CN116947932A - Nickel-based supermolecule light conversion material, preparation method thereof and application thereof in preparation of white light LED - Google Patents
Nickel-based supermolecule light conversion material, preparation method thereof and application thereof in preparation of white light LED Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 239000000463 material Substances 0.000 title claims abstract description 67
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 62
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
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- 238000000034 method Methods 0.000 claims abstract description 13
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000001257 hydrogen Substances 0.000 claims description 21
- 229910052739 hydrogen Inorganic materials 0.000 claims description 21
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 9
- 230000003993 interaction Effects 0.000 claims description 9
- ZHUXMBYIONRQQX-UHFFFAOYSA-N hydroxidodioxidocarbon(.) Chemical group [O]C(O)=O ZHUXMBYIONRQQX-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
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- CLWRFNUKIFTVHQ-UHFFFAOYSA-N [N].C1=CC=NC=C1 Chemical group [N].C1=CC=NC=C1 CLWRFNUKIFTVHQ-UHFFFAOYSA-N 0.000 claims description 3
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- 229910001220 stainless steel Inorganic materials 0.000 description 3
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- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
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- YLFZBPFYWIFYCP-UHFFFAOYSA-N 4-(4-carboxyphenyl)phthalic acid Chemical group C1=CC(C(=O)O)=CC=C1C1=CC=C(C(O)=O)C(C(O)=O)=C1 YLFZBPFYWIFYCP-UHFFFAOYSA-N 0.000 description 1
- QRZWEROLVZUPJH-KQQUZDAGSA-N 4-[(e)-2-[4-[(e)-2-pyridin-4-ylethenyl]phenyl]ethenyl]pyridine Chemical group C=1C=NC=CC=1/C=C/C(C=C1)=CC=C1\C=C\C1=CC=NC=C1 QRZWEROLVZUPJH-KQQUZDAGSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
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- 229910002804 graphite Inorganic materials 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
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K50/00—Organic light-emitting devices
- H10K50/80—Constructional details
- H10K50/84—Passivation; Containers; Encapsulations
- H10K50/844—Encapsulations
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- H—ELECTRICITY
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- H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
- H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
- H10K85/30—Coordination compounds
- H10K85/331—Metal complexes comprising an iron-series metal, e.g. Fe, Co, Ni
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- C—CHEMISTRY; METALLURGY
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- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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- C07B2200/13—Crystalline forms, e.g. polymorphs
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/187—Metal complexes of the iron group metals, i.e. Fe, Co or Ni
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Abstract
The application provides a nickel-based supermolecule light conversion material, the molecular composition of which is Ni (o-Hbpt) (bpeb) (H) 2 O) 4 Belonging to monoclinic system, the space group is P2 1 N space group, unit cell parameters In the chemical composition, the component o-Hbpt 2‑ Is a rigid ternary organic carboxylic acid o-H 3 The bpt is obtained by removing 2 protons, and the o-H is 3 The bpt structure is shown as the formula IThe method comprises the steps of carrying out a first treatment on the surface of the The bpeb structure of the component is shown as a formula IIThe material is a fluorescent nickel-organic coordination supermolecule crystalline material, and the abundant supermolecules in the monocrystal structure drive to weave complex three-dimensional supermolecules. The new material has mild preparation condition and the yield is about 79%; the crystal sample emits fluorescence in a wider range of 425-700nm at room temperature, and the fluorescence covers red, green and blue three primary color wave bands; the prepared white light LED device has the excellent performances of low energy consumption, near continuous spectrum, low blue light hazard, softer white light and the like.
Description
Technical Field
The application belongs to the field of advanced luminescent materials, and particularly relates to a nickel-based supermolecule light conversion material, a preparation method thereof and application thereof in preparing a white light LED.
Background
The Light-emitting Diode (LED) is called a fourth generation illumination Light source or a green Light source, has the characteristics of energy saving, environmental protection, long service life, small volume and the like, and is mainly applied to three fields of backlight sources, color screens and indoor illumination, wherein a white Light Diode (WLED) for indoor illumination is definitely the type with the widest use and the most favored. The LED industry chain can be divided into three links of chip manufacturing, packaging and application. The current mainstream technology for packaging the WLED is light conversion, which is based on the complementary principle of color light, and yellow fluorescent powder is coated on a blue LED chip so as to obtain the WLED; the fluorescent powder is mainly inorganic compound containing rare earth. However, the quality of most of the existing white LED devices needs to be improved, such as blue hazard needs to be further reduced, spectrum continuity is poor (mainly blue light needs to be supplemented), and the like. In view of the problems of limited types of inorganic composite fluorescent powder, non-renewable rare earth strategic resources, to-be-improved device quality and the like, development of a single-component non-rare earth-based light conversion new material has an important promotion effect on improving the quality of an LED light source and is a national strategic requirement for sustainable development.
Nickel is a common important element, the content of the nickel in the crust is larger than that of common lead, tin and the like, and the nickel and the compound thereof are mainly used for manufacturing alloys, electromagnetic materials, catalysts, dyes and the like; at present, doping with nickel compounds to produce inorganic composite phosphors is also being explored. In the advanced materials field, fluorescent metal-organic supermolecules (Fluorescence Metal-organic Supermolecule, FMOS) based on chromophoric organic molecules are a favored type, which drive synthesis mainly by coordination bonds, hydrogen bonds, etc.; the material has the characteristics of novel structure, high order, multiple functions and the like, and has attractive application prospects in the fields of photocatalysis, optical detection and the like. To our knowledge, nickel-based FMOS has been recently reported for use in the field of LED devices.
Disclosure of Invention
Aiming at the defects in the prior art, the application aims to provide a novel nickel-based supermolecule light conversion material, the accurate microscopic electronic structure of which is measured, and the novel material emits fluorescence in the range of 425-700nm under the excitation of 396nm purple light, and covers red, green and blue three primary color wave bands; can be used for preparing white light LED devices.
In order to achieve the above purpose, the present application provides the following technical solutions: a nickel-base supermolecule light-converting material has a molecular composition of Ni (o-Hbpt) (bpeb) (H) 2 O) 4 Belonging to monoclinic system, the space group is P2 1 N space group, unit cell parametersIn the molecular composition, the component o-Hbpt 2- Is a rigid ternary organic carboxylic acid o-H 3 The bpt is obtained by removing 2 protons, and the o-H is 3 The bpt structure is shown as a formula I; the bpeb structure of the component is shown as a formula II, and (2)>
Further, the asymmetric unit of the crystal structure of the nickel-based supermolecule light conversion material comprises 1 Ni which are independent in crystallography 2+ Ion, 1 o-Hbpt 2- 1 bpeb and 4 coordinated water molecules, and the whole structure is electrically neutral; organic composition o-Hbpt 2- And bpeb and Ni 2+ Ion monodentate coordination, each Ni 2+ The ion coordinates with 1 carboxyl oxygen atom, 1 pyridine nitrogen atom and four water molecules, and the coordination mode is shown as III; the partial numbers to the right of the element symbols in formula III are the numbers of atoms in the asymmetric units, H 2 O or OH 2 Water molecule, upper right corner of figureThe number # is the crystallographic symmetry transformation,
further, in the spatial structure of the nickel-based supermolecule light conversion material, a secondary structural unit [ Ni (H) 2 O) 4 ] 2+ Through O-H … O hydrogen bonds among water molecules, zigzag hydrogen bond chains [ Ni (H) 2 O) 4 ] n 2n+ In-chain Ni … Ni distance ofAndcomponent o-Hbpt 2- The carboxyl oxygen atom O5 of (2) connects the Z-shaped chain into a two-dimensional layer through hydrogen bond, and the layer contains a macrocyclic ring.
Further, in the periodically extended structure, there is a strong pi … pi interaction between adjacent bpeb components, bpeb and o-Hbpt 2- O-H … N hydrogen bond exists between O4 and O #4 … N2 distance isSupermolecule synthon Ni (o-Hbpt) (bpeb) (H) 2 O) 4 Through the interaction of rich O-H … O, O-H.N and pi … pi, a 3D supermolecule aggregate is formed; in the 3D structure, o-Hbpt 2- Alternately staggered with bpeb like wall bricks.
Further, the nickel-based supermolecule light conversion material is prepared by o-H 3 bpt、bpeb、Ni(NO 3 ) 2 ·6H 2 O and HBF 4 The solvent is prepared by using a mixed solution of acetonitrile and water as a solvent and adopting a solvothermal synthesis method.
Further, the preparation method specifically comprises the following steps:
(1) Mixing the raw materials and a solvent to form a reaction system, and placing the reaction system in a closed container; the raw material o-H 3 bpt：bpeb：Ni(NO 3 ) 2 ·6H 2 O and HBF 4 The mass ratio of the substances is 1:1:1.5:3 to8, 8; the volume ratio of the solvent acetonitrile to the water is 3-5: 5 to 7;
(2) Stirring the reaction system at room temperature for 10-30 min, heating the reaction temperature to 130-160 ℃, reacting for 3-5 days, naturally cooling, filtering and drying to obtain the massive crystal.
Further, the o-H in step (1) 3 bpt：bpeb：Ni(NO 3 ) 2 ·6H 2 O and HBF 4 The mass ratio of the substances is 1:1:1.5:4.5.
further, o-H in the reaction system 3 The initial material concentration of bpt or bpeb was 3.5mmol/L.
Further, the reaction temperature in the step (2) is 140 ℃, and the drying refers to natural drying in air at room temperature after the crystal is washed by distilled water.
The nickel-based supermolecule light conversion material prepared by the method is applied to the preparation of LED devices and composite fluorescent materials.
Compared with the prior art, the application has the following beneficial effects:
(1) The nickel-based supermolecule light conversion material prepared by the application is a three-component metal-organic coordination supermolecule crystalline material, and in the single crystal space structure, a secondary structural unit [ Ni (H) 2 O) 4 ] 2+ Through O-H … O hydrogen bond, zig-zag hydrogen bond chain [ Ni (H) 2 O) 4 ] n 2n+ The method comprises the steps of carrying out a first treatment on the surface of the Component o-Hbpt 2- The carboxyl oxygen atom O5 of (2) connects the Z-shaped chain into a two-dimensional layer through hydrogen bond; in the periodic expansion structure, stronger pi … pi interaction exists between adjacent bpeb components, so that a larger conjugated system is formed; ni (o-Hbpt) (bpeb) (H 2 O) 4 As a supermolecule synthon, a complex 3D supermolecule is formed by rich O-H … O and O-H. Cndot. N and pi … pi interactions, wherein the organic component O-Hbpt 2- And the bpeb is alternately staggered with each other like a wall brick. These novel structural features provide examples for the study of novel fluorescent crystalline materials.
(2) The nickel-based supermolecule light conversion material prepared by the application has mild preparation conditions, high purity and yield of about 79%, and the novel substance emits fluorescence in a wider range of 425-700nm under the excitation of 396 blue light, and covers red, green and blue three primary color wave bands; fluorescence excitation spectrum shoulder was at 451 nm.
(3) The white light LED device prepared by the nickel-based supermolecule light conversion material can work under the steady current of 3V 20mA, the CCT value is 5524K, positive white light is adopted, and the light color coordinate (0.3445,0.4493) is positioned in the white light area of the chromaticity diagram; the LED device has the excellent performances of low energy consumption, near continuous spectrum, low blue light hazard, softer white light and the like.
Drawings
FIG. 1 is an X-ray powder diffraction diagram of a nickel-based supramolecular light conversion material prepared according to the present application;
FIG. 2 is a thermogravimetric graph of a nickel-based supramolecular light conversion material prepared according to the present application;
FIG. 3 is an infrared spectrogram of the nickel-based supermolecule light conversion material prepared by the application;
FIG. 4 is a diagram showing the coordination mode and a partial crystal structure of the nickel-based supermolecule light conversion material prepared according to the present application, wherein the diagram (a) shows the coordination mode and the crystal structure of each component in the molecule, and the diagram (b) shows the secondary structural unit [ Ni (H) 2 O) 4 ]Zig-zag supermolecular chain constructed by hydrogen bond between coordinated water molecules, and the graph (c) is water molecules and o-Hbpt of Z-type chain 2- The carboxyl oxygen O5 of (2) forms hydrogen bonds and further expands into a two-dimensional supermolecular layer (the inner large ring is highlighted by ellipse);
FIG. 5 shows the spatial structure of the nickel-based supermolecule light-converting material of the present application, wherein strong pi.pi interaction exists between adjacent bpeb, ni (o-Hbpt) (bpeb) (H) 2 O) 4 Forming complex three-dimensional supermolecular bodies through rich molecular interactions;
FIG. 6 is a fluorescence spectrum of the nickel-based supermolecule light conversion material prepared by the application;
fig. 7 is a luminescence spectrum diagram, a chromaticity diagram and a photo of a nickel-based supermolecule light conversion material packaged LED device before and after the device emits light.
Detailed Description
The process according to the application is described in detail below with reference to specific examples and to the accompanying drawings. The application carries out X-ray single crystal diffraction test on the product, and analyzes the product to obtain an accurate electronic structure; and subjecting the final product to a series of characterization, such as infrared, fluorescence, X-ray powder diffraction, thermogravimetry, etc., to determine its molecular composition as Ni (o-Hbpt) (bpeb) (H) 2 O) 4 . In o-H 3 The bpt amount is calculated based on the yield, i.e., based on the o-Hbpt in the product composition 2- The mass ratio of the material to the theoretical mass of the complex to be obtained is calculated, and the ratio of the mass of the product to the theoretical mass of the complex to be obtained is the yield. O-H in the present application 3 The Chinese culture name of bpt is 3,4', 4-tricarboxyl biphenyl, the Chinese name of the component bpeb is 1, 4-bis [2- (4-pyridyl) vinyl]Benzene.
1. Preparation of the nickel-based supermolecule light conversion material
Example 1
The materials are taken according to the following specific mass or volume: o-H 3 bpt(10mg,0.035mmol；Mr＝286.24),bpeb(10mg,0.035mmol；Mr＝284.35)，Ni(NO 3 ) 2 ·6H 2 O(15mg，0.052mmol；Mr＝290.79)，CH 3 CN(3mL)，H 2 O(7mL),40％HBF 4 Solution (25. Mu.L, 1.39g/mL,0.158 mmol). o-H 3 bpt:bpeb:Ni(NO 3 ) 2 ·6H 2 O：HBF 4 The mass ratio of the substances is 1:1:1.5:4.5. placing the materials into a 25mL polytetrafluoroethylene lining, stirring for about 30min, sealing in a stainless steel reaction kettle, placing the reaction kettle into an electrothermal blowing oven, heating to 140 ℃, reacting for 3 days, naturally cooling to room temperature to obtain a blocky crystal sample, filtering the blocky crystal sample from mother liquor, washing with distilled water, and naturally drying in air at room temperature.
And (3) carrying out powder diffraction test (see figure 1, abscissa-angle; ordinate-diffraction intensity) on the prepared crystal sample by using an Shimadzu XRD-6100 type X-ray diffractometer, wherein the peak of the test spectrum can be well matched with the peak of a crystal structure analog spectrum (software Mercury), so that the obtained crystal sample has the same structure as that obtained by single crystal data, and the phase purity of the sample is high.
Analysis of thermogravimetric data of the obtained crystalline sample showed (see fig. 2, nitrogen atmosphere, abscissa-temperature; ordinate-residue), and as can be seen from fig. 2, the supramolecular material has almost no weight loss at 110 ℃, which indicates that the crystal has no structural characteristics of guest small molecules; a platform appears at 110-190 ℃, which is likely to lose all coordinated water molecules, and the calculated weight loss value is 10.3%; actual value 10.2%. This shows that the nickel-based supermolecule light conversion material prepared by the application has certain thermal stability.
Measurement of single crystal structure: selecting a suitable single crystal, and performing a diffraction on the SMARTAPEXII single crystal diffractometer (Mo-Ka,graphite monochromator), X-ray diffraction data were collected at room temperature and corrected for Lp factor. The crystal structure is solved by a direct method, the analysis and the refinement of the structure are completed by a SHELXTL-97 program package, and then the full matrix least square method F is used 2 All non-hydrogen atoms were subjected to anisotropic finishing. The hydrogen atom coordinates of the organic ligands are obtained by theoretical hydrogenation. The main crystallographic data are shown in table 1; the coordination bond length is shown in Table 2; the partial hydrogen bond lengths are shown in Table 3.
TABLE 1 primary crystallographic data
*R 1 ＝Σ||F o |-|F c ||/Σ|F o |，wR 2 ＝[Σ w (F o 2 -F c 2 ) 2 /Σ w (F o 2 ) 2 ] 1/2
TABLE 2 coordination bond length
TABLE 3 partial hydrogen bond lengths
Based on the characterization data, the molecular composition of the prepared nickel-based supermolecule light conversion material is Ni (o-Hbpt) (bpeb) (H) 2 O) 4 The chemical formula is C 35 H 32 N 2 O 10 Ni, formula weight 699.34, where CHN elemental analysis, calculated (%): C60.11,H 4.61,N 4.01; actual measured (%): c60.13, H4.60, N4.02. FIG. 3 is an infrared spectrum (abscissa-wave number; ordinate-light transmittance) of the novel material of the present application. FT-IR (KBr, cm) -1 ): 3548 (w), 3030 (w), 1698 (m), 1607(s), 1544(s), 1394(s), 1285 (w), 1018 (m), 978(s), 836(s), 763(s), 557 (vs). Description: elemental analysis values were measured by a Perkin-Elmer 2400 elemental analyzer; the infrared spectrum is based on a Perkin-Elmer FT-IR Spectrometer with KBr of 400-4000cm -1 Measured in range.
The single crystal X-ray diffraction data resolves the exact electronic structure. As shown in FIG. 4a and formula III, the asymmetric unit of the crystal structure of the nickel-based supermolecule light conversion material comprises 1 Ni which is independent of the crystal 2+ Ion, 1 o-Hbpt 2- 1 bpeb and 4 coordinated water molecules, and the whole structure is electrically neutral; organic composition o-Hbpt 2- And bpeb and Ni 2+ Ion monodentate coordination, each Ni 2+ The ion coordinates to 1 carboxyl oxygen atom, 1 pyridine nitrogen atom and four water molecules. o-Hbpt 2- In the crystal structure, the twist angle between the C6 and C14 aromatic rings is 12.2 degrees, which indicates that the electronic system has a larger degree of conjugation; in the bpeb crystal structure, the twist angle between the aromatic ring to which N2 and C29 belong and the CH=CH group is 12.5 degrees, and the twist angle between the rest adjacent functional groups is within 10 degrees, so that a large conjugated electron system exists in the bpeb structure; these conjugated electron systems and coordinated Ni 2+ And water molecules influence the transition and radiation of electrons between complex energy levels, and determine the optical performance of the light conversion material.
In the spatial structure of single crystal data analysis, the secondary structural unit [ Ni (H) 2 O) 4 ] 2+ (FIG. 4 b) through O-H … O hydrogen bonding (O7.cndot.cndot.O8) #2 O7 #2 ···O10 #3 />) (Hydrogen bonds are shown in Table 3) to form zig-zag hydrogen bond chains [ Ni (H) 2 O) 4 ] n 2n+ In-chain Ni … Ni distance is +.>And->Further, the component o-Hbpt 2- The carboxyl oxygen atom O5 of (c) connects the Z-type chains into two-dimensional layers by hydrogen bonds, the layers containing a hydrogen-bonded macrocyclic structure (fig. 4 c). FIG. 5 shows that there is a strong pi … pi interaction between adjacent bpeb components in the periodically extended structure; bpeb and o-Hbpt 2- Stronger O-H … N hydrogen bond and N2 … O4 exist between #4 Distance is->(formula III and Table 3). Ni (o-Hbpt) (bpeb) (H 2 O) 4 As a supermolecule synthon, complex 3D supermolecule aggregates are formed by abundant O-H … O and O-H. Cndot. N and pi … pi interactions, wherein the organic component O-Hbpt 2- And the bpeb is alternately staggered with each other like a wall brick. The data reveal that the structural features of the new material are key factors in determining its performance.
FIG. 6 is a fluorescence spectrum (abscissa-wavelength; ordinate-fluorescence intensity) of a crystal sample tested at room temperature. In the solid state fluorescence spectrum, fluorescence is emitted in the range of 425-700nm under the excitation of 396nm purple light, and the strongest peak wavelength is at 478 nm; the fluorescence wavelength range covers red, green and blue three primary color wave bands. The fluorescence excitation spectrum shoulder was at 451nm, indicating that fluorescence was also excited by blue light.
The example is repeated for a plurality of times, and the quality of the nickel-based supermolecule light conversion material is maintained at 15.2-19.4 mg based on o-H 3 The bpt is calculated to be 62.1-79.3% of the yield.
Example 2
The materials are taken according to the following specific mass or volume: o-H 3 bpt(10mg,0.035mmol),bpeb(10mg,0.035mmol)，Ni(NO 3 ) 2 ·6H 2 O(15mg，0.052mmol)，CH 3 CN(5mL)，H 2 O(5mL),40％HBF 4 Solution (16. Mu.L, 1.39g/mL,0.105 mmol). o-H 3 bpt:bpeb:Ni(NO 3 ) 2 ·6H 2 O：HBF 4 The mass ratio of the substances is 1:1:1.5:3. placing the materials into a 25mL polytetrafluoroethylene lining, stirring for about 30min, sealing in a stainless steel reaction kettle, placing the reaction kettle into an electrothermal blowing oven, heating to 130 ℃, reacting for 5 days, naturally cooling to room temperature to obtain a blocky crystal sample, filtering the blocky crystal sample from mother liquor, washing with distilled water, and naturally drying in air at room temperature.
The product powder was characterized by X-ray diffraction (see FIG. 1) and data was obtained similar to example 1. It was demonstrated that the crystal structure obtained in example 2 was unchanged and the purity of the product was higher.
The example is repeated for a plurality of times, and the quality of the nickel-based supermolecule light conversion material is kept between 13.1 and 15.8mg based on o-H 3 The bpt is calculated to be 53.5% -64.6% of the yield.
Example 3
The materials are taken according to the following specific mass or volume: o-H 3 bpt(10mg,0.035mmol),bpeb(10mg,0.035mmol)，Ni(NO 3 ) 2 ·6H 2 O(15mg，0.052mmol)，CH 3 CN(3mL)，H 2 O(7mL),40％HBF 4 Solution (45. Mu.L, 1.39g/mL,0.285 mmol). o-H 3 bpt:bpeb:Ni(NO 3 ) 2 ·6H 2 O：HBF 4 Substances of (2)The ratio of the amount of (2) is 1:1:1.5:8. placing the materials into a 25mL polytetrafluoroethylene lining, stirring for about 10min, sealing in a stainless steel reaction kettle, placing the reaction kettle into an electrothermal blowing oven, heating to 160 ℃, reacting for 3 days, naturally cooling to room temperature to obtain a blocky crystal sample, filtering the blocky crystal sample from mother liquor, washing with distilled water, and naturally drying in air at room temperature.
The product powder was characterized by X-ray diffraction (see FIG. 1) and data was obtained similar to example 1. It was demonstrated that the crystal structure obtained in example 3 was unchanged and the purity of the product was higher.
The example is repeated for a plurality of times, and the quality of the nickel-based supermolecule light conversion material is kept between 11.9 and 14.3mg based on o-H 3 The bpt is calculated to be 48.6-58.4 percent of yield.
2. Application of nickel-based supermolecule light conversion material
Example 4 white light LED device
In the experiment, the power of a common capped blue LED chip is about 1W. And packaging the nickel-based supermolecule light conversion material on an LED chip, and curing for 24 hours to obtain the white light LED device.
Fig. 7 is an emission spectrum, chromaticity diagram and device physical photograph (abscissa-wavelength, ordinate-normalized intensity) of an electrically driven LED device. The luminescence spectrum data shows that the Correlated color temperature (Correlated ColorTemperature, CCT) value is 5524K under the steady-state of 20mA (voltage of 3V), and can be attributed to positive white light; a dominant wavelength 562.0nm, color coordinates (0.3445,0.4493), in the white light region of the chromaticity diagram; the color rendering index CRI Ra 63.7, the smaller the number, may be mainly related to less blue and less violet, but is more environmentally friendly. In the light-emitting spectrum of the device, blue light with the wavelength below 470nm is less, and cyan light with the wavelength of 470-492nm is well supplemented; the luminescence wavelength range extends to near infrared 875 nm. The LED physical photo shows that the device emits softer white light when the LED physical photo works at 3V and 20mA, and the light color of the device is consistent with the color shown by the chromaticity diagram coordinate. The device data show that the prepared white light LED device has the excellent performances of low energy consumption, near continuous spectrum, low blue light hazard, softer white light and the like, is an environment-friendly white light device, and also reveals that the nickel-based supermolecule light conversion material of the application has good potential application prospect in the aspect of preparing energy-saving and environment-friendly LED devices.
Finally, it is noted that the above embodiments are only for illustrating the technical solution of the present application and not for limiting the same, and although the present application has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalents may be made thereto without departing from the spirit and scope of the technical solution of the present application, which is intended to be covered by the scope of the claims of the present application.
Claims (10)
1. A nickel-based supermolecule light conversion material is characterized in that the molecular composition is Ni (o-Hbpt) (bpeb) (H) 2 O) 4 Belonging to monoclinic system, the space group is P2 1 N space group, unit cell parameters In the molecular composition, the component o-Hbpt 2- Is a rigid ternary organic carboxylic acid o-H 3 The bpt is obtained by removing 2 protons, and the o-H is 3 The bpt structure is shown as a formula I; the bpeb structure of the component is shown as a formula II,
2. the nickel-based supermolecule light conversion material according to claim 1, wherein the asymmetric unit of the crystal structure of the nickel-based supermolecule light conversion material comprises 1 Ni which is independent of crystal 2+ Ion, 1 o-Hbpt 2- 1 bpeb and 4 coordinated water molecules, and the whole structure is electrically neutral; organic composition o-Hbpt 2- And bpeb and Ni 2+ Ion monodentate coordination, each Ni 2+ The ion coordinates with 1 carboxyl oxygen atom, 1 pyridine nitrogen atom and four water molecules, and the coordination modeThe formula is shown as III; the partial numbers to the right of the element symbols in formula III are the numbers of atoms in the asymmetric units, H 2 O or OH 2 Indicating water molecules, the number # of the right upper corner mark is the crystallographic symmetry conversion,
3. the nickel-based supermolecule light conversion material according to claim 2, wherein in the spatial structure of the nickel-based supermolecule light conversion material, the secondary structural unit [ Ni (H 2 O) 4 ] 2+ Through O-H … O hydrogen bonds among water molecules, zigzag hydrogen bond chains [ Ni (H) 2 O) 4 ] n 2n+ In-chain Ni … Ni distance ofAnd->Component o-Hbpt 2- The carboxyl oxygen atom O5 of (2) connects the Z-shaped chain into a two-dimensional layer through hydrogen bond, and the layer contains a macrocyclic ring.
4. The nickel-based supermolecule light conversion material according to claim 2, wherein there is strong pi … pi interaction between adjacent bpeb components in the periodically extended structure, bpeb and o-Hbpt 2- O-H … N hydrogen bond exists between O4 and O #4 … N2 distance isSupermolecule synthon Ni (o-Hbpt) (bpeb) (H) 2 O) 4 Through the interaction of rich O-H … O, O-H.N and pi … pi, a 3D supermolecule aggregate is formed; in the 3D structure, o-Hbpt 2- Alternately staggered with bpeb like wall bricks.
5. A method for preparing a nickel-based supermolecule light conversion material according to any one of claims 1-4Characterized in that the nickel-based supermolecule light conversion material adopts o-H 3 bpt、bpeb、Ni(NO 3 ) 2 ·6H 2 O and HBF 4 The solvent is prepared by using a mixed solution of acetonitrile and water as a solvent and adopting a solvothermal synthesis method.
6. The preparation method of the nickel-based supermolecule light conversion material according to claim 5, which is characterized by comprising the following steps:
(1) Mixing the raw materials and a solvent to form a reaction system, and placing the reaction system in a closed container; the raw material o-H 3 bpt：bpeb：Ni(NO 3 ) 2 ·6H 2 O and HBF 4 The mass ratio of the substances is 1:1:1.5:3 to 8; the volume ratio of the solvent acetonitrile to the water is 3-5: 5 to 7;
(2) Stirring the reaction system at room temperature for 10-30 min, heating the reaction temperature to 130-160 ℃, reacting for 3-5 days, naturally cooling, filtering and drying to obtain the massive crystal.
7. The method for preparing a nickel-based supramolecular light-converting material according to claim 6, wherein the o-H in step (1) 3 bpt：bpeb：Ni(NO 3 ) 2 ·6H 2 O and HBF 4 The mass ratio of the substances is 1:1:1.5:4.5.
8. the method for preparing a nickel-based supermolecule light conversion material according to claim 6 or 7, wherein o-H in the reaction system 3 The initial material concentration of bpt or bpeb was 3.5mmol/L.
9. The method for preparing a nickel-based supramolecular light-converting material according to claim 8, wherein the reaction temperature in the step (2) is 140 ℃, and the drying refers to natural drying of the crystal in air at room temperature after washing the crystal with distilled water.
10. The application of the nickel-based supermolecule light conversion material is characterized in that the nickel-based supermolecule light conversion material prepared by the method of any one of claims 5-8 is applied to the preparation of LED devices and composite fluorescent materials.
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