CN109456366B - { [ Ni (H) { [2O)4(phen)]SO4(C3H8N2O) } crystalline material - Google Patents
{ [ Ni (H) { [2O)4(phen)]SO4(C3H8N2O) } crystalline material Download PDFInfo
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- CN109456366B CN109456366B CN201811386629.9A CN201811386629A CN109456366B CN 109456366 B CN109456366 B CN 109456366B CN 201811386629 A CN201811386629 A CN 201811386629A CN 109456366 B CN109456366 B CN 109456366B
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- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 title claims abstract description 36
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000002178 crystalline material Substances 0.000 title claims description 15
- 239000013078 crystal Substances 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 27
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 claims description 11
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 claims description 10
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000012535 impurity Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- 230000008025 crystallization Effects 0.000 claims description 3
- 230000002269 spontaneous effect Effects 0.000 claims description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 abstract description 7
- 230000003287 optical effect Effects 0.000 abstract description 4
- 239000003446 ligand Substances 0.000 description 9
- 229910021645 metal ion Inorganic materials 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 150000004682 monohydrates Chemical class 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methylthiourea Natural products CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- XGEGHDBEHXKFPX-NJFSPNSNSA-N methylurea Chemical compound [14CH3]NC(N)=O XGEGHDBEHXKFPX-NJFSPNSNSA-N 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229940053662 nickel sulfate Drugs 0.000 description 2
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000000411 transmission spectrum Methods 0.000 description 2
- 150000003672 ureas Chemical class 0.000 description 2
- 229910017488 Cu K Inorganic materials 0.000 description 1
- 229910017541 Cu-K Inorganic materials 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000002050 diffraction method Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000002411 thermogravimetry Methods 0.000 description 1
- 238000002834 transmittance Methods 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
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
- G02B1/002—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials
- G02B1/005—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of materials engineered to provide properties not available in nature, e.g. metamaterials made of photonic crystals or photonic band gap materials
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
-
- 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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- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention belongs to the field of optical crystal materials, and particularly relates to { [ Ni (H) { [2O)4(phen)]SO4(C3H8N2O) } crystal material, preparation method and application thereof. The molecular formula of the crystal material is C15H24N4O9SNi, molecular weight 495.15, density 1.404g/cm3F (000) ═ 1032, belongs to the monoclinic system, and the space group is P21C, unit cell parameter of
α is 90 °, β is 100.67(12 °), γ is 90 °, unit cell volume is
The number of molecules in the unit cell, Z, is 4. The crystal material can be used as a filter material for manufacturing a crystal filter element.
Description
Technical Field
The invention belongs to the field of optical crystal materials, and particularly relates to { [ Ni (H) { [2O)4(phen)]SO4(C3H8N2O) } crystal material, preparation method and application thereof.
Background
Nickel is a commonly occurring element in coordination compounds and is well known for its wide range of applications. In recent years, experiments have been conducted on nickel-based materials to obtain a crystal structure. The research on the design, assembly, structural characterization and performance of the nickel sulfate-containing complex is a very popular research topic today. Because the structure of the complex is influenced by factors such as diversity of metal ions, diversity of ligands, diversity of coordination modes of metal ions and ligands, diversity of synthesis methods and the like, how to establish a spatial network on the basis of a molecular building module needs to be judged through experiments according to the geometric shape of central metal ions, the properties of a solvent, the chemical structure of ligands, the proportion of metal salts and organic ligands and the like, so that the differences in various aspects such as metal-ligands, symmetry of ligands, hydrogen bonds and the like can be generated, and the complex with different chemical compositions and spatial structures can be synthesized.
The phenanthroline is a bidentate heterocyclic compound ligand, and can be used as an auxiliary ligand in a crystal material to construct a crystal structure and improve the material performance. The metal ion chelate has strong chelation and can form a ring structure, so that the metal ion chelate can be used for forming a stable complex with most metal ions and is widely applied. For example, in 2007 researchers used nickel nitrate, phenanthroline and phthalic acid for self-assembly to obtain supramolecular complexes with three-dimensional structures, and determined their compositions and crystal structures by X-ray single crystal diffraction, elemental analysis, differential thermal-thermogravimetric analysis, infrared spectroscopy, and the like.
The study was carried out before this group using the methylurea of urea compounds as ligand. However, the product obtained by using methyl urea of urea compounds as the ligand of nickel sulfate does not have good transmission performance on blue light and does not have strong absorption on orange light. Therefore, there is still a need to develop new crystalline materials with suitable filter properties.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides { [ Ni (H) { [2O)4(phen)]SO4(C3H8N2O) } crystalline material of the formula C15H24N4O9SNi, molecular weight 495.15, density 1.404g/cm3F (000) ═ 1032, belongs to the monoclinic system, and the space group is P21C, unit cell parameter of
α＝90°，β＝100.67(12)°，γ＝90 DEG, cell volume of
The number of molecules in the unit cell, Z, is 4. In the present invention, phenanthroline is simply referred to as "phen".
According to an embodiment of the present invention, the crystal has a crystal structure as shown in fig. 1.
According to an embodiment of the invention, the crystalline material is in the form of a blue block.
According to an embodiment of the present invention, the transmission spectrum of the crystalline material has a maximum transmission peak position at a wavelength of 475.4 nm.
Further, the present invention also provides a method for preparing the above crystalline material, comprising: crystallizing after the reaction of nickel sulfate hexahydrate, phenanthroline and dimethyl urea to obtain { [ Ni (H)2O)4(phen)]SO4(C3H8N2O) } crystals;
NiSO4·6H2O+C12H8N2+C3H8N2O→[Ni(H2O)4(phen)]SO4(C3H8N2O)+2H2O。
according to an embodiment of the present invention, the phenanthroline may be selected from crystalline hydrates thereof, such as monohydrate.
According to the embodiment of the invention, the molar ratio of the nickel sulfate hexahydrate, the phenanthroline and the dimethyl urea is 1 (1-10) to (1-10), and for example, the molar ratio may be 1 (1-3) to (1-5), and further, for example, the molar ratio may be 1:1 (2-4).
According to an embodiment of the present invention, the temperature of the reaction is 40 to 80 ℃, preferably 50 to 70 ℃.
According to an embodiment of the present invention, the above method further comprises a step of filtering to remove impurities after the reaction is completed and before the crystallization.
As an example, the preparation method comprises the steps of:
mixing and dissolving nickel sulfate hexahydrate, phenanthroline and dimethyl urea serving as raw materials in water, heating and heating, stirring, and obtaining the productThe solution was filtered to remove foreign particles contained, and then the filtrate was cooled to room temperature to evaporate, to prepare { [ Ni (H) by spontaneous crystallization2O)4(phen)]SO4(C3H8N2O) } crystals.
According to an embodiment of the invention, the stirring is performed until the raw material is completely dissolved.
According to the embodiment of the invention, the filtration is performed by using a filter membrane with the diameter of 0.05-0.2 μm.
Furthermore, the invention also provides application of the crystal material as a filter material in manufacturing a crystal filter element.
The invention has the beneficial effects that:
the invention discloses { [ Ni (H) { [2O)4(phen)]SO4(C3H8N2O) } crystal material, the crystal material is prepared by spontaneous crystallization after the reaction of nickel sulfate hexahydrate, phenanthroline and dimethyl urea serving as raw materials is completed, and the preparation method is simple and convenient to operate. The spectral characteristics show that the crystal material has good transmission performance on blue light with the wavelength of about 475nm, has strong absorption on orange light with the wavelength of about 600nm, can be used for manufacturing crystal filter devices, is applied to optical devices, and has high practicability.
Drawings
FIG. 1 shows a crystalline material { [ Ni (H) { [2O)4(phen)]SO4(C3H8N2O) } and the atom number diagram.
FIG. 2 shows a crystal material { [ Ni (H) { [2O)4(phen)]SO4(C3H8N2O) }.
FIG. 3 shows a crystal material { [ Ni (H) { [2O)4(phen)]SO4(C3H8N2O) } and simulated powder diffraction patterns.
FIG. 4 shows a crystalline material { [ Ni (H) { [2O)4(phen)]SO4(C3H8N2O) }.
Detailed Description
The technical solution of the present invention will be further described in detail with reference to specific embodiments. It is to be understood that the following examples are only illustrative and explanatory of the present invention and should not be construed as limiting the scope of the present invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1: crystalline material { [ Ni (H) { [2O)4(phen)]SO4(C3H8N2O) } preparation of
Taking 2g of nickel sulfate hexahydrate (98.5 percent or more), 1.508g of orthophenanthrene (99 percent or more) (monohydrate) and 2.682 g of dimethyl urea (98 percent) as raw materials, mixing and dissolving the raw materials in a molar ratio of 1:1:4 in pure water, heating to about 60 ℃, sufficiently heating and stirring for a period of time by using a stirrer, filtering the obtained solution by using a filter membrane with the pore diameter of 0.15 mu m after the solution is completely dissolved, removing impurity particles in the solution, cooling the filtrate to room temperature, slowly evaporating the filtrate, and obtaining { [ Ni (H) after one week of evaporation2O)4(phen)]SO4(C3H8N2O) } blue block crystals.
Example 2: crystalline material { [ Ni (H) { [2O)4(phen)]SO4(C3H8N2O) } preparation of
Taking 2g of nickel sulfate hexahydrate (98.5 percent or more), 1.508g of orthophenanthrene (99 percent or more) (monohydrate) and 1.353 g of dimethylurea (98 percent) as raw materials, mixing and dissolving the raw materials in a molar ratio of 1:1:2 in pure water, heating to about 60 ℃, sufficiently heating and stirring the mixture for a period of time by using a stirrer, filtering the obtained solution by using a filter membrane with the pore diameter of 0.15 mu m after the solution is completely dissolved, removing impurity particles contained in the solution, cooling the filtrate to room temperature for slow evaporation, filtering mother liquor after evaporation for several days, and standing to prepare the { [ Ni (H) which is a compound of formula I, formula II and formula II) and the2O)4(phen)]SO4(C3H8N2O) } blue blockAs crystals.
Selecting blue block crystals with the size of 0.05mm multiplied by 0.04mm multiplied by 0.03mm prepared by the method, placing the blue block crystals on an UltraX-Saturn 724 single crystal diffractometer for diffraction experiment, and performing single crystal diffraction analysis by using Mo-K α rays (lambda is 0.071073nm) under 293K in an omega-2 theta scanning mode, wherein the result shows that the molecular formula of the blue block crystals is C15H24N4O9SNi, molecular weight 495.15, density 1.404g/cm3F (000) ═ 1032, belongs to the monoclinic system, and the space group is P21C, unit cell parameter of
α is 90 °, β is 100.67(12 °), γ is 90 °, unit cell volume is
The number of molecules in the unit cell, Z, is 4. The unit cell stacking diagram is shown in FIG. 2.
Will obtain [ Ni (H) ]2O)4(phen)]SO4(C3H8N2O) crystal was ground into a fine powder with an agate mortar, X-ray diffraction data of the powder was collected using Cu-K α radiation on a Miniflex 600 diffractometer after tabletting, and the simulated powder diffraction pattern of the data collected by single crystal diffraction was compared with the actual diffraction pattern, and it was found that the two patterns were consistent in peak position, as shown in fig. 3.
The transmission spectrum of the crystal sample was measured by an ultraviolet spectrophotometer, and the results are shown in FIG. 4. The crystal material has a maximum peak position at 475.4nm and a transmittance of 50.9%, which shows that the crystal material has good transmission performance for blue light with a wavelength of about 475.4nm and strong absorption for orange light with a wavelength of about 600nm, and the spectral characteristics show that the crystal material can be used for manufacturing crystal filters and applied to optical devices.
Example 3: crystalline material { [ Ni (H) { [2O)4(phen)]SO4(C3H8N2O) } preparation of
1.32g of nickel sulfate hexahydrate (98.5 percent or more), 1g of orthophenanthrene (99 percent or more) (monohydrate) and 1.32g of dimethyl urea (98 percent) are used as raw materials in a molar ratioDissolving in pure water at a ratio of 1:1:3, heating to about 60 ℃, sufficiently heating and stirring with a stirrer for a period of time, filtering the obtained solution with a filter membrane with a pore diameter of 0.15 mu m after completely dissolving, removing impurity particles, cooling the filtrate to room temperature for slow evaporation, filtering the mother liquor after evaporation for several days, and standing to prepare { [ Ni (H) Ni2O)4(phen)]SO4(C3H8N2O) } blue block crystals.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. { [ Ni (H) { [2O)4(phen)]SO4(C3H8N2O) } crystalline material, characterised in that the molecular formula is C15H24N4O9SNi, molecular weight 495.15, density 1.404g/cm3F (000) ═ 1032, belongs to the monoclinic system, and the space group is P21C, unit cell parameter of
α is 90 °, β is 100.67(12 °), γ is 90 °, unit cell volume is
The number of molecules Z in the unit cell is 4;
wherein C is3H8N2O is dimethyl urea.
2. A method for preparing the crystalline material of claim 1, comprising: crystallizing after the reaction of nickel sulfate hexahydrate, phenanthroline and dimethyl urea to obtain { [ Ni (H)2O)4(phen)]SO4(C3H8N2O) } crystals;
NiSO4·6H2O+C12H8N2+C3H8N2O→[Ni(H2O)4(phen)]SO4(C3H8N2O)+2H2O。
3. the method according to claim 2, wherein the molar ratio of nickel sulfate hexahydrate, phenanthroline and dimethylurea is 1 (1-10) to (1-10).
4. The method according to claim 2 or 3, wherein the reaction temperature is 40 to 80 ℃.
5. The method according to claim 4, further comprising a step of filtering to remove impurities after the reaction is completed and before the crystallization.
6. The method of manufacturing according to claim 5, comprising the steps of:
mixing and dissolving nickel sulfate hexahydrate, phenanthroline and dimethyl urea serving as raw materials in water, heating and stirring, filtering the obtained solution to remove impurity particles, cooling the filtrate to room temperature for evaporation, and preparing the { [ Ni (H) through spontaneous crystallization2O)4(phen)]SO4(C3H8N2O) } crystals.
7. Use of the crystalline material of claim 1 as a filter material in the manufacture of a crystalline filter element.
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