CN114292286A - Chiral organic-inorganic hybrid copper (I) halide crystal and preparation method and application thereof - Google Patents
Chiral organic-inorganic hybrid copper (I) halide crystal and preparation method and application thereof Download PDFInfo
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- -1 copper (I) halide Chemical class 0.000 title claims abstract description 75
- 239000013078 crystal Substances 0.000 title claims abstract description 52
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- 238000000034 method Methods 0.000 claims abstract description 10
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- 238000001816 cooling Methods 0.000 claims abstract description 5
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- 229910021590 Copper(II) bromide Inorganic materials 0.000 claims description 16
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(II) bromide Substances [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 8
- 229910021589 Copper(I) bromide Inorganic materials 0.000 claims description 7
- 238000004891 communication Methods 0.000 claims description 5
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- 150000004982 aromatic amines Chemical group 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 claims description 2
- 238000012984 biological imaging Methods 0.000 claims description 2
- 230000033228 biological regulation Effects 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 2
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 claims description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 claims description 2
- 229940045803 cuprous chloride Drugs 0.000 claims description 2
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 2
- 229940112669 cuprous oxide Drugs 0.000 claims description 2
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 16
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- RQEUFEKYXDPUSK-SSDOTTSWSA-N (1R)-1-phenylethanamine Chemical compound C[C@@H](N)C1=CC=CC=C1 RQEUFEKYXDPUSK-SSDOTTSWSA-N 0.000 description 3
- RQEUFEKYXDPUSK-ZETCQYMHSA-N (1S)-1-phenylethanamine Chemical compound C[C@H](N)C1=CC=CC=C1 RQEUFEKYXDPUSK-ZETCQYMHSA-N 0.000 description 3
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- 238000000411 transmission spectrum Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
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- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a chiral organic-inorganic hybrid copper (I) halide crystal and a preparation method and application thereof, relating to the field of optical materials. Compared with copper (II) halide with d-d transition, chiral copper (I) halide prepared by taking copper (I) as central metal of the material shows larger second-order nonlinear optical coefficient, has wider light transmission window and better light stability and thermal stability in ultraviolet, visible light region and infrared light region; the synthesis method comprises the steps of mixing hydrohalic acid solutions respectively dissolved with chiral organic amine and cuprous halide, adding a certain amount of hypophosphorous acid, heating to dissolve, and cooling and crystallizing to obtain corresponding chiral copper (I) halide colorless transparent crystals. The preparation method and the process steps are simple, the scale production of the chiral hybrid copper (I) halide crystal and the application in the field of second-order nonlinear optics can be realized, and a new thought is provided for the design and development of second-order nonlinear optical materials.
Description
Technical Field
The application relates to the field of organic-inorganic hybrid copper (I) halide, in particular to a preparation method of a novel chiral organic-inorganic hybrid copper (I) halide crystal and application thereof in second-order nonlinear optics-Second Harmonic Generation (SHG).
Background
Organic-inorganic hybrid metal halides are widely used in the fields of solar cells, light emitting diodes, lasers, photodetectors, catalysis, etc. due to their excellent characteristics such as high carrier mobility, excellent charge transport properties, low trap density, and low-cost solution processability. The rich chemical and structural diversity, large oscillation strength and adjustable band gap of the organic-inorganic hybrid metal halide also enable the application thereof in the field of nonlinear optics (NLO). SHG is widely used in communication, military, industrial production, and life as a second-order nonlinear optical phenomenon that is most widely used. However, the realization of second-order nonlinear optics requires materials with non-centrosymmetric structures, which is a challenge for organic-inorganic hybrid metal halides.
Chiral materials have intrinsic non-central symmetry and typically exhibit unique optical properties, such as Circular Dichroism (CD) and Circular Polarized Luminescence (CPL). It is exciting that the organic-inorganic hybrid metal halides allow the introduction of chiral amines, which provides the possibility of inducing the non-centrosymmetric structure required for the formation of second order NLO effects. Over the last few years, many researchers have developed chiral organic-inorganic hybrid metal halide materials for use in SHG applications, such as chiral halides based on metals like lead (II), tin (II), bismuth (III), cadmium (II), etc., which have nonlinear optical coefficients mostly comparable to commercial potassium dihydrogen phosphate (KDP). And the copper-based organic-inorganic hybrid metal halide can avoid the toxicity problem of lead/cadmium halide and the instability problem of tin halide. More recently, Guo et al reported a chiral hybrid copper (II) halide (R-/S-MBA)2CuCl4[ (R/S-MBA) is (R) - (+) -1-phenylethylamine or (S) - (-) -1-phenylethylamine]A film. The film was proved to haveSHG properties. However, (R-/S-MBA)2CuCl4Extends to 450nm in the visible region, resulting in severe self-absorption, which negatively affects the transparent window and the Laser Damage Threshold (LDT), similar to many other organic-inorganic hybrid metal halides.
The existing chiral organic-inorganic hybrid copper (II) halide has the problems of poor stability, poor optical transparency, small nonlinear response, low laser damage threshold and the like, and directly influences the application of the material as a nonlinear crystal. The metal copper (I) without d-d transition is innovatively used as the central metal, the hybrid metal halide is constructed, the problem of self-absorption of the crystal in a visible region is solved ingeniously, the obtained material has a stronger SHG signal, a higher laser damage threshold value and a wider transmission window than the copper (II) halide with d-d transition, and a new thought is provided for the design and development of the chiral metal halide as a second-order nonlinear optical material.
Disclosure of Invention
The invention provides a preparation method and application of a chiral organic-inorganic hybrid copper (I) halide, which is a nonlinear optical material with wider light-transmitting wave band, larger second-order nonlinear optical coefficient, easy preparation and better stability, for solving the problems. The metal halide has the characteristics that no obvious absorption is generated at the position of more than 280nm, and the metal halide has a larger band gap compared with most organic-inorganic hybrid metal halides, so that the problem of self absorption of chiral organic-inorganic copper (II) halides and most other organic-inorganic hybrid metal halides in a visible light region is solved, the spectrum application range of SHG properties is widened, the metal halide has good permeability in an ultraviolet-visible-infrared region, and the laser damage threshold is increased by a plurality of times compared with the corresponding copper (II) halides. Illustrative of the invention (R/S-MBA) CuBr2The material has the following characteristics: an excellent SHG signal in the entire visible region; extremely high polarization ratio (97%); a transparent window (290nm-3220nm) with ultra-wide deep ultraviolet-visible light region and infrared light region; good laser damage threshold; excellent air stability and thermal stability.
The chiral hybrid copper (I) halide crystal is (R-MBA) CuBr2For example, the crystal is monoclinic, and the space group is P21The main crystallographic parameters are
The chiral organic-inorganic hybrid copper (I) halide crystal prepared by the invention is applied to the field of second-order nonlinear optics.
The technical scheme adopted by the invention is as follows:
a preparation method of chiral organic-inorganic hybrid copper (I) halide crystals comprises the steps of mixing hydrohalic acid solutions respectively dissolved with chiral organic amine and cuprous halide, adding a certain amount of hypophosphorous acid, heating to dissolve, cooling and crystallizing to obtain corresponding chiral copper (I) halide colorless transparent crystals.
Furthermore, the chiral organic amine has rich structure, and can be selected from one or more of cyclic or chain chiral alicyclic amines, chiral aromatic amines and other groups substituted amines. The chiral alicyclic amines include compounds of the following formulas IA1-IA12, the chiral aromatic amines include compounds of the following formulas IB1-IB6, the halogen-substituted amines include compounds of the following formulas IC1-IC12, and the other group-substituted amines include compounds of the following formulas ID1-ID 2:
in the scheme, the hydrohalic acid comprises one or more of hydroiodic acid, hydrobromic acid and hydrochloric acid, and the effective regulation and control of the chiral hybrid copper (I) halide energy band can be realized.
In the scheme, the copper halide is used for expanding one of cuprous chloride, cuprous bromide, cuprous iodide and cuprous oxide.
In the above scheme, the method for heating, dissolving and cooling crystallization comprises the following steps: mixing hydrohalic acid solutions respectively dissolved with chiral organic amine and cuprous halide, adding a certain amount of hypophosphorous acid, heating to dissolve, cooling and crystallizing at room temperature, and crystallizing after a preset time to obtain the chiral hybrid copper (I) halide micron crystal.
The invention has the following technical advantages and positive effects:
the preparation method of the chiral hybrid copper (I) halide crystal has simple process and easy control, can be used for mass production of the chiral organic-inorganic hybrid copper (I) halide crystal, and can be applied to the aspect of SHG. The central metal copper (I) of the crystal is in a monovalent state, and d-d transition does not exist, so that the crystal has wider light transmission windows and better light stability and thermal stability in ultraviolet, visible light and infrared light regions, shows larger second-order nonlinear optical coefficient, and is expected to be applied in the fields of biological imaging, optical communication and military affairs.
Drawings
The invention is described in further detail below with reference to the following figures and detailed description:
FIG. 1 is a synthetic route diagram of an embodiment of the present application;
FIG. 2 is a schematic illustration of a heated dissolution-cooled crystallization process according to an embodiment of the present application;
FIG. 3 is a representation under bright field microscope and polarizing microscope of chiral organic-inorganic hybrid copper (I) halide nanoplates of the present application example;
FIG. 4 is a scanning electron microscope and elemental analysis characterization of chiral organic-inorganic hybrid copper (I) halide nanoplates of the present application example;
FIG. 5 is a schematic diagram of a crystal structure of chiral organic-inorganic hybrid copper (I) halide single crystal analyzed by X-ray diffraction according to an embodiment of the present application;
FIG. 6 is an ultraviolet-visible absorption spectrum and a circular dichroism spectrum of chiral organic-inorganic hybrid copper (I) halide nanoplates of embodiments of the present application;
FIG. 7 is a transmission spectrum of chiral organic-inorganic hybrid copper (I) halide nanoplates of examples of the present application;
FIG. 8 is an SHG spectrum of chiral organic-inorganic hybrid copper (I) halide nanoplates of examples of the present application;
FIG. 9 shows the left picture of the same thickness organic-inorganicOrganic hybrid copper (I) halide (R-MBA) CuBr2Micron tablet (strongest), urea micron tablet (middle) and (R-MBA)2CuCl4SHG relative intensity contrast spectra of the (weakest) micron sheet. The right picture is (R-MBA) CuBr2Micron sheet (upper) and (R-MBA)2CuCl4SHG intensity versus excitation power for the micro-slabs (below).
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples. Unless otherwise specified, all materials and reagents used in the present application were purchased commercially and used as received without treatment, and the equipment used was the manufacturer's recommended protocol and parameters.
In the examples, single crystal X-ray diffraction data were obtained using Cu Ka radiation from a RigakuXtalAB PRO MM007 DW diffractometer
Or Mo Ka radiation
And (6) collecting. The UV-vis absorption spectrum was collected by a UV-vis spectrophotometer (UV 2600). Infrared (IR) transmission spectra were obtained on a fourier transform infrared spectrometer (tens or 37). Linear Circular Dichroism (CD) spectra were collected using a JASCO J-810 CD spectrometer.
Next, a method for producing a chiral hybrid copper (I) halide nanocrystal and examples of the chiral hybrid copper (I) halide nanocrystal according to the present invention will be described.
The synthetic route of this example is shown in FIG. 1.
In a separate beaker, (R) - (+) -1-phenylethylamine or (S) - (-) -1-phenylethylamine (121mg, 1.0mmol) was reacted with HBr (40 wt.%, 0.5mL, 3.5mmol) under ice bath conditions; CuBr powder (143.4mg1mmol) was dissolved in a solution of H3PO2In a beaker of aqueous HBr (40 wt.%, 1mL, 7mmol) (170 μ L, 1.9mmol) a clear solution formed. The solutions in the two beakers were then mixed, dissolved by heating, and cooled to room temperature, during which time colorless crystals began to crystallize. After about 2 days the crystal growth was considered complete.
And (3) morphology characterization:
referring to fig. 3 and 4, fig. 3 shows the morphology of the chiral hybrid copper (I) halide nanosheet crystal characterized by the conventional electron microscope and the polarizing microscope, which visually shows the size and shape of the chiral hybrid copper (I) halide nanosheet crystal; fig. 4 shows the crystal morphology of the chiral hybrid copper (I) halide nanosheet characterized by the scanning electron microscope, and as shown in the figure, the chiral hybrid copper (I) halide nanosheet is a rectangular nanosheet with a diameter of about 20-60 μm, and the elements Cu, Br, and C are uniformly distributed as can be seen from elemental analysis. In order to further explain that the obtained micron sheet is chiral hybrid copper (I) halide, the structure of the micron sheet is analyzed through single crystal X-ray diffraction,
structural characterization:
referring to fig. 5, the crystal structure of the chiral hybrid copper (I) halide nanosheet crystals was characterized by X-ray single crystal diffractometry. The chiral micron sheet crystal is (R) - (+) -1-phenylethylamine or (S) - (-) -1-phenylethylamine, which takes copper (I) as the center and bromine atoms as the tetrahedron of the vertex to form ordered chain distribution; the center of the tetrahedron is copper atom, the vertex of the tetrahedron is nitrogen atom, the tetrahedron forms a one-dimensional long chain through edge sharing, and organic amine ligands surrounding the periphery of the chain interact with each other through coulomb effect and hydrogen bonds, wherein, the lighter color is carbon atom, and the darker color is nitrogen atom. (R-MBA) CuBr2And (S-MBA) CuBr2The two nanosheet structures are mirror-symmetric and are chiral hybrid copper (I) halide materials. The obtained chiral hybrid copper (I) halide micron-sheet crystal material has a non-centrosymmetric structure.
Optical properties:
referring to FIG. 6, the upper part is the UV-visible absorption spectrum of the chiral hybrid copper (I) halide micron-sized plate crystal, and the lower part is the circular dichroism spectrum of the chiral hybrid copper (I) halide micron-sized crystal, wherein the solid line corresponds to (R-MBA) CuBr2The dotted line corresponds to (S-MBA) CuBr2Of (c) is used. In a circular dichroism chart, (R-MBA) CuBr2And (S-MBA) CuBr2The spectra of (A) show strong circular dichroism signals at 221nm,263nm and 283nm, and the signals are opposite. Obviously, these circular dichroicsShould be prepared from (R-MBA) CuBr2And (S-MBA) CuBr2The Coriton effect of the intrinsic exciton absorption band of the chiral hybrid copper (I) halide micron-sheet crystal is generated, and corresponds to the absorption peak at 283nm (4.38eV) of an ultraviolet-visible absorption spectrogram. This is a good demonstration that the chiral hybrid copper (I) halide nanosheet crystals are chirally symmetric and necessarily also non-centrosymmetric. Therefore, the chiral hybrid copper (I) halide material has wide application prospect in the fields of nonlinear optics, ferroelectric piezoelectricity and the like.
FIG. 7 shows the transmission spectrum of the chiral hybrid copper (I) halide, which shows that the chiral hybrid copper (I) halide has a transmittance of approximately 90% at 280-3200nm, which effectively increases the laser damage threshold; and directly demonstrates the potential for a wide range of applications of the copper (I) halides in the uv-vis-ir region.
Nonlinear optical properties:
the invention utilizes the self-built femtosecond laser testing system to characterize the frequency doubling performance of single crystal of a sample. Selecting a chiral hybrid metal halide single crystal with a proper size, placing the chiral hybrid metal halide single crystal on a quartz substrate of a sample carrying platform, taking femtosecond pulse laser (spectrum-Physics Mai Tai, 690-1040nm, <100fs, 80 MHz; spectrum Physics Mai Tai) as a light source, leading fundamental frequency light to pass through a polaroid and enter a sample, collecting reflected SHG signals after passing through an objective lens, wherein the incident angle and the reflection angle are both 45 degrees. Imaging on CCD, and coupling the spectral signal to spectrometer via optical fiber for measurement.
Referring to FIG. 8, a single (R-MBA) CuBr is shown at the same energy2Wavelength dependent SHG spectra of the micro-slabs. The SHG spectrum is obtained by exciting the excitation wavelengths from 800-1040nm (100fs, 80MHz) and 1200-1500nm (<50fs, 1000Hz) with a step size of 20nm, and graph a shows the relative intensities of the SHG signals with different wavelengths, and it can be seen that the incident light has the strongest signal at 940nm, which can be up to 323 times that of the reference Y-cut quartz. Panel b shows (R-MBA) CuBr under the same test conditions2The signal intensity of each wavelength of the microchip is a multiple relation of a reference Y-cut quartz signal. FIG. c is (R-MBA) CuBr2Normalized by micron sheetIn the spectrum of the SHG signal, we can see that the SHG has better response in the whole visible light region (400-750 nm). And the incident laser range is expected to have better SHG response signal (300- & ltSUB & gt 1600nm) within 600- & ltSUB & gt 3200nm, and can cover the common communication waveband.
Referring to FIG. 9, the left graph depicts (R-MBA) CuBr with the same thickness2Micron sheet (strongest, urea micron sheet (middle) and (R-MBA)2CuCl4SHG spectrum of the (weakest) micron sheet. Impressively, (R-MBA) CuBr at 940nm pump2The SHG signal intensity of (A) is 2 times that of urea, and is divalent copper (II) halide (R-MBA)2 CuCl 420 times of the micron sheet. Shown on the right as (R-MBA) CuBr2Micron sheet (upper) and (R-MBA)2CuCl4The SHG intensity and excitation power of the micrometer (lower) sheet are plotted, and the slope of the two straight lines is 2, which shows that the signal intensity and the power are in a quadratic relation, and further confirms that the SHG intensity and the excitation power are the second-order nonlinear physical mechanism. The intensity decreased above 105mW, indicating a divalent copper (II) halide (R-MBA)2CuCl4The laser damage threshold of the micron sheet is 105 mW. Notably, monovalent copper (I) halides (R-MBA) CuBr2The laser damage threshold of the microchip was determined to be 415mW, which is approximately the corresponding divalent copper (II) halide (R-MBA)2CuCl4The laser damage threshold is 4 times that of the laser, and the laser threshold is obviously improved. Therefore, the chiral organic-inorganic hybrid copper (I) halide material has wide application prospects in the fields of nonlinear optics, cell imaging, information communication and the like.
Although the present application has been described with reference to preferred embodiments, it is not intended to limit the scope of the claims, and many possible variations and modifications may be made by one skilled in the art without departing from the spirit of the application.
Claims (9)
1. A preparation method of chiral organic-inorganic hybrid copper (I) halide crystals is characterized by comprising the following steps: mixing the hydrohalic acid solutions respectively dissolved with chiral organic amine and cuprous halide, adding a certain amount of hypophosphorous acid, heating to dissolve, and cooling and crystallizing to obtain corresponding chiral copper (I) halide colorless transparent crystals.
2. The method for preparing a chiral organic-inorganic hybrid copper (I) halide crystal according to claim 1, characterized in that: the chiral organic amine comprises one or more of chiral alicyclic amine, chiral aromatic amine, halogen substituted amine and other group substituted amine; the chiral alicyclic amines include compounds of the following formulas IA1-IA12, the chiral aromatic amines include compounds of the following formulas IB1-IB6, the halogen-substituted amines include compounds of the following formulas IC1-IC12, and the other group-substituted amines include compounds of the following formulas ID1-ID 2:
3. the method for preparing a chiral organic-inorganic hybrid copper (I) halide crystal according to claim 1, characterized in that: the hydrohalic acid comprises one or more of hydriodic acid, hydrobromic acid and hydrochloric acid, and is used for realizing effective regulation and control of chiral hybrid copper (I) halide energy bands.
4. The method for preparing a chiral organic-inorganic hybrid copper (I) halide crystal according to claim 1, characterized in that: copper halide is used for expanding one of cuprous chloride, cuprous bromide, cuprous iodide and cuprous oxide.
5. A chiral organic-inorganic hybrid copper (I) halide crystal is characterized in that: prepared by the method for preparing chiral organic-inorganic hybrid copper (I) halide crystals as claimed in any one of claims 1 to 4.
6. The chiral organic-inorganic hybrid copper (I) halide crystal according to claim 5, characterized in that: the crystal is based on (R) - (+) -1-phenylethylamineChiral hybrid copper (I) halide of (R-MBA) CuBr2The crystal is monoclinic system, and the space group is P21The main crystallographic parameters are
α＝90°，β＝108.826(10)°，γ＝90°，Z＝4，
7. Use of chiral organic-inorganic hybrid copper (I) halide crystals obtained by the method according to any one of claims 1 to 4 for second order nonlinear optics, Second Harmonic Generation (SHG).
8. Use of a chiral organic-inorganic hybrid copper (I) halide crystal according to claim 7, characterized in that: by introducing chiral amine, an intrinsic non-centrosymmetric structure required by a second-order nonlinear optical effect is induced to form, and fundamental frequency light with frequency omega is converted into frequency doubled light with frequency 2 omega in an ultraviolet-visible-infrared band; the central metal copper (I) of the crystal is in a univalent state, and d-d transition does not exist, so that the crystal has wider light transmission windows, better light stability and thermal stability in ultraviolet, visible light and infrared light regions, and shows a larger second-order nonlinear optical coefficient.
9. Use of a chiral organic-inorganic hybrid copper (I) halide crystal according to claim 7, characterized in that: the method is used for the fields of biological imaging, optical communication and military affairs.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114875472A (en) * | 2022-04-25 | 2022-08-09 | 河南大学 | Organic-inorganic hybrid chiral perovskite helical structure micron sheet and preparation method and application thereof |
| CN114957335A (en) * | 2022-06-24 | 2022-08-30 | 南开大学 | Method for preparing chiral metal halide from achiral precursor by chiral induction |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102069014A (en) * | 2010-09-15 | 2011-05-25 | 罗梅 | Chiral zinc complex and copper complexes of alpha-phenylethylamine |
| CN112520781A (en) * | 2020-12-03 | 2021-03-19 | 吉林大学 | Copper-doped ternary metal halide and preparation method thereof |
| CN113337277A (en) * | 2021-05-20 | 2021-09-03 | 华中科技大学 | Organic-inorganic hybrid copper-based halide scintillator and preparation and application thereof |
-
2021
- 2021-12-30 CN CN202111651261.6A patent/CN114292286B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102069014A (en) * | 2010-09-15 | 2011-05-25 | 罗梅 | Chiral zinc complex and copper complexes of alpha-phenylethylamine |
| CN112520781A (en) * | 2020-12-03 | 2021-03-19 | 吉林大学 | Copper-doped ternary metal halide and preparation method thereof |
| CN113337277A (en) * | 2021-05-20 | 2021-09-03 | 华中科技大学 | Organic-inorganic hybrid copper-based halide scintillator and preparation and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| "STN REGISTRY数据库公开记录", STN REGISTRY数据库公开记录 * |
| BECKER SABINE 等: "Investigations Concerning [Cu4OX6L4] Cluster Formation of Copper(II) Chloride with Amine Ligands Related to Benzylamine", EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, no. 14, pages 2437 - 2447, XP072126725, DOI: 10.1002/ejic.201500115 * |
| ZI GUOFU 等: "Synthesis, structure, and activity of (PhCH2NH2)2CuCl2 for oxidative coupling of 2-naphthylamine", APPLIED ORGANOMETALLIC CHEMISTRY, vol. 21, no. 03, pages 177 - 182, XP071530731, DOI: 10.1002/aoc.1197 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114875472A (en) * | 2022-04-25 | 2022-08-09 | 河南大学 | Organic-inorganic hybrid chiral perovskite helical structure micron sheet and preparation method and application thereof |
| CN114875472B (en) * | 2022-04-25 | 2023-11-03 | 河南大学 | Organic-inorganic hybrid chiral perovskite helical structure micron sheet and preparation method and application thereof |
| CN114957335A (en) * | 2022-06-24 | 2022-08-30 | 南开大学 | Method for preparing chiral metal halide from achiral precursor by chiral induction |
| CN114957335B (en) * | 2022-06-24 | 2024-04-05 | 南开大学 | Method for preparing chiral metal halide from achiral precursor through chiral induction |
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