum Methods 0.000 description 4
- LNVPVHHEAWDMAX-UHFFFAOYSA-N CC(C1=CC=CN=C1C1=NC=CC=C1)=O.I Chemical compound CC(C1=CC=CN=C1C1=NC=CC=C1)=O.I LNVPVHHEAWDMAX-UHFFFAOYSA-N 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000012925 reference material Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- AJKVQEKCUACUMD-UHFFFAOYSA-N 2-Acetylpyridine Chemical compound CC(=O)C1=CC=CC=N1 AJKVQEKCUACUMD-UHFFFAOYSA-N 0.000 description 2
- KMRMUZKLFIEVAO-UHFFFAOYSA-N 7,7-dimethylbicyclo[3.1.1]hept-3-ene-4-carbaldehyde Chemical compound C1C2C(C)(C)C1CC=C2C=O KMRMUZKLFIEVAO-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- KMRMUZKLFIEVAO-RKDXNWHRSA-N Myrtenal Natural products C1[C@H]2C(C)(C)[C@@H]1CC=C2C=O KMRMUZKLFIEVAO-RKDXNWHRSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
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- 238000004020 luminiscence type Methods 0.000 description 2
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- 239000007777 multifunctional material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
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- 230000010287 polarization Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
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- 125000006575 electron-withdrawing group Chemical group 0.000 description 1
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- 230000001747 exhibiting effect Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000010365 information processing Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/04—Nickel compounds
- C07F15/045—Nickel compounds without a metal-carbon linkage
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/3551—Crystals
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/35—Non-linear optics
- G02F1/355—Non-linear optics characterised by the materials used
- G02F1/361—Organic materials
- G02F1/3619—Organometallic 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
- C07B2200/07—Optical isomers
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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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- Organic Chemistry (AREA)
- General Physics & Mathematics (AREA)
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- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a crystalline molecular base material generated by chiral mononuclear nickel third-order harmonic and a preparation method thereof, belonging to the technical field of chiral molecular base functional materials. The molecular formula of the chiral mononuclear nickel third-order harmonic generation crystalline molecular base material is Ni (hfac)2L, wherein hfac is hexafluoroacetylacetone anion, L is S configuration chiral bidentate N-containing organic ligand: (+) -4, 5-pinene-2, 2' -bipyridine. The preparation method provided by the invention comprises the following steps: mixing Ni (hfac)2·2H2And adding the ethanol solution of O into the chloroform solution of L, stirring, filtering, transferring the obtained filtrate into a test tube, placing the test tube into a gas collecting bottle of n-hexane, performing solvent diffusion to obtain dark green crystals, washing with the n-hexane, and drying to obtain the chiral mononuclear nickel third-order harmonic generation crystalline molecular base material. The inventionThe preparation method provided is simple in process, easy in post-treatment and high in yield, and the THG test based on the crystal sample is more convenient and practical.
Description
Technical Field
The invention belongs to the technical field of chiral molecular base functional materials, and particularly relates to a chiral mononuclear nickel third-order harmonic generation crystalline molecular base material and a preparation method thereof.
Background
Chirality is a fundamental property of nature and plays an important role in the fields of chemistry, biology, medicine, material science, and the like. Due to the non-central symmetry of the molecular structure, the chiral complex may have unique physical properties related to the chiral molecular structure, such as nonlinear optical activity, second-order harmonic generation, circular polarization luminescence, and the like.
Nonlinear optics (NLO) has evolved dramatically since its discovery and has brought about significant economic effects. The nonlinear optical material is mainly applied to the conversion of light wave frequency to open up a new laser light source and perform optical signal processing such as control, switching, amplification, storage and the like, so that various optical devices can be made, and the nonlinear optical material is widely applied to a plurality of fields such as optical communication, optical information processing, optical storage, military industry, medical treatment and the like.
Currently, a great deal of research effort is devoted to organic and inorganic materials exhibiting non-linearity (NLO), in particular Second Harmonic Generation (SHG), which are mainly borate-series materials (including BBO, LBO, KBBF, etc.), KTP (KTiO)2PO4) Type material, KDP (KH)2PO4) Mold material, and the like. However, these materials inevitably have some disadvantages, such as BBO has influence on material strength and optical uniformity due to crystal defects caused by dislocation; for another example, KDP, as a high-quality nonlinear optical material, is relatively widely applied to the field of laser nonlinear optics, but since large KDP crystals have a series of characteristics that are not conducive to optical processing, the application range is also limited; compared with the molecular base material with SHG activity, hasThe THG response has a small amount of molecular-based materials, and the main reason is that most of the third harmonic generation processes are weak and are not easy to detect. In addition, the study of the third-order nonlinear optical response of materials is usually carried out in a dilute solution by using a Z-scanning technology, and the study result is inevitably influenced by the solvent effect, especially for the molecular-based materials which are difficult to dissolve in an organic solvent, the THG performance test and study of the materials are definitely restricted by the Z-scanning technology.
In addition, chiral information is introduced into the molecular structure of the third-order harmonic generation material, so that the material is crystallized in a polar point group, thereby further meeting the requirements of special physicochemical properties such as ferroelectric, piezoelectric and circular polarization luminescence, and becoming a potential molecular-based multifunctional material, and the development and research of the multifunctional material are the subjects of intense research of researchers in related fields.
Disclosure of Invention
In view of the background technology, the invention provides a crystalline molecular base material generated by chiral mononuclear nickel third-order harmonic and a preparation method thereof.
In order to achieve the above purpose, the invention provides the following technical scheme:
the invention discloses a crystalline molecular base material generated by chiral mononuclear nickel third-order harmonic, wherein the molecular formula of the crystalline molecular base material generated by the chiral mononuclear nickel third-order harmonic is Ni (hfac)2And L, wherein hfac is hexafluoroacetylacetone anion, and L is a chiral bidentate N-containing organic ligand with S configuration.
Preferably, the chiral bidentate N-containing organic ligand is (+) -4, 5-pinene-2, 2' -bipyridine, and the structural formula is as follows:
preferably, the chiral mononuclear nickel third-order harmonic generation material is crystallized from monoclinic non-centrosymmetric space group P21The unit cell parameters are as follows:
α＝γ＝90°，β＝101.599(4)°，
Z＝4，Dc＝1.568g·cm–1，μ＝0.742mm–1，R1＝0.0684，wR2＝0.1346。
the invention provides a preparation method of a crystalline molecular base material generated by chiral mononuclear nickel third-order harmonic, which is characterized by comprising the following steps:
(1) mixing Ni (hfac)2·2H2Dissolving O in ethanol to obtain Ni (hfac)2·2H2Ethanol solution of O;
(2) dissolving the L in chloroform to obtain a chloroform solution of the L;
(3) mixing the Ni (hfac) of the step (1)2·2H2Adding the ethanol solution of O into the chloroform solution of L in the step (2), stirring for 20-30min, filtering, transferring the obtained filtrate into a test tube, placing the test tube into a gas collection bottle filled with n-hexane, and diffusing through a solvent to obtain dark green crystals;
(4) and (4) washing the dark green crystal obtained in the step (3) by normal hexane, and drying at room temperature to obtain the chiral mononuclear nickel third-order harmonic generation crystalline molecular base material.
Preferably, Ni (hfac) in the step (1)2·2H2The preparation method of O comprises the following steps: will dissolve Ni (ClO)4)2·6H2Adding O water solution into hexafluoroacetylacetone water solution, stirring for 10-15min, standing for 3-4 days to obtain dark green crystalline Ni (hfac)2·2H2O。
Preferably, the Ni (ClO)4)2·6H2The mass ratio of O to hexafluoroacetylacetone is (1.0-1.2) to (0.5-0.8).
Preferably, the Ni (ClO)4)2·6H2O aqueous solution Ni (ClO)4)2·6H2The concentration of O is 0.125-0.24 g/mL; the hexafluoroacetyl groupThe concentration of hexafluoroacetylacetone in the acetone aqueous solution is 0.083-0.267 g/mL.
Preferably, Ni (hfac) in the step (1)2·2H2Ethanol solution of O containing Ni (hfac)2·2H2The concentration of O is 0.013-0.025 mol/L.
Preferably, the concentration of L in the chloroform solution of L in the step (2) is 0.013-0.035 mol/L.
Preferably, said Ni (hfac)2·2H2The mass ratio of O to L is (1-1.2): 1.
The invention has the beneficial effects that:
(1) the invention adopts chiral bidentate N-containing organic ligand L with enantiomer pure S configuration: (+) -4, 5-pinene-2, 2' -bipyridine with Ni (hfac)2·2H2O reaction to obtain the final crystalline molecular base material with the third harmonic generated by the chiral mononuclear nickel, and the crystalline molecular base material has strong THG response because the molecular structure contains strong electron-withdrawing group (-CF)3) And the chiral L ligand has electron donating characteristics, so that the whole molecule has larger polarity, and the THG response is polarity-dependent, so that the molecular base material has strong THG response.
According to the test results, the following test results are obtained: chiral mononuclear nickel third-order harmonic generation material Ni (hfac)2L shows a strong THG response at 517nm (about 1/3 at the wavelength of the incident laser), and is similar to that of the reference material alpha-SiO in the same particle size range2In contrast, the THG intensity of the chiral mononuclear nickel third-order harmonic generation crystalline molecular-based material is alpha-SiO29.3 times of the crystalline molecular base material, and the third-order nonlinear activation rate chi of the crystalline molecular base material(3)＝653pm2/V2The value is alpha-SiO2Third order nonlinear activation Rate (214 pm)2/V2) 3.05 times of the total weight of the powder.
(2) The invention provides a preparation method of a crystalline molecular base material generated by chiral mononuclear nickel third-order harmonic, which has the advantages of simple process, mild synthesis condition, high yield, good stability and easy separation and purification, and is expected to have wide application prospect in the fields of laser, photoelectric technology, biological marking and the like as a novel nonlinear optical material.
Drawings
In order to illustrate the embodiments of the invention more clearly, the drawings that are needed in the description of the embodiments will be briefly described below, it being apparent that the drawings in the following description are only some embodiments of the invention, and that other drawings may be derived from those drawings by a person skilled in the art without inventive effort.
FIG. 1 shows example 1 third harmonic generation of chiral mononuclear nickel crystalline molecular base material Ni (hfac)2The molecular structure of L, the H atom has been omitted for clarity.
FIG. 2 shows the example 1 of producing crystalline molecular based material Ni (hfac) by third harmonic of chiral mononuclear nickel2Ni in the molecular structure of L2+Coordination geometry of the ions.
FIG. 3 shows the example 1 of producing crystalline molecular based material Ni (hfac) by third harmonic of chiral mononuclear nickel2Chiral Circular Dichroism (CD) spectrum of L.
FIG. 4 shows the example 1 of producing crystalline molecular based material Ni (hfac) by third harmonic of chiral mononuclear nickel2The third harmonic of L produces The (THG) spectrum.
FIG. 5 shows the example 1 of producing crystalline molecular based material Ni (hfac) by third harmonic of chiral mononuclear nickel2L and reference material alpha-SiO2THG spectrum of (a).
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without inventive effort based on the embodiments of the present invention, are within the scope of the present invention.
The invention discloses a crystalline molecular base material generated by chiral mononuclear nickel third-order harmonic and a preparation method thereofThe molecular formula of the crystalline molecular base material generated by the chiral mononuclear nickel third-order harmonic is Ni (hfac)2L, wherein hfac is hexafluoroacetylacetone anion, L is a chiral bidentate N-containing organic ligand of S configuration: (+) -4, 5-pinene-2, 2' -bipyridine, the structural formula is:
wherein the chiral mononuclear nickel third-order harmonic generation material is crystallized in monoclinic system non-centrosymmetric space group P21The unit cell parameters are as follows:
α＝γ＝90°，β＝101.599(4)°，
Z＝4，Dc＝1.568g·cm–1，μ＝0.742mm–1，R1＝0.0684，wR2＝0.1346。
the invention provides a preparation method of a crystalline molecular base material generated by chiral mononuclear nickel third-order harmonic, which is characterized by comprising the following steps:
(1) mixing Ni (hfac)2·2H2Dissolving O in ethanol to obtain Ni (hfac) with concentration of 0.013-0.025mol/L2·2H2Ethanol solution of O;
(2) dissolving L in chloroform to obtain a chloroform solution of L with the concentration of 0.013-0.035 mol/L;
(3) mixing the Ni (hfac) of the step (1)2·2H2Adding the ethanol solution of O into the chloroform solution of L in the step (2), stirring, filtering, transferring the obtained filtrate into a test tube, placing the test tube into a gas collection bottle filled with n-hexane, and diffusing through a solvent to obtain dark green crystals;
(4) and (4) washing the dark green crystal obtained in the step (3) by normal hexane, and drying at room temperature to obtain the chiral mononuclear nickel third-order harmonic generation crystalline molecular base material.
The chiral mononuclear nickel third-order harmonic generates crystalline molecular baseIn the preparation method of the material, Ni (hfac)2·2H2The preparation method of O comprises the following steps:
will dissolve Ni (ClO)4)2·6H2Adding O water solution into hexafluoroacetylacetone water solution, stirring for 10-15min, standing for 3-4 days to obtain dark green crystalline Ni (hfac)2·2H2And O. Wherein said Ni (ClO)4)2·6H2The mass ratio of O to hexafluoroacetylacetone is (1.0-1.2): (0.5-0.8), Ni (ClO)4)2·6H2O aqueous solution Ni (ClO)4)2·6H2The concentration of O is 0.125-0.24g/mL, the concentration of hexafluoroacetylacetone in hexafluoroacetylacetone water solution is 0.083-0.267g/mL, and the yield is 95%. Elemental analysis: according to the formula C10H6O6F12Ni (molecular weight 508.83): calculated (%) C, 23.60; h, 1.19. Found (%) C, 23.73; h, 1.32. Infrared Spectrum IR (KBr, cm)–1)：3212(w)，1643(s)，1416(m)，1322(s)，1135(m)。
In the preparation method of the crystalline molecular base material generated by the third harmonic of the chiral mononuclear nickel, the preparation method of the (+) -4, 5-pinene-2, 2' -bipyridyl comprises the following steps:
(a) preparation of 2- (acetylpyridyl) pyridine iodide salt intermediate: adding 3.2g of 2-acetylpyridine into a flask, dissolving the 2-acetylpyridine with 15mL of pyridine solution, adding 12mL of pyridine solution dissolved with 10g of iodine into the flask, heating to 115 ℃, reacting for 3.5h, cooling to room temperature, filtering, washing twice with 5mL of pyridine, and drying in vacuum to obtain the required intermediate 2- (acetylpyridyl) pyridine iodonium salt;
(b) synthesis of a bidentate N-containing organic ligand L of chiral S configuration: 2.8g of the 2- (acetylpyridyl) pyridinium iodonium salt intermediate prepared in step (a) was reacted with 2.5g of ammonium acetate (NH)4Ac) was placed in a three-necked flask, and 25mL of formamide (HCONH) was added2) Adding 1.5g of S-configuration myrtenal (+) -myrtenal under stirring, heating to 75 ℃, stirring under nitrogen for reaction for 11.5h, adding the product obtained after the reaction into 200mL of saturated sodium bicarbonate solution, continuously stirring to generate brown solid, filtering, dissolving the obtained solid with 10mL of ethanol, adding 120mL of waterThe solid is separated out, the process is repeated twice, white flocculent solid is finally obtained, and the (+) -4, 5-pinene-2, 2' -bipyridine is prepared after drying at room temperature, wherein the yield is 86 percent (calculated according to the intermediate). Elemental analysis: according to the formula C17H18N2(molecular weight 250.33): calculated value (%): c, 81.56; h, 7.25; n, 11.19; found (%): c, 81.63; h, 7.36; n, 11.25. Infrared spectrum ir (kbr): 2948(s), 2993(m), 2861(v), 1582(m), 1456(s), 1383(m), 798(m), 750(s).
The technical solution of the present invention is further illustrated by the following specific examples
Example 1
This example of chiral mononuclear nickel third-order harmonic generation crystalline molecular base material Ni (hfac)2Preparation of L: 5mL of a solution containing Ni (hfac)2·2H2Adding an ethanol solution of O (50mg, 0.1mmol) into 4mL of chloroform solution dissolved with S-configuration chiral bidentate N-containing ligand L (25mg, 0.1mmol), stirring at room temperature for 10min, filtering, transferring the obtained filtrate into a test tube, placing the test tube in a gas collection bottle of N-hexane for 3 days to obtain dark green crystals, washing with N-hexane, and drying at room temperature to obtain the chiral mononuclear nickel third harmonic generation crystalline molecular base material with the yield of 92% (calculated according to Ni).
Generating crystalline molecular base material Ni (hfac) for chiral mononuclear nickel third harmonic by adopting Perkin-Elmer 240C element analyzer2L is subjected to content analysis of C, H and N elements and is represented by the formula C27H20N2O4F12Calculated (%) for Ni (molecular weight 723.16): c, 44.85; h, 2.79; and N, 3.87. Found (%): c, 44.73; h, 2.91; and (3) N3.69.
The molecular structure of the third-order harmonic generation crystalline molecular base material in this example was determined at room temperature using a Bruker SMART APEX II CCD diffractometer single crystal diffractometer, as shown in FIG. 1, the chiral nickel third-order harmonic generation crystalline molecular base material is a mononuclear molecular structure comprising a Ni2+Ions, a chiral bidentate N-containing ligand L and two hfac anion ligands; as can be seen from FIG. 2, the center Ni of six coordinates2+Ions are separately coupled with 2N atoms provided by a chiral L ligandThe bond of the two hfac ligands provides 4O atoms to form NiN2O4The octahedral geometry of (1), wherein the N1 and O3 atoms occupy the upper and lower vertices of the octahedron, respectively.
The solid state Circular Dichroism (CD) spectrum of the third-order harmonic generation crystalline molecular-based material of this example was tested at room temperature using a Biologic MS-500spectropolarimeter and, as shown in fig. 3, showed a negative Cotton effect at a wavelength λ of 325nm, confirming the chiral optical activity of the third-order harmonic generation material.
At normal temperature, THG performance test is performed on the crystalline molecular base material generated by the third harmonic in this embodiment, a crystal sample with a particle size of less than 30 μm is selected, 1550nm excitation light is generated by an ultrafast fiber laser (NPI Lasers, Rainbow 1550OEM), the repetition frequency of the laser pulse is 80MHz, the pulse width is 100fs, and the power is 100mW, image information of the sample is collected by a CCD camera (MI chrome 5Pro), and spectral information is obtained by a refrigeration type fiber spectrometer (ideopatics, NOVA). The sample is placed on an electric displacement platform (the stepping precision is 0.1 mu m, and the scanning precision is 1 mu m), the appearance of the sample is observed through a CCD, and a scanning area is selected. The test result shows that: chiral mononuclear nickel third-order harmonic generation material Ni (hfac)2L exhibits a strong THG response at 517nm (about 1/3 at the wavelength of the incident laser), as shown in fig. 4; with reference material alpha-SiO of the same particle size range2In comparison with the results obtained under the same test conditions, the THG intensity of the chiral mononuclear nickel third-order harmonic generation crystalline molecular base material is alpha-SiO29.3 times of the material, as shown in fig. 5, the third-order nonlinear activation rate χ of the material is obtained through correlation calculation(3)＝653pm2/V2The value is alpha-SiO2Third order nonlinear activation Rate (214 pm)2/V2) 3.05 times of the crystal state of the chiral mononuclear nickel, the chiral mononuclear nickel crystal state molecular base material has strong THG response.
In this embodiment, Ni (hfac)2·2H2The preparation method of O comprises the following steps:
1.0g of Ni (ClO)4)2·6H2O dissolved in 8mL of water, and Ni (ClO)4)2·6H2The aqueous solution of O was added to 6mL of an aqueous solution containing 0.5g of hexafluoroacetylacetone, stirred for 10min, and allowed to stand for 3 days to obtain dark green crystalline Ni (hfac)2·2H2O。
Example 2
This example of chiral mononuclear nickel third-order harmonic generation crystalline molecular base material Ni (hfac)2Preparation of L: 10mL of a solution containing Ni (hfac)2·2H2Adding an ethanol solution of O (75mg, 0.15mmol) into 10mL of chloroform solution dissolved with S-configuration chiral bidentate N-containing ligand L (37.5mg, 0.15mmol), stirring at room temperature for 8min, filtering, transferring the obtained filtrate into a test tube, placing the test tube in a gas collection bottle of N-hexane for 3 days to obtain dark green crystals, washing with N-hexane, and drying at room temperature to obtain the chiral mononuclear nickel third-harmonic generation crystalline molecular base material.
In this embodiment, Ni (hfac)2·2H2The preparation method of O comprises the following steps:
1.1g of Ni (ClO)4)2·6H2O dissolved in 6mL of water, and Ni (ClO)4)2·6H2Adding O aqueous solution into 6mL of aqueous solution dissolved with 0.6g hexafluoroacetylacetone, stirring for 15min, standing for 3 days to obtain dark green crystalline Ni (hfac)2·2H2O。
Example 3
This example of chiral mononuclear nickel third-order harmonic generation crystalline molecular base material Ni (hfac)2Preparation of L: 20mL of a solution containing Ni (hfac)2·2H2Adding an ethanol solution of O (100mg, 0.2mmol) into 14mL of chloroform solution dissolved with S-configuration chiral bidentate N-containing ligand L (50mg, 0.2mmol), stirring at room temperature for 8min, filtering, transferring the obtained filtrate into a test tube, placing the test tube in a gas collection bottle of N-hexane for 3 days to obtain dark green crystals, washing with N-hexane, and drying at room temperature to obtain the chiral mononuclear nickel third harmonic generation crystalline molecular base material.
In this embodiment, Ni (hfac)2·2H2The preparation method of O comprises the following steps:
1.2g of Ni (ClO)4)2·6H2O dissolved in 5mL of waterIn (2), Ni (ClO) is added4)2·6H2Adding the O aqueous solution into 3mL of aqueous solution dissolved with 0.8g of hexafluoroacetylacetone, stirring for 15min, and standing for 3 days to obtain dark green crystalline Ni (hfac)2·2H2O。
Example 4
This example of chiral mononuclear nickel third-order harmonic generation crystalline molecular base material Ni (hfac)2Preparation of L: 5mL of a solution containing Ni (hfac)2·2H2Adding an ethanol solution of O (60mg, 0.12mmol) into 5mL of chloroform solution dissolved with S-configuration chiral bidentate N-containing ligand L (25mg, 0.1mmol), stirring at room temperature for 10min, filtering, transferring the obtained filtrate into a test tube, placing the test tube in a gas collection bottle of N-hexane for 3 days to obtain dark green crystals, washing with N-hexane, and drying at room temperature to obtain the chiral mononuclear nickel third harmonic generation crystalline molecular base material.
In this embodiment, Ni (hfac)2·2H2The preparation method of O comprises the following steps:
1.0g of Ni (ClO)4)2·6H2O dissolved in 7mL of water, and Ni (ClO)4)2·6H2The aqueous solution of O was added to 4mL of an aqueous solution containing 0.5g of hexafluoroacetylacetone, stirred for 10min, and allowed to stand for 3 days to obtain dark green crystalline Ni (hfac)2·2H2O。
Example 5
This example of chiral mononuclear nickel third-order harmonic generation crystalline molecular base material Ni (hfac)2Preparation of L: 8mL of a solution containing Ni (hfac)2·2H2Adding an ethanol solution of O (60mg, 0.12mmol) into 4mL of chloroform solution dissolved with S-configuration chiral bidentate N-containing ligand L (30mg, 0.12mmol), stirring at room temperature for 10min, filtering, transferring the obtained filtrate into a test tube, placing the test tube in a gas collection bottle of N-hexane for 3 days to obtain dark green crystals, washing with N-hexane, and drying at room temperature to obtain the chiral mononuclear nickel third harmonic generation crystalline molecular base material.
In this embodiment, Ni (hfac)2·2H2The preparation method of O comprises the following steps:
1.1g of Ni (ClO)4)2·6H2O dissolved in 8mL of water, and Ni (ClO)4)2·6H2The aqueous solution of O was added to 6mL of an aqueous solution containing 0.8g of hexafluoroacetylacetone, stirred for 15min, and allowed to stand for 3 days to obtain dark green crystalline Ni (hfac)2·2H2O。
The chiral mononuclear nickel third-order harmonic generation crystalline molecular base material and the preparation method thereof provided by the invention are described in detail above. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and its core concepts. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. A crystalline molecular base material generated by chiral mononuclear nickel third harmonic is characterized in that: the molecular formula of the chiral mononuclear nickel third-order harmonic generation crystalline molecular base material is Ni (hfac)2And L, wherein hfac is hexafluoroacetylacetone anion, and L is a chiral bidentate N-containing organic ligand with S configuration.
2. The chiral mononuclear nickel third-order harmonic generation crystalline molecular based material of claim 1, characterized in that: the chiral bidentate N-containing organic ligand is (+) -4, 5-pinene-2, 2' -bipyridine, and the structural formula is as follows:
3. the chiral mononuclear nickel third-order harmonic generation crystalline molecular based material of claim 1, characterized in that: the chiral mononuclear nickel third-order harmonic generation material is crystallized in monoclinic system non-centrosymmetric space group P21The unit cell parameters are as follows:
α＝γ＝90°，β＝101.599(4)°，
Z＝4，Dc＝1.568g·cm–1，μ＝0.742mm–1，R1＝0.0684，wR2＝0.1346。
4. a method of preparing a chiral mononuclear nickel third-order harmonic generation crystalline molecular based material according to any one of claims 1 to 3, comprising the steps of:
(1) mixing Ni (hfac)2·2H2Dissolving O in ethanol to obtain Ni (hfac)2·2H2Ethanol solution of O;
(2) dissolving the L in chloroform to obtain a chloroform solution of the L;
(3) mixing the Ni (hfac) of the step (1)2·2H2Adding the ethanol solution of O into the chloroform solution of L in the step (2), stirring, filtering, transferring the obtained filtrate into a test tube, placing the test tube into a gas collection bottle filled with n-hexane, and diffusing through a solvent to obtain dark green crystals;
(4) and (4) washing the dark green crystal obtained in the step (3) by normal hexane, and drying at room temperature to obtain the chiral mononuclear nickel third-order harmonic generation crystalline molecular base material.
5. The method of claim 4, wherein the step (1) comprises Ni (hfac)2·2H2The preparation method of O comprises the following steps: will dissolve Ni (ClO)4)2·6H2Adding O water solution into hexafluoroacetylacetone water solution, stirring for 10-15min, standing for 3-4 days to obtain dark green crystalline Ni (hfac)2·2H2O。
6. The method of claim 5, wherein the chiral mononuclear nickel third-order harmonic generation crystalline molecular based material is prepared by: the Ni (ClO)4)2·6H2The mass ratio of O to hexafluoroacetylacetone is (1.0-1.2) to (0.5-0.8).
7. The method of claim 6, wherein the chiral mononuclear nickel third-order harmonic generation crystalline molecular based material is prepared by: the Ni (ClO)4)2·6H2Ni (ClO) in O aqueous solution4)2·6H2The concentration of O is 0.125-0.24 g/mL; the concentration of hexafluoroacetylacetone in the hexafluoroacetylacetone aqueous solution is 0.083-0.267 g/mL.
8. The method of claim 4, wherein the chiral mononuclear nickel third-order harmonic generation crystalline molecular based material is prepared by: in the step (1), Ni (hfac)2·2H2Ethanol solution of O containing Ni (hfac)2·2H2The concentration of O is 0.013-0.025 mol/L.
9. The method of claim 4, wherein the chiral mononuclear nickel third-order harmonic generation crystalline molecular based material is prepared by: the concentration of L in the chloroform solution of L in the step (2) is 0.013-0.035 mol/L.
10. The method of preparing a chiral mononuclear nickel third-order harmonic generation crystalline molecular based material according to any one of claims 8-9, characterized in that: the Ni (hfac)2·2H2The mass ratio of O to L is (1-1.2): 1.
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