CN114891029B - Cd (cadmium sulfide) 2+ Base coordination compound SUST-WJ-12, and preparation method and application thereof - Google Patents
Cd (cadmium sulfide) 2+ Base coordination compound SUST-WJ-12, and preparation method and application thereof Download PDFInfo
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- 150000001875 compounds Chemical class 0.000 title claims abstract description 62
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 title claims abstract description 4
- 229910052980 cadmium sulfide Inorganic materials 0.000 title claims abstract description 4
- 238000000034 method Methods 0.000 claims abstract description 18
- UEYQJQVBUVAELZ-UHFFFAOYSA-N 2-Hydroxynicotinic acid Chemical compound OC(=O)C1=CC=CN=C1O UEYQJQVBUVAELZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000008569 process Effects 0.000 claims abstract description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 40
- 239000000203 mixture Substances 0.000 claims description 20
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 16
- 239000013078 crystal Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
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- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims 1
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- 238000004020 luminiscence type Methods 0.000 abstract description 13
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F3/00—Compounds containing elements of Groups 2 or 12 of the Periodic Table
- C07F3/003—Compounds containing elements of Groups 2 or 12 of the Periodic Table without C-Metal linkages
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
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- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
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- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
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Abstract
Cd (cadmium sulfide) 2+ Base coordination compound SUST-WJ-12, preparation method and application thereof, and organic ligand 2-hydroxynicotinic acid (H) 2 L) and Cd 2+ Self-assembled polynuclear cluster coordination compounds. The organic ligand H 2 The molecular formula of L is: c (C) 6 H 5 NO 3 By solvothermal reaction with Cd 2+ The self-assembly preparation obtains a coordination compound SUST-WJ-12 with long afterglow performance, the coordination compound can show different luminescent colors at different excitation wavelengths and different temperatures, white luminescence can be obtained in the process, and when a light source is removed, the coordination compound SUST-WJ-12 emits yellow long afterglow, and multicolor anti-counterfeiting can be realized by utilizing the characteristic; simultaneously SUST-WJ-12 is nontoxic and nonvolatile, can be prepared into nano-scale, is doped with a polymer material to prepare ink with stable physical characteristics and luminescence and a spinnable polymer compound, and is applied to optical anti-counterfeiting ink and a film.
Description
Technical Field
The present invention belongs to the field of polychromatic antifake technologyRelates to a coordination compound SUST-WJ-12, a preparation method and application thereof, in particular to an organic ligand 2-hydroxynicotinic acid (H) 2 L) and Cd 2+ A preparation method and application of self-assembled polynuclear cluster coordination complex.
Background
In recent years, the long afterglow materials are widely applied to various fields of OLED, display and decoration, sensing, anti-counterfeiting bar codes, military night vision, biological imaging and the like. The long afterglow material based on the metal-organic framework is formed by simple self-assembly of various metal ions or metal clusters and different types of organic ligands due to the stability of inorganic materials and the diversity of organic ligands, so that the defects of harsh synthesis conditions, high price, difficult control and modification of morphology, low thermal stability and poor aging resistance of the organic materials are avoided, and the defects of wide attention of academia and industry are paid.
Based on the metal-organic framework long afterglow material, the metal ions related to heavy atom effect can accelerate spin orbit coupling of excited electrons, generally enhance rigidity of the framework, limit movement/vibration of molecules, reduce non-radiative loss of excitons, and promote phosphorescence emission. Meanwhile, the organic light-emitting material is a space structure constructed by metal nodes and organic ligands, so that the cooperative coupling of different light-emitting centers and light-emitting mechanisms can be realized, and target optical response can be generated through interaction of the structure and external stimuli such as solvents, objects, photo-thermal compression and the like, so that the organic light-emitting material has unique advantages in the aspect of designing intelligent and tunable long-afterglow luminescent materials, and is developed gradually.
At present, materials for constructing the long afterglow metal-organic framework are rich in metal ion types, so that the metal inorganic structural units are various, and the metal inorganic structural units can be divided into single-core metal ions and multi-core metal clusters (multi-core clusters) according to the number of (SBUs) metal ions participating in constructing the inorganic second structural units. In most cases, the mononuclear metal ions are directly and only connected with the electron donor in the ligand, the connection number and the spatial configuration mainly depend on the coordination mode of the metal, so that the connection mode of the mononuclear metal SBUs is relatively single, the types of the constructed long-afterglow MOFs framework structure are limited, and when the size of the ligand becomes large, the constructed framework structure has large porosity, intense molecular thermal vibration, serious non-radiative transition of the material and short phosphorescent life, and thus the macroscopic long afterglow phenomenon cannot be generated. However, in the multi-core metal cluster structural unit, metal ions are connected with ligands and also connected with bridging oxygen ions or hydroxyl ions at the same time, a multi-core cluster structure is formed by jointly connecting a plurality of metal ions with the ligands and the bridging groups, the space configuration of the multi-core clusters is more complex, the number of the connections is more and more stable, and particularly the multi-core clusters with regular structures and high symmetry are widely applied to design and synthesis of MOFs materials with specific topological structures, high stability and functionalization, however, the research on metal-organic framework long afterglow materials taking the multi-core clusters as the centers is less.
Therefore, research and development of a novel high-stability and functional MOFs long-afterglow luminescent material induced by polynuclear clusters have important significance.
Disclosure of Invention
The object of the present invention is to provide a complex SUST-WJ-12 (organic ligand is denoted as H 2 L) and a preparation method and application thereof, SUST-WJ-12 not only shows different luminescent colors under the excitation of different light sources, but also emits white light under the excitation of 280nm with specific wavelength, and especially shows bright orange-yellow long afterglow after the light source is removed. Meanwhile, the material can be prepared into nano-scale small particles by grinding, ultrasonic and other methods, and the nano-scale small particles and cellulose and the like are uniformly compounded together to prepare a stable luminous anti-counterfeiting film; the anti-counterfeiting ink can be blended with a water-based polymer, and the water-based anti-counterfeiting ink suitable for screen printing can be prepared through formula adjustment, so that the anti-counterfeiting purpose is achieved. Therefore, the material can be used as a multicolor luminous anti-counterfeiting material, and overcomes the defects of poor long afterglow performance and low signal to noise ratio under the induction of single-core metal in the prior art.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a coordination compound SUST-WJ-12, characterized by the formula: c (C) 6 H 3 CdNO 3 Belongs to triclinic system, and belongs to the empty of triclinic systemThe interstice is P-1 and the molecular weight is 249.49.
The coordination compound SUST-WJ-12 is H 2 L and cadmium chloride are used as raw materials to prepare the coordination compound SUST-WJ-12.
A process for the preparation of a coordination compound SUST-WJ-12, comprising the steps of:
s1, cadmium chloride and H 2 Mixing L according to the mol ratio of 1-5:1, and putting the mixture into a stainless steel high-pressure reaction kettle, wherein the volume ratio of water to N, N-dimethylformamide is 1-5: 1 to 5 are added into a reaction kettle and then are stirred uniformly, wherein water and H 2 The dosage ratio of L is 1-5 mL:0.05mmol, and the N, N-dimethylformamide and H 2 The dosage ratio of L is 1-5 mL:0.05mmol;
s2, heating in a sealed pressure-resistant reaction kettle for 1-3 hours, heating from room temperature to 100-120 ℃, keeping the temperature for 40-60 hours, and cooling to room temperature for 8-12 hours;
s3, cooling to room temperature to obtain yellow needle-like crystals, filtering and washing with N, N-dimethylformamide to obtain pure crystals.
Further, the step S1 is the cadmium chloride, H 2 The molar ratio of L is 1:1.
Further, the volume ratio of the water to the N, N-dimethylformamide in the step S1 is 5:1.
further, the step S1 is performed by using the water and H 2 The amount ratio of L was 5mL:0.05mmol.
Further, the step S1 is performed by using N, N-dimethylformamide and H 2 The dosage ratio of L is 1mL:0.05mmol.
Further, the step S2 is to heat for 2 hours to 120 ℃, keep the temperature for 50 hours, and then cool to room temperature for 10 hours.
Further, a process for preparing a complex SUST-WJ-12 comprising reacting H 2 L (100 mg,0.7 mmol), cadmium chloride (130 mg,0.7 mmol) mixture is added into a 50mL reaction kettle polytetrafluoroethylene lining, then 5mL water and 1mL N, N-dimethylformamide are added, the mixture is stirred uniformly, and the mixture is capped and filled into a matched stainless steel reaction kettle; then put the reaction kettle into a baking kettleA box, heating for 2 hours to 120 ℃, keeping the temperature for 50 hours, and cooling to room temperature for 10 hours; finally, the mixture is filtered to obtain yellow coordination complex monocrystal.
Furthermore, the coordination compound SUST-WJ-12 is applied to the field of multicolor anti-counterfeiting and data encryption.
Further, the preparation of the luminous anti-counterfeiting film based on the coordination compound SUST-WJ-12 comprises the following steps: the coordination compound SUST-WJ-12 is sufficiently ground to obtain powder, SUST-WJ-12 monocrystal powder is dispersed in a nonpolar organic solvent, the nonpolar organic solvent is common low-boiling point nonpolar organic solvents such as n-heptane or acetone, cellulose is added, uniform dispersion is carried out, ultrasonic treatment is carried out for 8-15 minutes, a mucilage glue transparent mixture is obtained, then the mixed solution is filled in a mould, and standing is carried out for 2-4 hours at room temperature, so that the solvent is sufficiently volatilized, and the luminous anti-counterfeiting film is obtained.
Further, the preparation of the luminous anti-counterfeiting film based on the coordination compound SUST-WJ-12 comprises the following steps: dispersing SUST-WJ-12 powder in an organic solvent (preferably, the organic solvent is a low-boiling point organic solvent such as common methanol, ethanol, ethyl acetate, dichloromethane, chloroform, hexane, n-hexane or n-pentane and the like), and uniformly coating on non-fluorescent paper (namely, any other type of paper which is not fluorescent paper, such as filter paper, non-fluorescent drawing paper and the like) to obtain the multicolor luminous anti-counterfeiting film.
Further, the film is obtained by the following method: fully grinding a coordination compound SUST-WJ-12, dispersing complex SUST-WJ-12 powder in an acetone solution, adding cellulose, carrying out ultrasonic treatment for 10 minutes to uniformly compound the mixture, filling the mixture into a mold, standing at room temperature for 2-4 hours to fully volatilize a solvent, and thus obtaining a stable multicolor luminous anti-counterfeiting film;
further, the SUST-WJ-12 is fully grinded into crystals, the coordination compound SUST-WJ-12 powder is dispersed in methanol solvent and uniformly smeared on non-fluorescent paper (namely, any other type of paper which is not fluorescent paper, such as filter paper, non-fluorescent drawing paper and the like) to obtain the multicolor luminous anti-counterfeiting film with paper as a matrix.
Further, in the above-mentioned method for producing a luminescent anti-counterfeiting film, it is preferable that the usage ratio of the complex SUST-WJ-12 powder to acetone is 0.01 to 0.05g/mL.
Further, the dosage ratio of the complex SUST-WJ-12 powder to acetone was 0.03g/mL.
Further, the mass ratio of the complex SUST-WJ-12 powder to cellulose is 1:5 to 10.
Further, the mass ratio of the complex SUST-WJ-12 powder to cellulose is 1:8.
further, the time of the ultrasound was 10 minutes.
Further, the solvent was allowed to evaporate sufficiently by standing at room temperature for 3 hours.
Further, the dosage ratio of the SUST-WJ-12 complex powder to the methanol is 0.01-0.05 g/mL.
Further, the dosage ratio of the complex SUST-WJ-12 powder and methanol was 0.03g/mL.
Further, the solvent was allowed to evaporate sufficiently by standing at room temperature for 3 hours.
In addition, the application of the coordination compound SUST-WJ-12 or the multicolor luminous anti-counterfeiting film is within the protection scope of the invention.
In particular, the application of the complex SUST-WJ-12 in multicolor anti-counterfeiting is within the protection scope of the invention.
A luminous anti-counterfeiting ink is obtained by the following steps: (Complex SUST-WJ-12 is sufficiently ground to obtain powder), SUST-WJ-12 single crystal powder is prepared into nano-scale, and then the nano-scale powder is blended with an aqueous polymer (preferably, the aqueous polymer comprises poly (vinyl pyrrolidone) (PVP), poly (vinyl acetate) (PVA) and Acrylate Resin (AR) (ultrasonic treatment is carried out for 10-15 minutes), so that the highly stable luminous anti-counterfeiting ink is successfully prepared, and the luminous anti-counterfeiting ink can be suitable for screen printing and achieves the anti-counterfeiting purpose.
Further, the noctilucent anti-counterfeiting ink is obtained by the following method: fully grinding the coordination compound SUST-WJ-12, mixing nanoscale powder of the coordination compound SUST-WJ-12 with PVP, and carrying out ultrasonic treatment for 10 minutes to uniformly compound the powder together to prepare the highly stable luminous anti-counterfeiting ink.
In the preparation method of the luminescent anti-counterfeiting ink, preferably, the dosage ratio of the complex SUST-WJ-12 to PVP is 1:5 to 10.
Further, the dosage ratio of the complex SUST-WJ-12 to PVP is 1:8.
further, as a referenceable embodiment, the method of application may be as follows:
(1) SUST-WJ-12 is fully milled and uniformly smeared on a seal carved with a logo, a two-dimensional code, SUST-WJ and 2022 of Shanxi university of science and technology and chemical university, the seal is covered on non-fluorescent paper, and the seal pattern with multicolor luminescence can be observed by irradiation of an ultraviolet lamp.
(2) After the luminous anti-counterfeiting film is irradiated by an ultraviolet lamp, the light source is removed, the fluorescent film can be observed to display yellow long-afterglow luminescence, and the fluorescent film can also display stable long-afterglow luminescence after repeated for a plurality of times and can be reused for a plurality of times. The film can show different colors under different excitation wavelengths and after the light source is removed, so that multicolor anti-counterfeiting is realized.
(3) The coordination compound SUST-WJ-12 is sufficiently milled and ultrasonically prepared into nano-scale, then is blended with water-based polymers (including poly (vinyl pyrrolidone), poly (vinyl acetate) and acrylate resin) to prepare highly stable luminescent ink, and the anti-counterfeiting ink suitable for screen printing is prepared through formula adjustment, so that the anti-counterfeiting purpose is achieved. The anti-counterfeiting luminous pattern can be screen printed on non-fluorescent paper, and the encryption and decryption of information can be accurately and conveniently realized by switching ultraviolet irradiation.
The invention has the following beneficial effects:
(1) The multi-core cluster adopted by the invention induces and increases spin orbit coupling, and inhibits non-radiative transition so that the coordination compound has more stable long afterglow luminescence performance;
(2) The long afterglow luminous signal-to-noise ratio is improved, and the performance of the coordination compound is optimized;
(3) The coordination compound SUST-WJ-12 belongs to a single material and has the advantage of stable luminescence performance; white light emission can be realized by changing the excitation wavelength, so that the white light emission is nontoxic and nonvolatile, is easier to recycle and has environmental friendliness;
(4) The luminous anti-counterfeiting film can be prepared based on the coordination compound, is easy to process, has good physical properties and luminous stability, and can be used for multiple times for a long time.
(5) The noctilucent anti-counterfeiting ink prepared based on the coordination compound is safe and stable, can accurately and conveniently realize encryption and decryption of information by switching ultraviolet irradiation, and can be used for printing and writing.
Drawings
FIG. 1 is H 2 L molecular structure and coordination compound SUST-WJ-12 preparation diagram.
FIG. 2 is a crystal structure of SUST-WJ-12. a) An asymmetric unit and a coordination environment of metal ions; b, c) a metal and H 2 The L ligand self-assembles to form a 2D structure with 2 nuclear clusters; d) And 3D framework structure formed by hydrogen bond interaction.
FIG. 3 is an infrared spectrum of SUST-WJ-12.
FIG. 4 is a TGA curve of SUST-WJ-12.
FIG. 5 is a PXRD spectrum of a simulated and synthesized SUST-WJ-12.
FIG. 6 is H 2 A) excitation spectrum and b) emission spectrum of the L ligand and a gating spectrum delayed by 1 ms.
FIG. 7 is a gating spectrum of SUST-WJ-12 with a) excitation spectrum and b) emission spectrum and delay of 1 ms.
FIG. 8 shows the variable excitation spectrum of SUST-WJ-12 and the corresponding CIE coordinates.
FIG. 9 is a time resolved fluorescence spectrum of SUST-WJ-12.
FIG. 10 is a decay lifetime graph of SUST-WJ-12 in air and vacuum.
FIG. 11 is an emission spectrum of SUST-WJ-12 (air, vacuum).
FIG. 12 is a temperature change emission spectrum of SUST-WJ-12 at 77-300K.
FIG. 13 is a temperature swing lifetime spectrum of SUST-WJ-12 at 77-300K.
FIG. 14 shows the LPL spectrum of SUST-WJ-12 over time and the corresponding CIE coordinates (lambda ex ＝365nm)。
FIG. 15 is the corresponding CIE coordinates of SUST-WJ-12 temperature dependent emission spectra.
FIG. 16 is an energy transfer mechanism of SUST-WJ-12.
FIG. 17 is a powder photograph of SUST-WJ-12 under sunlight and ultraviolet rays.
FIG. 18 is a schematic illustration of the use of SUST-WJ-12 in imaging, decoration and security.
FIG. 19 shows the application of SUST-WJ-12 noctilucent anti-counterfeiting film in anti-counterfeiting.
Detailed Description
The present invention will be further described with reference to the accompanying drawings, but the present invention is not limited to the following examples. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Through a great deal of research and exploration, the invention prepares the high-performance coordination compound based on multi-core cluster induction. The invention uses the organic ligand H 2 The molecular formula of the coordination compound SUST-WJ-12 synthesized by adopting a solvothermal reaction method is as follows: c (C) 6 H 3 CdNO 3 . The coordination compound SUST-WJ-12 is crystallized in a triclinic system and belongs to the P-1 space group. The asymmetric unit consists of 1L 2- Ligand and 1 Cd 2+ Composition is prepared. Wherein Cd is 2+ Is hexacoordinated, in which four O atoms from three ligands lie in the equatorial plane, while one N atom and one oxygen atom in the axial direction come from the other two ligands, respectively, exhibiting overall an octahedral geometry. In SUST-WJ-12, the Cd (II) atom passes through 2. Mu.s 2 The carboxyl groups O bridge to form 2 nucleus Cd 2 O 5 N clusters, whereas binuclear clusters pass μ 2 Hydroxyl groups O bridge to form double rows of 1-dimensional metal chains, and the metal chains are further connected through ligands to form a 2D coordination framework structure. In general, intermolecular non-covalent interactions play a critical role in the crystal packing process, such as weak interactions of C-h..o, C-h..n, C-H … pi and pi-pi, which can make the crystals arranged sufficiently dense during packing to have better photophysical properties. The 2-dimensional framework structure is further assembled by C-h..o intermolecular hydrogen bond interactionsA dense 3-dimensional structure is formed (the crystal structure of coordination compound SUST-WJ-12 is shown in fig. 2).
The invention is based on polynuclear cluster induced high-performance coordination compound, adopts polynuclear cluster induced spin orbit coupling increase, and inhibits non-radiative transition so that the complex has more stable long afterglow luminescence performance. The coordination compound can show different luminescent colors after being excited by different light sources and the light sources are removed, thereby realizing multicolor anti-counterfeiting. The luminous anti-counterfeiting film and the printing ink prepared by the coordination compound have good physical properties and luminous stability, and can be repeatedly used.
Reagents and materials used in the following examples are commercially available unless otherwise specified.
The applied instrument is: single crystal data on copper targetsMeasuring by a single crystal X-ray diffractometer on a Rigaku-Oxford ultra-new star X-ray diffractometer system; the infrared data were measured at 4000-400cm using a Nicolet/Nexus-670 Fourier infrared spectrometer -1 The sample is collected by a potassium bromide tabletting method in a range, and a Specac small tabletting machine is adopted for tabletting the sample; powder X-ray diffraction (PXRD) was measured using a Rigaku SmartLab diffractometer (Bragg-Brentano geometry, cu kα1 radiation, λ= 1.54056 a); thermogravimetry at 10 ℃ min under nitrogen and 1atm pressure -1 Thermogravimetric analysis (TGA) was performed on the NETZSCH TG209 system; recording the ultraviolet-visible absorption spectrum using a Shimadzu UV-2450 spectrophotometer; fluorescence spectra were measured by an Edinburgh FLS 980 spectrometer. Long-lasting luminescence was tested using a Q65 Pro instrument; the anti-counterfeiting encrypted picture is obtained by photographing a mobile phone by using China.
EXAMPLE 1 preparation of coordination Compound SUST-WJ-12
Preparation of coordination Compound SUST-WJ-12:
will H 2 L (100 mg,0.7 mmol) and cadmium chloride (130 mg,0.7 mmol) were added to a 50mL polytetrafluoroethylene-lined reaction vessel containing 1.0 mL DMF and 5mL distilled water and heated at 120℃for 3 days. Then yellow of (SUST-WJ-12) was obtained by DMF washingNeedle-like crystals.
EXAMPLE 2 determination of Crystal Structure of coordination Compound SUST-WJ-12
In the presence of copper targetsSingle crystal X-ray diffraction data of SUST-WJ-12 were collected on a Rigaku-Oxford supernova X-ray diffractometer system at 50kV and 0.80 mA.
The structure is solved by adopting a direct method, and is refined by adopting a full matrix least square method by utilizing a SHELXL-2014 program package. All hydrogen atoms are obtained by a theoretical hydrogenation method and refined along the anisotropic direction; l in SUST-WJ-12 2- The upper atoms were not positive and were refined using the color command, and the crystallographic data for SUST-WJ-12 are shown in Table 1.
Table 1 shows the crystallographic data of the coordination compound SUST-WJ-12
As can be seen from FIG. 2, SUST-WJ-12 is a 3D network structure of multi-core clusters, which may have better intersystem crossing efficiency, providing a basis for effective long afterglow luminescence.
Example 3 determination of fluorescence Properties of SUST-WJ-12
H 2 L ligands, as well as coordination compounds, have both fluorescent and phosphorescent emissions. SUST-WJ-12 the relative intensity of IP/IF (IP and IF average of phosphorescence intensity and fluorescence intensity, respectively) gradually increases as the excitation wavelength increases from 280nm to 440nm, and the luminescence color of SUST-WJ-12 changes from blue to cyan to yellow-green. The coordination compound SUST-WJ-12 is introduced with Cd 2+ After metal clusters, cluster-based atomic weight effects are created, resulting in a greatly enhanced phosphorescent lifetime. And the complex compound is in vacuum or air, the obtained emission spectrum isThe lines are basically matched, and the luminous performance of the material is proved to be very stable whether the material is in air or vacuum.
In the temperature range of 77K to 300K, the decay lifetime of the coordination compound SUST-WJ-12 is significantly reduced from about 200ms to 64ms as the temperature increases. Meanwhile, the coordination compound SUST-WJ-12 has phosphorescence emission with temperature response, and by increasing the temperature (in the range of 77K to 300K), the luminescence color shows a transition from yellow-green to cyan to blue region.
H 2 The excitation spectrum, emission spectrum and gating spectrum delayed by 1ms for L and SUST-WJ-12 are shown in FIGS. 6 and 7.
The variable excitation spectrum of SUST-WJ-12 and the corresponding CIE coordinates are shown in FIG. 8.
The decay lifetime curves of SUST-WJ-12 in air and vacuum are shown in FIG. 10.
The emission spectrum of SUST-WJ-12 (air, vacuum) is shown in FIG. 11.
The corresponding CIE coordinates of the SUST-WJ-12 temperature dependent emission spectrum are shown in FIG. 15.
Example 4 preparation of noctilucent anti-counterfeiting film
And (3) fully grinding SUST-WJ-12, dispersing SUST-WJ-12 powder in an acetone solution, adding cellulose, carrying out ultrasonic treatment for 10 minutes to uniformly compound the powder together, filling the mixed solution into a mold, and standing at room temperature for 3 hours to fully volatilize the solvent to obtain the stable luminous anti-counterfeiting film.
A thin film plot of SUST-WJ-12 after sunlight, ultraviolet excitation and removal of the light source is shown in FIG. 17.
The method comprises the following steps: fully grinding a complex SUST-WJ-12, dispersing 0.010g of powder in 10mL of acetone solvent, adding cellulose, carrying out ultrasonic treatment for 10 minutes to uniformly compound the mixture, filling the mixture into a mold, standing at room temperature for 3 hours to fully volatilize the solvent, and thus obtaining a stable flexible luminous anti-counterfeiting film;
the second method is as follows: the complex SUST-WJ-12 is fully ground, 0.010g of powder is taken and dispersed in 10mL of methanol solvent, and the mixture is uniformly smeared on non-fluorescent paper (namely, any other type of paper which is not fluorescent paper, such as filter paper, non-fluorescent drawing paper and the like) to obtain a fluorescent film with a matrix of paper.
EXAMPLE 5 use of SUST-WJ-12 Complex
1. Multicolor anti-counterfeiting working example:
under Sunlight (SL), the coordination compound SUST-WJ-12 is yellowish at room temperature. Under 365nm ultraviolet radiation, the complex can be observed to appear blue and emit light at room temperature, and after the ultraviolet light source is removed, the complex appears yellow afterglow.
SUST-WJ-12 is fully milled and uniformly smeared on a seal carved with a logo, a two-dimensional code, SUST-WJ and 2022 of Shanxi university of science and technology and chemical university, and the seal is covered on non-fluorescent paper and irradiated by an ultraviolet lamp, so that a long-lasting luminous seal pattern can be observed. The excitation wavelength of the ultraviolet lamp is changed, and the luminous color is correspondingly changed.
A crystal plot of SUST-WJ-12 after 365nm UV excitation and removal of the light source is shown in FIG. 18.
Application of SUST-WJ-12 to stamps of different patterns is shown in FIG. 19.
2. Working examples of luminous anti-counterfeiting film:
fully grinding a coordination compound SUST-WJ-12, dispersing SUST-WJ-12 powder in an acetone solution, adding cellulose, carrying out ultrasonic treatment for 10 minutes to uniformly compound the mixture, filling the mixture into a mold, standing at room temperature for 3 hours to fully volatilize a solvent, and thus obtaining a stable luminous anti-counterfeiting film;
the film is irradiated by light sources with different irradiation luminous anti-counterfeiting film excitation wavelengths, so that different luminous colors and long-lasting luminescence can be shown.
3. Working examples of luminous anti-counterfeiting ink:
fully grinding the coordination compound SUST-WJ-12, mixing nanoscale powder of the coordination compound SUST-WJ-12 with PVP, and carrying out ultrasonic treatment for 10 minutes to uniformly compound the powder together to prepare the highly stable luminous anti-counterfeiting ink.
The ink can be used as a fluorescent body, and the water-based anti-counterfeiting ink suitable for screen printing is prepared through formula adjustment so as to achieve the anti-counterfeiting purpose. The anti-counterfeiting luminous pattern can be screen printed on non-fluorescent paper and PET, and information can be encrypted and decrypted accurately and conveniently by switching ultraviolet irradiation. The prepared safety ink can be used for printing and writing.
It should be noted that the above embodiments are merely for illustrating the technical solution of the present invention and not for limiting the scope of the present invention, and that other various changes and modifications can be made by one skilled in the art based on the above description and the idea, and it is not necessary or exhaustive to all embodiments. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the invention are desired to be protected by the following claims.
Claims (6)
1. Cd (cadmium sulfide) 2+ A base coordination compound SUST-WJ-12, characterized by the formula: c (C) 6 H 3 CdNO 3 The coordination compound SUST-WJ-12 is prepared from 2-hydroxy nicotinic acid and cadmium chloride as raw materials, belongs to triclinic, and belongs to the space group of triclinic systemP-1, a is 3.7667 (5) a; b is 7.4075 (15) a; c is 11.1091 (17) a; alpha is 97.921 (15) °; beta is 99.701 (12) °; gamma is 98.519 (14) °.
2. A Cd according to claim 1 2+ A process for the preparation of a base coordination compound SUST-WJ-12, comprising the steps of:
s1, mixing cadmium chloride and 2-hydroxynicotinic acid according to the mol ratio of 1-5:1, and putting the mixture into a stainless steel high-pressure reaction kettle, wherein the volume ratio of water to N, N-dimethylformamide is 1-5: 1-5, adding the mixture into a reaction kettle, and uniformly stirring, wherein the dosage ratio of water to 2-hydroxynicotinic acid is 1-5 mL, 0.05mmol, and the dosage ratio of N, N-dimethylformamide to 2-hydroxynicotinic acid is 1-5 mL, 0.05mmol;
s2, heating in a sealed pressure-resistant reaction kettle for 1-3 hours, heating from room temperature to 100-120 ℃, keeping the temperature for 40-60 hours, and cooling to room temperature for 8-12 hours;
s3, cooling to room temperature to obtain yellow needle-like crystals, filtering and washing with N, N-dimethylformamide to obtain pure crystals.
3. A Cd according to claim 2 2+ A process for producing a radical complex SUST-WJ-12, characterized in that the chlorination is carried out in the step S1Cadmium (Cd)The molar ratio of the 2-hydroxynicotinic acid is 1:1; the volume ratio of the water to the N, N-dimethylformamide in the step S1 is 5:1, a step of; the dosage ratio of the water to the 2-hydroxynicotinic acid in the step S1 is 5mL:0.05mmol; the dosage ratio of the N, N-dimethylformamide to the 2-hydroxynicotinic acid in the step S1 is 1mL:0.05 And (5) mmol.
4. A Cd according to claim 2 2+ The preparation method of the base coordination compound SUST-WJ-12 is characterized in that the step S2 is to heat for 2 hours to 120 ℃, keep the temperature for 50 hours and then cool to room temperature for 10 hours.
5. A Cd according to claim 2 2+ The preparation method of the basic coordination compound SUST-WJ-12 is characterized in that a mixture of 100mg of 2-hydroxynicotinic acid and 130mg of cadmium chloride is added into a polytetrafluoroethylene lining of a 50mL reaction kettle, then 5mL of water and 1mL of N, N-dimethylformamide are added, the mixture is stirred uniformly, and the mixture is capped and filled into a matched stainless steel reaction kettle; then placing the reaction kettle into a baking oven, heating the reaction kettle for 2 hours to 120 ℃, keeping the temperature and heating for 50 hours, and cooling to room temperature for 10 hours; finally, the mixture is filtered to obtain yellow coordination complex monocrystal.
6. A Cd according to claim 1 2+ The application of the base coordination compound SUST-WJ-12 is characterized in that the coordination compound SUST-WJ-12 is applied to the field of multicolor anti-counterfeiting and data encryption.
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