CN111205271A - Ligand compound, functionalized metal-organic framework compound prepared from ligand compound, and preparation method and application of functionalized metal-organic framework compound - Google Patents
Ligand compound, functionalized metal-organic framework compound prepared from ligand compound, and preparation method and application of functionalized metal-organic framework compound Download PDFInfo
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Abstract
The invention discloses a ligand compound, a functionalized metal-organic framework compound prepared from the ligand compound, and a preparation method and application of the functionalized metal-organic framework compound. The ligand compound has a structure shown in formula (I), is used as a ligand, and is self-assembled with cadmium chloride to form a functionalized metal-organic framework compound, and the functionalized metal-organic framework compound has the advantages of high fluorescence quantum yield, long room-temperature phosphorescence service life, high emission intensity and stable luminescence performance; and under the vacuum condition, the light still continuously emits light for a long time after the excitation light source is switched off. The LIFM-ZCY-1 does not contain mercury, is non-toxic and non-volatile, is easy to recycle and has environmental friendliness; the complex may beThe room temperature phosphorescence material is used for anti-counterfeiting, shows the optical property negatively related to the oxygen content, can be prepared into a luminescent device, an anti-counterfeiting material and/or an oxygen sensor for application, and has wide application value.
Description
Technical Field
The invention relates to the technical field of luminescent metal-organic framework materials, and particularly relates to a ligand compound, namely 9- (4- (2, 6-bis (4- (1H-tetrazole-5-yl) phenyl) pyridine-4-yl) phenyl) -9H-carbazole, a functionalized metal-organic framework compound prepared by self-assembly of the ligand compound serving as a ligand and cadmium chloride, and a preparation method and application of the functionalized metal-organic framework compound.
Background
Long Persistent Luminescence (LPL) refers to the phenomenon in which a material can continue to emit light for a period of time after the excitation light source is turned off. The history of afterglow luminescence dates back to the beginning of the 17 th century when a strong afterglow was observed by an italian shoemaker from the mineral barite. The materials which are researched and applied at the earliest time belong to inorganic long afterglow materials, and a plurality of natural ores which have long afterglow luminescence characteristics exist in the nature, and a known luminous pearl is one of the natural ores. People often make the ores into various artworks like a noctilucent material 'noctilucent cup' common in daily life. The inorganic long-afterglow luminescence is mainly prepared by capturing charges through impurities, crystal defects, doped ions and the like and generally by high-temperature methods such as a high-temperature solid phase method, a sol-gel method, combustion and the like. The existing synthesis process of the inorganic long afterglow material is complex and the reaction condition is harsh; the rare earth materials with high doping price and large toxicity are needed; furthermore, grinding is required for use and is difficult to apply to flexible substrates. Due to the disadvantages of the inorganic long afterglow materials, further development is limited.
Compared with inorganic long-afterglow materials, the metal-organic long-afterglow luminescent material has attractive application prospects in various high-tech fields such as optical recording, biological imaging, information storage, anti-counterfeiting systems and the like due to the advantages of simple and convenient synthesis, low price, flexibility, easy modification of functional groups, good biocompatibility and the like.
The Metal-organic frameworks (MOFs) is a novel organic-inorganic hybrid porous material, and has the characteristics of clear structure, good stability, easiness in modification and the like. The metal-organic framework is formed by arranging organic ligands and metal nodes in a certain rule in space, and has the light-emitting characteristics of organic matters and metal ions. The principle of luminescence can be mainly divided into the following aspects: (1) organic ligand-centered light emission (LC); (2) metal/cluster centered luminescence (MC); (3) charge transfer between metal and ligand (MLCT, LMCT); (4) charge transfer of ligand to the inner core of the metal cluster (LMCCCT); (5) metal-metal interaction perturbation (LMMC), and the like. And the metal atoms in the metal-organic framework have heavy atom effect, greatly quicken the intersystem crossing process, have positive influence on phosphorescence and afterglow properties, and are expected to obtain ideal long afterglow materials, however, the reports on the long afterglow metal-organic framework are still few at present.
Disclosure of Invention
The invention aims to provide a ligand compound aiming at the defect that the research on long afterglow metal-organic framework compounds in the prior art is deficient. The ligand compound has a novel structure, can be used as a ligand, forms a functionalized metal-organic framework compound with cadmium chloride through self-assembly, belongs to a single material, is a colorless transparent flaky crystal, has high fluorescence quantum yield and long-lasting luminescence, has the advantages of high emission intensity and stable luminescence performance, and has the phosphorescence intensity and service life influenced by oxygen content; under vacuum condition, the excitation light source is closed and the red afterglow still visible to naked eyes still exists. The functionalized metal-organic framework material does not contain mercury, has no toxicity and nonvolatility, has stable property, is easier to recycle, and has environmental friendliness.
A second object of the present invention is to provide a method for preparing the ligand compound.
The third purpose of the invention is to provide the application of the ligand compound as a raw material in the preparation of a functionalized metal-organic framework compound.
The fourth object of the present invention is to provide a functionalized metal-organic framework compound prepared using the ligand compound as a starting material.
The fifth purpose of the invention is to provide a preparation method of the functionalized metal-organic framework compound.
The sixth object of the present invention is to provide the use of said functionalized metal-organic framework compounds.
The above object of the present invention is achieved by the following scheme:
a ligand compound, wherein the ligand compound has the structure of formula (i):
the preparation method of the ligand compound is also within the protection scope of the invention, and comprises the following steps:
s1, preparation of an intermediate 1: under the inert gas atmosphere, carbazole and 4-bromobenzaldehyde are subjected to Buchwald-Hartwig reaction to obtain an intermediate 1 (namely 4- (carbazole-9-yl) benzaldehyde);
s2, preparing an intermediate 2: dissolving the intermediate 1, p-cyanoacetophenone and inorganic base in an alcohol organic solvent for reaction, then adding ammonia water for reaction, and separating a product after the reaction is finished to obtain an intermediate 2 (namely 4, 4' - (4- (4- (4- (9H-carbazole-9-yl) phenyl) pyridine-2, 6-di) dibenzonitrile);
s3, preparing a target compound: and (2) adding the N-methylpyrrolidone solution dissolved with the intermediate 2 into the sodium azide aqueous solution, carrying out reflux reaction at the temperature of 120-150 ℃ under the stirring condition, and separating a product after the reaction is finished to obtain the target compound shown in the formula (I).
Preferably, in step S1, the Buchwald-Hartwig reaction is performed in the presence of potassium carbonate, palladium acetate and tri-tert-butylphosphine; more preferably, the reaction process is: under the inert gas atmosphere, mixing and dissolving carbazole, 4-bromobenzaldehyde, potassium carbonate, palladium acetate and tri-tert-butylphosphine in an anhydrous organic solvent, heating and refluxing for reaction, and separating a product after the reaction is finished to obtain an intermediate 1.
Preferably, in the step S1, the ratio of carbazole to 4-bromobenzaldehyde to potassium carbonate is 12: 12-16: 24-36; more preferably, the ratio is 12:13.5: 30.
Preferably, in step S1, the organic solvent is toluene, N dimethylformamide, or N, N dimethylacetamide.
Preferably, in the step S1, the time of the reflux reaction is 36 to 72 hours.
Preferably, in step S1, after the reaction is finished, the product separation process is as follows: the reaction solution was cooled to room temperature, filtered, the filtrate was taken, then extracted with water and dichloromethane, the organic phase was taken, the solvent was removed, and finally the residue was purified by column chromatography to give intermediate 1.
More preferably, the step S1 is a step of separating the product, and the mobile phase in the step of column chromatography is petroleum ether and dichloromethane in a volume ratio of 1: 1.
Preferably, in the step S2, the mass ratio of the intermediate 1 to the cyanoacetophenone to the sodium hydroxide is 15-25: 40: 30-50; more preferably, the ratio is 20:40: 40.
Preferably, in step S2, the organic base is a base material commonly used in the art, such as sodium hydroxide, potassium hydroxide, and the like.
Preferably, in step S2, the alcohol organic solvent is an alcohol having 4 or less carbon atoms, such as methanol, ethanol, propanol, isopropanol, etc., which are commonly used in the art.
Preferably, in step S2, after the reaction is finished, the product separation process is as follows: filtering the reaction solution, taking a filter cake, and purifying by column chromatography to obtain an intermediate 2.
More preferably, the step S2 product separation process is a column chromatography process, and the mobile phase is petroleum ether and dichloromethane in a volume ratio of 1: 2.
Preferably, in the step S3, the molar ratio of the intermediate 2 to the sodium azide is 1: 5-10; more preferably, the ratio is 1: 8.
Preferably, in the step S3, the volume ratio of the water to the N-methyl pyrrolidone is 1: 3-7; more preferably, the ratio is 1: 5.
Preferably, in step S3, the temperature of the reaction is 150 ℃.
Preferably, in step S3, after the reaction is finished, the product separation process is as follows: and cooling the reaction liquid to room temperature, adding an HCl aqueous solution to acidify the mixture until the pH value is 1, filtering, taking a filter cake, and drying to obtain the target product.
The invention also protects the application of the ligand compound in preparing the functionalized metal-organic framework compound.
A functionalized metal-organic framework compound, LIFM-ZCY-1, with molecular formula of C37H32CdN10O4The crystal is monoclinic system, and the space group of the monoclinic system is C2/C, which is also in the protection scope of the invention.
Preferably, the functionalized metal-organic framework compound is formed by self-assembling a compound of formula (I) serving as a ligand and cadmium chloride.
The invention also provides a preparation method of the functionalized metal-organic framework compound, which comprises the steps of dissolving the compound shown in the formula (I) and cadmium chloride in N, N-dimethylacetamide and ethanol aqueous solution, carrying out sealed reaction at the temperature of 80-100 ℃, and separating a product after the reaction is finished to obtain the functionalized metal-organic framework compound.
Preferably, the mass ratio of the compound of the formula (I) to the cadmium chloride is 5-10: 10.
Preferably, the mass ratio of the compound of formula (I) to cadmium chloride is 5: 10.
Preferably, the mass ratio of the N, N-dimethylacetamide to the ethanol to the water is 1: 0.5-2.
The invention also protects the application of the functionalized metal-organic framework compound in preparing luminescent devices, anti-counterfeiting materials and/or oxygen sensors.
Preferably, the oxygen sensor is an oxygen sensor with multi-dimensional visualization.
Compared with the prior art, the invention has the following beneficial effects:
the ligand compound has a novel structure, can be used as a ligand, forms a functionalized metal-organic framework compound with cadmium chloride through self-assembly, belongs to a single material, is a colorless transparent flaky crystal, has high fluorescence quantum yield and long-lasting luminescence, and has the advantages of high emission intensity and stable luminescence performance, and the phosphorescence intensity and the service life are influenced by the oxygen content; under vacuum condition, the excitation light source is closed and the red afterglow still visible to naked eyes still exists. The functionalized metal-organic framework material does not contain mercury, has no toxicity and nonvolatility, has stable property, is easier to recycle, has environmental friendliness, can be prepared into a luminescent device, an anti-counterfeiting material and/or an oxygen sensor for application, and has wide application value.
Drawings
FIG. 1 is a NMR chart of 9- (4- (2, 6-bis (4- (1H-tetrazol-5-yl) phenyl) pyridin-4-yl) phenyl) -9H-carbazole, a ligand compound prepared in example 1.
FIG. 2 is a schematic chemical structure diagram of LIFM-ZCY-1 prepared in example 1.
FIG. 3 is a graph of fluorescence excitation and emission of LIFM-ZCY-1 prepared in example 1 under 365nm wavelength excitation.
FIG. 4 is a CIE graph showing fluorescence emission at different temperatures under 365nm excitation of LIFM-ZCY-1 prepared in example 1.
FIG. 5 is a graph of steady state versus delayed spectra at 365nm wavelength excitation, and lifetime at 560nm wavelength emission for LIFM-ZCY-1 prepared in example 1 and a sample LIFM-ZCY-1-heated after heating.
FIG. 6 is a graph of fluorescence spectrum and lifetime decay curve of LIFM-ZCY-1 prepared in example 1 under 365nm excitation at different oxygen contents.
Detailed Description
The present invention is further described in detail below with reference to specific examples, which are provided for illustration only and are not intended to limit the scope of the present invention. The test methods used in the following examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are, unless otherwise specified, commercially available reagents and materials.
All analytical grade reagents used in the following examples were purchased from Innochem and used without further purification.
The applied instrument is as follows: the infrared data was obtained at 4000--1The range was collected using potassium bromide pellet method.
The samples were tabletted using a Specac mini-tablet press.
Powder X-ray diffraction (PXRD) was measured using a Rigaku SmartLab diffractometer (Bragg-Brentano geometry, cuk α 1 radiation, λ 1.54056 a).
Thermogravimetric heating under nitrogen and 1atm pressure at 10 ℃ min-1Thermogravimetric analysis (TGA) was performed in NETZSCH TG209 system.
1HNMR spectra were obtained using a JEOL EX270 spectrometer (400MHz) instrument.
The UV-vis absorption spectrum was recorded using a Shimadzu UV-2450 spectrophotometer.
The fluorescence microscope photograph was taken under a 365nm UV lamp.
Fluorescence spectra were measured by Edinburgh FLS 980 spectrometer.
Fluorescence quantum yield data are obtained by measuring on a Hamamatsu C9920-02G absolute fluorescence quantum yield measuring system.
Two-photon excitation fluorescence spectra were obtained using an Astrella/Opera-Solo femtosecond laser.
EXAMPLE 1 preparation of a functionalized Metal-organic framework Compound LIFM-ZCY-1
A functionalized metal-organic framework compound LIFM-ZCY-1 is formed by self-assembling 9- (4- (2, 6-bis (4- (1H-tetrazole-5-yl) phenyl) pyridine-4-yl) phenyl) -9H-carbazole serving as a ligand and chromium chloride dihydrate.
The specific preparation process comprises the following steps:
wherein the preparation process of the 9- (4- (2, 6-bis (4- (1H-tetrazole-5-yl) phenyl) pyridine-4-yl) phenyl) -9H-carbazole is as follows:
s1, preparation of an intermediate product 4- (carbazole-9-yl) benzaldehyde (intermediate 1):
carbazole (2.0g, 12mmol), 4-bromobenzaldehyde (2.5g, 13.5mmol), potassium carbonate (4.1 mmol)5g, 30mmol), palladium acetate (0.2g, 1.0mmol), and tri-tert-butylphosphine (0.3mL) in 20mL of anhydrous toluene under nitrogen atmosphere were refluxed for 48 hours. After the reaction is finished, cooling to room temperature, and filtering to obtain filtrate. The filtrate was extracted with water and dichloromethane to obtain an organic phase. After removal of the solvent using a rotary evaporator, the residue was purified by column chromatography (petroleum ether/CH)2Cl2V/V1: 1) to yield 2.3g of a white solid (yield 71%).
S2. preparation of intermediate 4, 4' - (4- (4- (4- (9H-carbazol-9-yl) phenyl) pyridine-2, 6-bis) dibenzonitrile (intermediate 2):
p-cyanoacetophenone (5.8g, 40mmol), 4- (carbazol-9-yl) benzaldehyde (5.42g, 20mmol) and sodium hydroxide (1.6g, 40mmol) were stirred in 200mL of ethanol solution at room temperature for about 15 hours, then 80mL of aqueous ammonia was added and stirred at room temperature for another 24 hours. Filtration, taking the filter cake and purifying the residue by column chromatography (petroleum ether/dichloromethane, V/V1: 2) to give the desired product 4.0g as a pale yellow solid, 38% yield;
s3, preparation of ligand 9- (4- (2, 6-bis (4- (1H-tetrazol-5-yl) phenyl) pyridin-4-yl) phenyl) -9H-carbazole:
to a 25mL round bottom flask was added sodium azide (1.12g, 16mmol) and 2mL water. 4, 4' - (4- (4- (4- (9H-carbazol-9-yl) phenyl) pyridine-2, 6-bis) dibenzonitrile (2mmol) was dissolved in 10mL of N-methylpyrrolidone and poured into an aqueous solution of sodium azide. The reaction mixture was refluxed for 24 hours at an elevated temperature of 150 ℃ with vigorous stirring. After the reaction is finished, the reaction product is cooled to room temperature, the mixture is acidified to pH 1 by using HCl aqueous solution (1M), precipitates appear under the condition of vigorous stirring, and a filter cake is obtained by filtering and dried to obtain a white solid product.
The nuclear magnetic resonance hydrogen spectrum of the ligand 9- (4- (2, 6-bis (4- (1H-tetrazol-5-yl) phenyl) pyridine-4-yl) phenyl) -9H-carbazole is shown in figure 1, and the structure is shown in (I):
self-assembly process of 9- (4- (2, 6-bis (4- (1H-tetrazol-5-yl) phenyl) pyridin-4-yl) phenyl) -9H-carbazole, cadmium chloride: respectively weighing 5mg of the product 9- (4- (2, 6-bis (4- (1H-tetrazol-5-yl) phenyl) pyridin-4-yl) phenyl) -9H-carbazole in the step S3 and 10mg of cadmium chloride dihydrate in a 10mL glass vial, adding 1mL of N, N-dimethylacetamide, 1mL of water and 1mL of ethanol for dissolving, sealing the glass vial, and placing the glass vial into a ninety-degree oven for reacting for two days to obtain a colorless and transparent flaky crystal, namely the target product metal-organic framework compound LIFM-ZCY-1.
EXAMPLE 2 determination of the Crystal Structure of the functionalized Metal-organic framework Compound LIFM-ZCY-1
Is provided with a copper target
Single crystal X-ray diffraction data of LIFM-ZCY-1 were collected at 50kV and 0.80mA on a Rigaku-Oxford Ulnovarus X-ray diffractometer system.
The structure is solved by adopting a direct method, and is refined by utilizing a SHELXL-2014 program package and adopting a full matrix least square method. All hydrogen atoms were obtained in a theoretical hydrogenation process and refined in the anisotropic direction, using the iso command to fix the framework. The relevant crystallographic data of LIFM-ZCY-1 are shown in Table 1, and the topology is shown in FIG. 2.
TABLE 1 is the crystallographic data of the metal-organic framework complex LIFM-ZCY-1
Wherein, FIG. 2 is a crystal structure diagram of LIFM-ZCY-1, a) an asymmetric unit structure of LIFM-ZCY-1; b) a one-dimensional chain structure of LIFM-ZCY-1; c) LIFM-ZCY-1 chain stacking diagram.
Example 3 measurement of fluorescence Properties of LIFM-ZCY-1
The LIFM-ZCY-1 solid powder shows blue fluorescence under the excitation light with the wavelength of 365nm, the maximum emission peak is about 460nm, and the maximum excitation peak is about 370nm, as shown in FIG. 3.
Meanwhile, LIFM-ZCY-1 showed a thermochromic effect, as shown in FIG. 4. When the temperature is gradually increased from 300K to 460K, a new peak of about 560nm appears behind the original fluorescence peak of about 460 nm. In addition, the position of the peak can be red-shifted with the rise of the temperature, and when the temperature exceeds 460K, the newly appeared peak is no longer red-shifted at about 600 nm. The light emitting color of LIFM-ZCY-1 changes from 300K blue to 460K orange red along with the temperature rise, and the CIE coordinates change from (0.21, 0.19) to (0.54, 0.42). The LIFM-ZCY-1 is heated and returns to the room temperature, the sample still keeps the light emission of orange red, and the heated sample is named LIFM-ZCY-1-heated.
EXAMPLE 4 measurement of LIFM-ZCY-1 Room temperature Phosphorescence Properties
Optical properties of LIFM-ZCY-1 and LIFM-ZCY-1-heated solid powders were obtained by optical testing of LIFM-ZCY-1 and heated LIFM-ZCY-1-heated solid powders, respectively (FIG. 5).
As can be seen from FIG. 5, the LIFM-ZCY-1 has an emission peak at 460nm of nanosecond lifetime and a fluorescence peak. As can be seen from the phosphorescence spectrum (Delay) of LIFM-ZCY-1, the phosphorescence peak is located at 560nm, and the phosphorescence lifetime is as high as 5.57 ms. The steady state fluorescence spectrum (Prompt) of LIFM-ZCY-1-treated showed two emission peaks at 460nm and 600nm, respectively, where the 460nm emission peak was assigned to the ligand-based fluorescence emission. Through the phosphorescence spectrum (Delay) test of LIFM-ZCY-1-treated, the phosphorescence spectrum is found to be 620nm, and the phosphorescence lifetime is as long as 10 milliseconds. From this, it can be concluded that the peak at 600nm in the LIFM-ZCY-1-treated steady-state fluorescence spectrum is a combination of excimer emission caused by stacking and triplet phosphorescence. In addition, from the test results, it was found that LIFM-ZCY-1 under vacuum has a lifetime as long as 18 milliseconds, which is much longer than the phosphorescence lifetime under air, indicating that the lifetime is seriously affected by oxygen. Meanwhile, this example tested the phosphorescence lifetime under heated LIFM-ZCY-1-heated vacuum and found that the lifetime was as long as thirty milliseconds. In addition, it was found that LIFM-ZCY-1-treated samples emitted macroscopic red afterglow when the excitation light source was turned off under vacuum.
EXAMPLE 5 LIFM-ZCY-1 optical Properties testing at different oxygen levels
Because of the unique long-room-temperature phosphorescence properties of LIFM-ZCY-1 and the long lifetime under vacuum conditions, it is presumed that the room-temperature phosphorescence intensity and lifetime of LFM-ZCY-1 will vary with the oxygen content in the environment. Therefore, the steady state spectrum and lifetime of LIFM-ZCY-1-heated under different oxygen content atmosphere were tested, and the results are shown in FIG. 6.
The experimental results show that the peak intensity of LIFM-ZCY-1-treated at 600nm is obviously quenched with the increase of the oxygen concentration under the 365nm excitation. The CIE coordinates changed from (0.41, 0.25) in vacuum to (0.32, 0.20) in pure oxygen due to the emission at 600 nm. However, even in pure oxygen, the peak at 600nm does not completely disappear. LIFM-ZCY-1-heated samples have a lifetime of only 5 milliseconds after heating in pure oxygen, and as long as 30 milliseconds in vacuum. Furthermore, the phosphorescence lifetime at 620nm shows different quenching rates in high oxygen (>300mbar) and low oxygen (<300mbar), showing better sensitivity at low oxygen content, indicating that the quenching process involves multiple quenching mechanisms, including quenching of room temperature phosphorescence at 620nm by oxygen and quenching of excimer luminescence.
The LIFM-ZCY-1 has excellent luminescence property and stable optical property, has the potential of being applied to illumination and optical coding information transmission, and can be applied to an oxygen sensor due to high sensitivity to oxygen. The sensor can be used as a multi-dimensional visual oxygen sensor because the sensor can generate different degrees of response to oxygen in four dimensions of luminous intensity, luminous color, luminous life and afterglow time.
It should be finally noted that the above examples are only intended to illustrate the technical solutions of the present invention, and not to limit the scope of the present invention, and that other variations and modifications based on the above description and thought may be made by those skilled in the art, and that all embodiments need not be exhaustive. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. A ligand compound, wherein the ligand compound has the structure of formula (i):
2. a process for preparing a ligand compound according to claim 1, comprising the steps of:
s1, preparation of an intermediate 1: under the inert gas atmosphere, carbazole and 4-bromobenzaldehyde are subjected to Buchwald-Hartwig reaction under the inert gas atmosphere to obtain an intermediate 1;
s2, preparing an intermediate 2: dissolving the intermediate 1, p-cyanoacetophenone and inorganic base in an alcohol organic solvent for reaction, then adding ammonia water for reaction, and separating a product after the reaction is finished to obtain an intermediate 2;
s3, preparing a target compound: and (2) adding the N-methylpyrrolidone solution dissolved with the intermediate 2 into the sodium azide aqueous solution, carrying out reflux reaction at the temperature of 120-150 ℃ under the stirring condition, and separating a product after the reaction is finished to obtain the target compound shown in the formula (I).
3. Use of the ligand compound according to claim 1 for the preparation of a functionalised metal-organic framework compound.
4. A functionalized metal-organic framework compound characterized by having a molecular formula of C37H32CdN10O4The space group of the monoclinic system is C2/C.
5. The functionalized metal-organic framework compound of claim 4, wherein the functionalized metal-organic framework compound is formed by self-assembly of a compound of formula (I) as a ligand with cadmium chloride.
6. The preparation method of the functionalized metal-organic framework compound as claimed in claim 4 or 5, characterized in that the compound of formula (I) and cadmium chloride are mixed and dissolved in N, N-dimethylacetamide and ethanol aqueous solution, sealed reaction is carried out at 80-100 ℃, and after the reaction is finished, the product is separated to obtain the functionalized metal-organic framework compound.
7. The method for preparing the functionalized metal-organic framework compound according to claim 6, wherein the mass ratio of the compound of formula (I) to the cadmium chloride is 5-10: 10.
8. The method for preparing a functionalized metal-organic framework compound according to claim 7, wherein the mass ratio of the compound of formula (I) to the cadmium chloride is 5: 10.
9. The method for preparing a functionalized metal-organic framework compound according to claim 6, wherein the mass ratio of N, N-dimethylacetamide to ethanol to water is 1: 0.5-2.
10. Use of the functionalized metal-organic framework compound according to claim 1 for the preparation of light emitting devices, security materials and/or oxygen sensors.
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| CN111944163A (en) * | 2020-08-25 | 2020-11-17 | 洛阳师范学院 | 5-carbazolyl isophthalic acid cadmium complex and preparation method and application thereof |
| WO2021139092A1 (en) * | 2020-01-09 | 2021-07-15 | 中山大学 | Ligand compound, and functionalized metal-organic framework compound prepared by same, preparation method therefor and application thereof |
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| CN114316951B (en) * | 2021-12-23 | 2023-12-22 | 南京邮电大学 | Cadmium-based two-dimensional hybridization perovskite long afterglow material, and preparation method and application thereof |
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