CN111004182A - Small-molecule long-afterglow complex and preparation method thereof - Google Patents

Small-molecule long-afterglow complex and preparation method thereof Download PDF

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CN111004182A
CN111004182A CN201911358558.6A CN201911358558A CN111004182A CN 111004182 A CN111004182 A CN 111004182A CN 201911358558 A CN201911358558 A CN 201911358558A CN 111004182 A CN111004182 A CN 111004182A
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afterglow
complex
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张召
李新平
马宁宁
常慧
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Shaanxi University of Science and Technology
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Abstract

The invention provides a micromolecule long afterglow complex and a preparation method thereof, wherein the preparation of the complex crystal comprises the step 1 of mixing MXnPlacing the organic matter A and the organic matter A in distilled water, adjusting the pH value of the obtained mixed system to 5.7-5.8 to obtain a mixed system A, and carrying out hydrothermal reaction on the mixed system A at 150-160 ℃ to obtain a product liquid; step 2, washing and drying the product in the product liquid; the preparation method of the powder comprises the following steps of (0.1-0.15): (0.2 to 0.3) molar ratio of MX to MXnMixing with organic A, grinding to obtain mixture A, and making the mixture A have long afterglow under the condition of UV light. The preparation method of the invention has low toxicity, high yield and good product solubility, can be used for large-scale actual production, improves the stability of the synthesized long-afterglow luminescent material, and has high luminescent efficiency, long fluorescence life and good long-afterglow effect.

Description

Small-molecule long-afterglow complex and preparation method thereof
Technical Field
The invention relates to the field of fluorescent luminescent material preparation, in particular to a micromolecule long afterglow complex and a preparation method thereof.
Background
The long afterglow luminescent material is called long afterglow luminescent material, also called light storage luminescent material, commonly called noctilucent powder or long afterglow powder. The most common long-lasting luminescent materials such as "glow cups" and "glow beads" are made from natural minerals; in addition, in the period of Song dynasty, oysters and other natural long afterglow materials are used and made into long afterglow pigments; the first long persistence substances recorded in the west were ones produced by an italian shoemaker in 1603 who roasted local ore and obtained some red-emitting substances in the dark. Through analysis, the ore contains barium sulfate, and some of the barium sulfate becomes barium sulfide long afterglow substances after reduction roasting. Since a long time ago, the fluorescent material has attracted great research interest of experts, is widely applied to commercial night vision or vision materials and has extremely high scientific value and economic value.
The long afterglow material has the principle of photoluminescence, stores energy when excited to an excited state by a light source, and releases the energy slowly in the form of light after excitation is stopped, so that the material can emit light in the dark for several seconds, minutes, hours or even days. Therefore, the long afterglow material can absorb the energy of sunlight and other artificial light sources, store part of the energy and slowly release phosphorescence in the form of light with different colors. Because the emission process is slow, the continuous lighting effect is achieved, and the night vision watch is widely commercialized as a night vision watch, a distress signal, a night indicator lamp, lighting and the like. In addition, the long afterglow material can solve the background fluorescence problem due to the long time emission characteristic, so that the long afterglow material can be applied to the biomedical field, such as in vivo biological imaging and the like.
Since the discovery of the long afterglow phenomenon in the beginning of the 20 th century, the development of long afterglow materials has made a long progress. From the discovery of the long afterglow phenomenon to the 90 s in the 20 th century, the long afterglow material with the best performance is a metal sulfide body series long afterglow material, the development of a novel aluminate long afterglow material appearing in the later period is very rapid, the luminous intensity, the luminous time and the chemical stability of the material are greatly improved compared with those of a first generation long afterglow material, and particularly the long afterglow decay time of the long afterglow material can reach 10 hours and has very high durability. Then the rare earth activated aluminate long afterglow material becomes the basis of the luminescent coating, gains the favor of the trade industry and is widely applied to instrument display and photoelectricitySub-devices, night emergency instructions, national defense and military and other important fields. And it was found that Eu2+The pyrosilicate compound with the structure of akermanite and the silicate compound with the structure of forskolite which are co-activated by Ln have the best afterglow luminescence performance, and the residual glow duration is longer than 20 h. Therefore, silicate-based long-afterglow materials are also receiving more and more attention and are being developed. However, the long-afterglow materials of general inorganic systems are difficult in preparation process, require high temperature of over 1000 ℃, are difficult to exploit rare earth elements added in raw materials, are high in cost and extremely high in energy consumption, and the pressure of natural resources and environment is increased greatly day by day. In addition, the long-lasting phosphor of the inorganic system has a problem of difficult dissolution, for example, the compound must be ground into micron-sized powder to be dissolved into a solvent by ultrasound, which not only causes poor compatibility of the long-lasting phosphor with common polymers, but also causes the light scattering degree of the ground powder to be large, thus reducing the transparency of the material. In view of the above problems, in 2017, experts have discovered the first real organic long afterglow system, which prompts many experts to focus on the long afterglow material based on the organic system.
So far, since the appearance of organic long afterglow phosphors is late and the development is not yet mature, very few reports have been made on organic long afterglow luminescent materials. The organic long afterglow material mainly adopts the physical composition of various organic compounds, namely an electron donor and an electron acceptor can generate stable free radical cations to form an energy donor-energy acceptor luminescence mechanism, but the stability and the dispersibility of the material are insufficient, the repeatability effect of a sample is poor, and a plurality of defects also exist; in recent years, with the mature technology of preparing fluorescent luminescent materials by organic-inorganic complexes, organic-inorganic hybrid coordination polymer materials with long afterglow characteristics are continuously available, but the preparation of the materials is very sensitive to the conditions of raw material concentration, reaction temperature and pH, so the preparation yield is not high. In addition, the complex is extremely stable, so that the solubility of the complex is poor, and the subsequent production application is not facilitated.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a micromolecule long afterglow complex and a preparation method thereof, which have the advantages of low toxicity, high yield and good solubility and can be used for large-scale actual production.
The invention is realized by the following technical scheme:
a preparation method of a micromolecule long afterglow complex crystal comprises the following steps,
step 1, MXnPlacing the organic matter A and the organic matter A in distilled water, adjusting the pH value of the obtained mixed system to 5.7-5.8 to obtain a mixed system A, and carrying out hydrothermal reaction on the mixed system A at 150-160 ℃ to obtain a product liquid;
wherein X ═ F, Cl, Br, I, OH, NO3Or OAc, n is 2 or 3, when n is 2, M is a metal ion with a valence of +2 which can be used as a coordination center in the periodic table of elements, and when n is 3, M is a metal ion with a valence of +3 which can be used as a coordination center in the periodic table of elements;
the structural formula of the organic substance A is as follows:
Figure BDA0002336590090000031
R1h, alkanes or aromatics, R2H, an alkane or aromatic hydrocarbon;
and 2, washing and drying the product in the product liquid to obtain the micromolecule long afterglow complex crystal.
Preferably, in step 1, MXnThe molar ratio of the organic matter A to the organic matter A is (0.1-0.15): (0.2-0.3).
Preferably, in the step 1, the mixed system A is reacted for 36-72 hours at the temperature.
Preferably, in step 1, when n is 2, M is Ca, Mg, Cu, Co, Ni, Cr, Cd, Zn, Mn, Pt or Pd, and when n is 3, M is Al, Fe, Cr, Ir, B, Nd, Yb, Er, Eu, Tb or Gd.
Preferably, in the step 2, the product in the product liquid is filtered, washed with distilled water and absolute ethyl alcohol for 2-3 times in sequence, and then dried at 45-60 ℃ for 12-18 hours.
A micromolecule long afterglow complex crystal obtained by the preparation method of any micromolecule long afterglow complex crystal.
A preparation method of small-molecule long-afterglow complex powder comprises the following steps of (0.1-0.15): (0.2 to 0.3) molar ratio of MX to MXnMixing with an organic matter A, grinding to obtain a mixture A until the mixture A has a long afterglow phenomenon under ultraviolet light, and obtaining micromolecular long afterglow complex powder;
wherein X ═ F, Cl, Br, I, OH, NO3Or OAc, n is 2 or 3, when n is 2, M is a metal ion with a valence of +2 which can be used as a coordination center in the periodic table of elements, and when n is 3, M is a metal ion with a valence of +3 which can be used as a coordination center in the periodic table of elements;
the structural formula of the organic substance A is as follows:
Figure BDA0002336590090000041
R1h, alkanes or aromatics, R2H, alkanes or aromatics.
Further, said MXnAnd the grinding time of the organic matter A is 1.5-2.5 h.
Still further, when n is 2, M is Ca, Mg, Cu, Co, Ni, Cr, Cd, Zn, Mn, Pt or Pd, and when n is 3, M is Al, Fe, Cr, Ir, B, Nd, Yb, Er, Eu, Tb or Gd.
The micromolecule long afterglow complex powder prepared by the preparation method of any micromolecule long afterglow complex powder.
Compared with the prior art, the invention has the following beneficial technical effects:
the invention relates to a preparation method of a micromolecule long afterglow complex crystal, which firstly MXnAfter the organic matter A and the organic matter A are placed in distilled water, the pH value is adjusted to be favorable for coordination of metal ions, and then the hydrothermal reaction is carried out, MXnThe complex and an organic substance A can generate a coordination reaction, and finally the product is washed and dried to obtain a micromolecule long afterglow complex crystal; MXnAnd organic matter A has wide source and low price, and the organic matter A are firmly connected through coordination bonds, so that the stability of the synthesized long-afterglow luminescent material is improved, the luminescent efficiency is high, the fluorescent life is long, and the long-afterglow luminescent material has long afterglowThe effect is good.
The preparation method of the micromolecule long afterglow complex powder has the advantages of wide source of adopted chemical reagents, low price, simple preparation process, MXnThe organic matter A and the organic matter A are mutually contacted and reacted through grinding, and the total free energy of the system is increased due to the intervention of no solvent and the local high concentration of the reactants and the grinding technology, so that the reaction system is activated, the reaction efficiency is improved, the coordination bonds of the reactants are stably connected, the stability of the synthesized long-afterglow luminescent material is improved, and the luminescent material has high luminescent efficiency, long fluorescence life and good long afterglow effect.
Drawings
FIG. 1 is a synthetic route of a small molecule long afterglow complex exemplified in the present invention;
FIG. 2 is a crystal structure diagram of Zn-Imdc prepared in examples 1 to 8 of the present invention;
FIG. 3 is a crystal structure diagram of Cd-Imdc prepared in embodiments 1-8 of the present invention;
FIG. 4 is a UV-VISIBLE absorption spectrum of Zn-Imdc and Cd-Imdc prepared in examples 1 and 2 of the present invention;
FIG. 5 is a PXRD pattern of Zn-Imdc and Cd-Imdc prepared in examples 1 and 2 of the present invention;
FIG. 6 is an infrared spectrum of Zn-Imdc and Cd-Imdc prepared in examples 1 and 2 of the present invention;
FIG. 7 is a graph showing emission spectra of Zn-Imdc and Cd-Imdc prepared in examples 1 and 2 of the present invention;
FIG. 8 is a graph showing the long persistence effects of Zn-Imdc and Cd-Imdc prepared in examples 1 and 2 of the present invention.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
The invention provides two preparation methods of micromolecule long-afterglow complex with easy synthesis, high yield and good solubility by a mechanical grinding method and a hydrothermal method.
The preparation method 1 specifically comprises the following steps:
adding 0.1-0.15 mmol of MXnMixing 0.2-0.3 mmol dicarboxylimidazole or derivatives thereof and 4-5 ml of distilled water to obtain a mixed system A, adjusting the pH of the mixed system A to 5.7-5.8 by using a buffer solution of HAC-NaAC (pH 5-7), wherein the pH value is not favorable for carboxylic acid dehydrogenation to form carboxylate anion and coordination of metal ions, placing the obtained system in a 25ml tetrafluoroethylene-lined autoclave, heating at 150-160 ℃ for 36-72 h, cooling to room temperature, filtering the product, washing the product with 5-10 ml of distilled water and 5-10 ml of anhydrous ethanol for 2-3 times, drying at 45-60 ℃ for 12-18 h to obtain small-molecular long-afterglow complex crystals, and preparing the small-molecular long-afterglow complex crystals from (m)Product of/mReactants) The product can be obtained by 100 percent calculation, and the yield is 90 to 92 percent.
The preparation method 2 specifically comprises the following steps:
weighing 0.1-0.15 mmol of MXnAnd 0.2 to 0.3mmol of dicarboxylimidazole or a derivative thereof, and grinding the mixture in the same direction for 1.5 to 2.5 hours to obtain a product in a powder form, wherein the product shows a long afterglow phenomenon after being irradiated by an ultraviolet lamp.
If the grinding is not carried out in one direction but is carried out in a turning way, the situation that the middle is small and the two ends are large can be caused, and the medicine can be splashed out due to the turning way.
And (4) grinding for 15-20 min, and then determining whether the long afterglow exists, and if the long afterglow does not exist, continuing grinding until the long afterglow occurs. If the values are taken according to the proportional relation, the grinding time can be shorter when the mass is less. During grinding, reactants collide violently to generate coordination reaction, and the prepared solid dispersion long afterglow material is sampled and placed in a drier, and the yield is 95-97%.
MX in the above 2 production ProcessnAnd n is 2 or 3, when n is 2, M is Ca, Mg, Cu, Co, Ni, Cr, Cd, Zn, Mn, Pt or Pd, that is, a + 2-valent metal ion that can serve as a coordination center in the periodic table, and when n is 3, M is Al, Fe, Cr, Ir, B, Nd, Yb, Er, Eu, Tb or Gd, that is, a + 3-valent metal ion that can serve as a coordination center in the periodic table. X may be F, Cl、Br、I、OH、NO3Or an OAc.
The structural formula of the dicarboxylimidazole or the derivative thereof is as follows:
Figure BDA0002336590090000071
R1h, alkanes or aromatics, R2H, an alkane or an aromatic hydrocarbon, the alkane may be CH3The aromatic hydrocarbon may be
Figure BDA0002336590090000072
The small molecule long afterglow complex of the invention has good solubility, and the specific reason is that the small molecule long afterglow complex can be fully dissolved in DMF, and then the small molecule long afterglow complex is smeared on a glass slide, and the residual substance is still in a long afterglow phenomenon even in distribution after the solvent DMF is volatilized.
The invention relates to metals where n is 2, M is Ca, Mg, Cu, Co, Ni, Cr, Cd, Zn, Mn, Pt or Pd, and where n is 3, M is Al, Fe, Cr, Ir, B, Nd, Yb, Er, Eu, Tb or Gd, X is F, Cl, Br, I, OH, NO3Or OAc, as shown in FIG. 1.
The following specific examples are further illustrative of the present technology and the starting materials in the examples are commercially available.
Example 1
n ═ 2, M ═ Zn, X ═ OAc, 0.1mmol of MX20.25mmol of imidazole-4, 5-dicarboxylic acid and 5ml of distilled water are mixed to obtain a mixed system A, the pH of the mixed system A is adjusted to 5.75 by HAC-NaAC buffer solution with the pH value of 5-7, then the mixed system A is placed in a 25ml high-pressure autoclave with a tetrafluoroethylene lining, heated at 150 ℃ for 36h, cooled to room temperature, filtered, washed for 3 times by 10ml of distilled water and 10ml of absolute ethyl alcohol in sequence, and dried in an oven at 60 ℃ for 12h, and the yield of the obtained small molecule long afterglow complex crystal is 90%.
Example 2
n 2, M Cd, X OAc, 0.1mmol MX20.25mmol of imidazole-4, 5-dicarboxylic acid and 4ml of distilled water were mixed to obtain a mixed system AAnd adjusting the pH of the mixed system A to 5.75 by using an HAC-NaAC buffer solution with the pH of 5-7, then placing the mixed system A into a 25ml high-pressure autoclave with a tetrafluoroethylene lining, heating the mixed system A at 150 ℃ for 36h, cooling the mixed system A to room temperature, filtering the product, washing the product for 3 times by using 5ml of distilled water and 5ml of absolute ethyl alcohol in sequence, and drying the product in an oven at 50 ℃ for 18h to obtain the micromolecule long afterglow complex crystal with the yield of 90%.
Example 3
n 2, M Cd, X Cl, 0.1mmol MX20.25mmol of imidazole-4, 5-dicarboxylic acid and 5ml of distilled water are mixed to obtain a mixed system A, the pH of the mixed system A is adjusted to 5.72 by HAC-NaAC buffer solution with the pH value of 5-7, then the mixed system A is placed in a 25ml high-pressure autoclave with a tetrafluoroethylene lining, heated at 160 ℃ for 36h, cooled to room temperature, filtered, washed by 10ml of distilled water and 10ml of absolute ethyl alcohol for 2 times, and dried in an oven at 45 ℃ for 18h, and the yield of the obtained small molecule long afterglow complex crystals is 92%.
Example 4
n ═ 2, M ═ Zn, X ═ Cl, 0.1mmol of MX20.25mmol of imidazole-4, 5-dicarboxylic acid and 5ml of distilled water are mixed to obtain a mixed system A, the pH of the mixed system A is adjusted to 5.72 by HAC-NaAC buffer solution with the pH value of 5-7, then the mixed system A is placed in a 25ml high-pressure autoclave with a tetrafluoroethylene lining, heated at 160 ℃ for 36h, cooled to room temperature, filtered, washed by 10ml of distilled water and 10ml of absolute ethyl alcohol for 2 times, dried in an oven at 60 ℃ for 12h, and the yield of the obtained small molecule long afterglow complex crystals is 92%.
Example 5
n ═ 2, M ═ Zn, X ═ OAc, 0.1mmol of MX20.25mmol of imidazole-4, 5-dicarboxylic acid is added into a mortar together and ground for 1.5h along the same direction, the long afterglow phenomenon can be seen after the irradiation of an ultraviolet lamp, reactants are reacted by violent collision during grinding, and the prepared solid dispersion long afterglow material is sampled and placed in a drier, and the yield is 95%.
Example 6
n 2, M Cd, X OAc, 0.1mmol MX20.25mmol of imidazole-4, 5-dicarboxylic acid were added together in a mortarGrinding in the same direction for 1.5h, and observing long afterglow after irradiation of an ultraviolet lamp, wherein reactants are violently collided to react during grinding to prepare the solid dispersion long afterglow material, and the solid dispersion long afterglow material is sampled and placed in a drier, wherein the yield is 95%.
Example 7
n 2, M Cd, X Cl, 0.1mmol MX20.25mmol of imidazole-4, 5-dicarboxylic acid is added into a mortar together and ground for 2 hours along the same direction, the long afterglow phenomenon can be seen after the irradiation of an ultraviolet lamp, reactants are reacted by violent collision during grinding, and the prepared solid dispersion long afterglow material is sampled and placed in a drier, and the yield is 97 percent.
Example 8
n ═ 2, M ═ Zn, X ═ Cl, 0.1mmol of MX20.25mmol of imidazole-4, 5-dicarboxylic acid is added into a mortar together and ground for 2 hours along the same direction, the long afterglow phenomenon can be seen after the irradiation of an ultraviolet lamp, reactants are reacted by violent collision during grinding, and the prepared solid dispersion long afterglow material is sampled and placed in a drier, and the yield is 97 percent.
For comparison, specific materials, amounts, milling times and yields in examples 1 to 8 are listed, as shown in tables 1 and 2.
TABLE 1 specific substances, amounts, pH values, reaction temperatures, times and yield values in examples 1 to 4
Figure BDA0002336590090000101
TABLE 2 specific materials, amounts, milling times and yield values for examples 5 to 8
Figure BDA0002336590090000102
The core principle of the invention is a coordination reaction, as long as the central ion or atom provides an empty orbit, the ligand provides a lone pair of electrons to react, the +2 and +3 valent ions are common valence state expression forms of metals, and the ions have at least more than two valence statesThe empty track can meet the requirements; the metal salt is coordinated by metal ions rather than anions, and OAc, F, Cl, Br, I, OH, NO3These anions are very common and are the most common metal salts that form ionic compounds with metal ions.
In the invention, R in the dicarboxylimidazole derivative1And R2The reasonable popularization is H, alkane or aromatic hydrocarbon, because the coordination center is reacted with the carboxylate ions in the ligand dicarboxylimidazole, the substituent groups R1 and R2 in the ligand do not influence the reaction as long as the substituent groups are not groups capable of reacting with the coordination center, and hydrocarbon and aromatic hydrocarbon substituent groups just meet the requirement.
MXnAnd dicarboxylimidazole or a derivative thereof in a theoretical molar ratio of 1: 2, there were some errors in the specific experimental procedure to ensure that there were sufficient organics A and MXnTherefore, 0.05mol of the compound is added to the reaction mixture in an appropriate amount, and finally the molar ratio is widened to (0.1 to 0.15): (0.2-0.3) to ensure the reaction can be normally carried out.
The reasonable range of pH values of 5.72 and 5.75 in examples 1 to 4 was set to 5.7 to 5.8 because of some error in the buffer range of the buffer solution. The reaction time is widened to 36-72 h, because the coordination centers of the reaction are different, the requirements on the reaction time are different, and 72h is required for lanthanide metal ions.
In embodiments 5 to 8, since the chemical environments of the coordination centers are different, the grinding time is different, the longer the grinding time is, the more sufficient the reaction is, the more 30min the grinding is performed, which is beneficial to the sufficient reaction, and thus the grinding time is popularized.
Examples 1 to 8 prepare cadmium small-molecule long afterglow materials and zinc small-molecule long afterglow materials, which are respectively Cd-Imdc (R) as shown in FIG. 3 and FIG. 21＝H,R2H) and Zn-Imdc (R)1＝H,R2H), we can see from the figure that the structures of the two small molecules are similar.
FIG. 4 is a UV-VISIBLE absorption spectrum of Zn-Imdc and Cd-Imdc; the absorption peak between 200nm and 300nm is mainly ligandDue to the central metal ion Zn of the complex2+And Cd2+Is fully filled d10The electronic configuration has no d-d electron transition absorption band, and therefore only the electron transition absorption band of the ligand is shown in the absorption spectrum. Other coordination center ion Ca2+、Fe3+、Co2+、Cr2+、Ni2+、Cu2+、Mn2+、Pd2+、Cr3+A d-d transition will occur, correspondingly showing an absorption band for the d-d electron transition, Ir3+、Yb3+、Er3+、Eu3+、Tb3+、Gd3+、Nd3+、Pt2+An f-f transition occurs and accordingly exhibits an f-f electron transition absorption band, which is coordinated with the central Mg2+、Al3+、B3+And is also only the pi-pi transition of the ligand.
FIG. 5 is a PXRD diagram of Zn-Imdc and Cd-Imdc; the peak of the two complexes is sharp and narrow and high, which shows that the crystal grains are large, the crystal is perfect, and the sample purity is high; the peak of Cd-Imdc is higher than that of Zn-Imdc, which shows that the crystal of Cd-Imdc has better crystal form, large crystal grain and high crystallinity than that of Zn-Imdc. Consistent with the results from the experiments.
FIG. 6 is an infrared spectrum of Zn-Imdc and Cd-Imdc; from the figure, the IR spectrum shapes of two small molecule complexes are similar, and the difference is the absorption intensity of Zn-Imdc and Cd-Imdc complexes. The IR spectrum of the complex shows mainly the characteristic absorption of the ligand. At 3236cm-1The wide band is O-H stretching vibration, 3362cm-1Under the action of N-H stretching vibration at 1750cm-1There is an absorption peak indicating the presence of a carboxyl group. Furthermore, it is located at 1226cm-1The band at (B) is related to the stretching vibration of C-N, which shows that C-N participates in metal coordination and Zn-N/Cd-N bonds appear at far infrared. At 1028cm-1The spectral band of (a) is associated with O-H in-plane bending vibration.
FIG. 7 is a graph of emission spectra of Zn-Imdc and Cd-Imdc; at λExUnder excitation of 387nm, the two small molecule complexes have a broadband emission in the range of 400-550 nm, and can be considered as a complexLLCT luminescence of the body. Since both Zn (II) and Cd (II) are fully charged with d10Electronic configuration, it is difficult to oxidize or reduce, so the emission band will not be either LMCT or MLCT luminescence. In conclusion, the complex obtains blue light region emission with the wavelength of 475nm under the excitation of ultraviolet light 387 nm.
FIG. 8 is a long persistence effect diagram of Zn-Imdc and Cd-Imdc, specifically showing the effect diagrams of 0s, 1s, 2s, 3s, 4s and 5s, respectively, where 0s corresponds to the UV lamps being turned on, and then 1s, 2s, 3s, 4s and 5s correspond to 1s, 2s, 3s, 4s and 5s and the UV lamps being turned off. Zn-Imdc shows bright blue at 0s, dark blue at 1s, light blue at 2s, bluish white at 3s, yellowish at 4s and yellowish at 5 s; Cd-Imdc showed bright blue at 0s, dark blue at 1s, light blue at 2s, bluish in white at 3s, yellowish at 4s and yellowish at 5 s. After the ultraviolet lamp is excited by 365nm, the ultraviolet lamp is turned off, the long afterglow effect captured by the single lens reflex is approximately maintained for about 5s, and the long afterglow effect disappears completely after 5s, so that the original color of the sample is presented.
For complexes with other central ions, the corresponding crystal structures are similar to those shown in fig. 2 and 3; because the central ion is Mg2+、Al3+、B3+The complex has no d-d electronic transition absorption band, so that the position of the ultraviolet absorption peak is the same as that in FIG. 4, and Co2+、Cr2+、Ni2+、Cu2+、Mn2+、Pd2+、Cr3+A d-d transition occurs and correspondingly also shows an absorption band for the d-d electron transition, Ir3+、Yb3+、Er3+、Eu3+、Tb3+、Gd3+、Nd3+、Pt2+F-f transition occurs and accordingly f-f electron transition absorption band is also shown; thus, different complexes will be excited at their characteristic excitation wavelengths and emit different fluorescent colors, but a long afterglow phenomenon similar to that of fig. 8 still occurs after the excitation is stopped, and the long afterglow phenomenon is maintained at least around 5 s.

Claims (10)

1. A preparation method of a micromolecule long afterglow complex crystal is characterized by comprising the following steps,
step 1, MXnPlacing the organic matter A and the organic matter A in distilled water, adjusting the pH value of the obtained mixed system to 5.7-5.8 to obtain a mixed system A, and carrying out hydrothermal reaction on the mixed system A at 150-160 ℃ to obtain a product liquid;
wherein X ═ F, Cl, Br, I, OH, NO3Or OAc, n is 2 or 3, when n is 2, M is a metal ion with a valence of +2 which can be used as a coordination center in the periodic table of elements, and when n is 3, M is a metal ion with a valence of +3 which can be used as a coordination center in the periodic table of elements;
the structural formula of the organic substance A is as follows:
Figure FDA0002336590080000011
R1h, alkanes or aromatics, R2H, an alkane or aromatic hydrocarbon;
and 2, washing and drying the product in the product liquid to obtain the micromolecule long afterglow complex crystal.
2. The method for preparing a small molecule long afterglow complex crystal according to claim 1, wherein in step 1, MXnThe molar ratio of the organic matter A to the organic matter A is (0.1-0.15):
(0.2～0.3)。
3. the preparation method of the small molecule long afterglow complex crystal according to claim 1, wherein in the step 1, the mixed system A is reacted for 36 to 72 hours at the temperature.
4. The method for preparing a small-molecule long-afterglow complex crystal according to claim 1, wherein in step 1, when n is 2, M is Ca, Mg, Cu, Co, Ni, Cr, Cd, Zn, Mn, Pt or Pd, and when n is 3, M is Al, Fe, Cr, Ir, B, Nd, Yb, Er, Eu, Tb or Gd.
5. The method for preparing a small molecule long afterglow complex crystal according to claim 1, wherein in the step 2, the product in the product liquid is filtered, washed with distilled water and absolute ethyl alcohol for 2-3 times, and then dried at 45-60 ℃ for 12-18 h.
6. A small molecule long afterglow complex crystal obtained by the method for preparing a small molecule long afterglow complex crystal according to any one of claims 1 to 5.
7. A preparation method of small-molecule long-afterglow complex powder is characterized by comprising the following steps of (0.1-0.15): (0.2 to 0.3) molar ratio of MX to MXnMixing with an organic matter A, grinding to obtain a mixture A until the mixture A has a long afterglow phenomenon under ultraviolet light, and obtaining micromolecular long afterglow complex powder;
wherein X ═ F, Cl, Br, I, OH, NO3Or OAc, n is 2 or 3, when n is 2, M is a metal ion with a valence of +2 which can be used as a coordination center in the periodic table of elements, and when n is 3, M is a metal ion with a valence of +3 which can be used as a coordination center in the periodic table of elements;
the structural formula of the organic substance A is as follows:
Figure FDA0002336590080000021
R1h, alkanes or aromatics, R2H, alkanes or aromatics.
8. The method for preparing a small molecule long persistence complex powder of claim 7, wherein the MX is a long persistence complex powder of the formulanAnd the grinding time of the organic matter A is 1.5-2.5 h.
9. The method for preparing a small-molecule long-afterglow complex powder according to claim 7, wherein when n is 2, M is Ca, Mg, Cu, Co, Ni, Cr, Cd, Zn, Mn, Pt or Pd, and when n is 3, M is Al, Fe, Cr, Ir, B, Nd, Yb, Er, Eu, Tb or Gd.
10. A small molecule long afterglow complex powder obtained by the method for preparing a small molecule long afterglow complex powder according to any one of claims 7 to 9.
CN201911358558.6A 2019-12-25 2019-12-25 Small-molecule long-afterglow complex and preparation method thereof Pending CN111004182A (en)

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