CN115746028A - Fluorescent rare earth complex and preparation method and application thereof - Google Patents
Fluorescent rare earth complex and preparation method and application thereof Download PDFInfo
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- CN115746028A CN115746028A CN202211259814.8A CN202211259814A CN115746028A CN 115746028 A CN115746028 A CN 115746028A CN 202211259814 A CN202211259814 A CN 202211259814A CN 115746028 A CN115746028 A CN 115746028A
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Abstract
The invention belongs to the technical field of luminescent materials, and particularly relates to a fluorescent rare earth complex as well as a preparation method and application thereof. The fluorescent rare earth complex has the following repeating structural unit: [ Ln 2 (ppip) 2 (PhCOO) 6 ]Wherein Ln is rare earth ion, ppip is 1, 2-diphenyl imidazo [4,5-f][1,10]Phenanthroline
Description
Technical Field
The invention belongs to the technical field of luminescent materials, and particularly relates to a fluorescent rare earth complex as well as a preparation method and application thereof.
Background
The identifiability of cultural relic repair is one of the important criteria for embodying the authenticity of the cultural relic and complying with the cultural preservation professional ethics. The protection rule of ancient Chinese cultural relics stipulates that the repaired part should be coordinated with and recognizable as the original part. Through the analysis of three aspects of the relationship between the authenticity of the cultural relics, the moral protection of the cultural relics, the recognizable difference of the Chinese and the western, and the like, the novel fluorescence recognizable method not only gives consideration to the aesthetic interest of the traditional culture, but also meets the requirement of the restoration and the recognition of the cultural relics of the present generation. Therefore, it is important to establish a simple, rapid and sensitive fluorescent identification method.
Due to the special 4f-4f emission of lanthanide (Ln) ions, the fluorescence of lanthanide complexes (formed by self-assembly of lanthanide ion organic ligands) has the advantages of large Stokes shift, high optical purity, characteristic narrow-band emission and millisecond-level decay time, and due to the excellent physical and chemical properties of the lanthanide complexes, the lanthanide complexes can be widely applied to imaging equipment, light sources, sensors, light conversion molecular devices, organic light emitting diodes and the like. However, because the fluorescence quantum yield of the lanthanide complexes is to be improved, some lanthanide complexes have colors, and have certain influence on the colors of the cultural relic repair materials, and reports of the lanthanide complexes in the field of cultural relic repair recognition are few.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides a fluorescent rare earth complex which has high fluorescence quantum yield.
The invention also provides a preparation method and application of the fluorescent rare earth complex.
Specifically, the invention adopts the following technical scheme:
the first aspect of the invention provides a fluorescent rare earth complex, which has the following repeating structural unit: [ Ln 2 (ppip) 2 (PhCOO) 6 ]Wherein Ln is rare earth ion, ppip is 1, 2-diphenyl imidazo [4,5-f][1,10]Phenanthroline
Compared with the prior art, the invention provides a novel rare earth complex, and the rare earth complex is found to have excellent fluorescence characteristic and high fluorescence quantum yield.
In some embodiments of the present invention, ln is selected from any one of Eu, tb, sm, la, gd, preferably Eu.
The second aspect of the present invention provides a preparation method of the fluorescent rare earth complex, comprising the following steps:
and carrying out hydrothermal reaction on rare earth ions, ppip and benzonitrile to obtain the fluorescent rare earth complex.
In some examples of the invention, the rare earth ions are derived from water-soluble salts of rare earth metals, such as sulfates, nitrates, sulfites, hydrochlorides, and the like of rare earth metals, and hydrates thereof.
In some embodiments of the invention, the molar ratio of rare earth ions to ppip is 1 to 4:1, preferably 2 to 3:1, including but not limited to 1:1,2:1,3:1,4:1, etc.
In some examples of the invention, the ratio of rare earth ions to benzonitrile is 1mmol: 200-400. Mu.L, preferably 1mmol: 200-300. Mu.L, including but not limited to 1mmol:200 μ L,1mmol:250 μ L,1mmol:300 μ L,1mmol:350 μ L,1mmol:400 μ L, etc.
In some embodiments of the present invention, the concentration of the rare earth ion in the hydrothermal reaction system is 0.01 to 0.1mmol/mL, preferably 0.01 to 0.05mmol/mL, including but not limited to 0.01mmol/mL,0.02mmol/mL,0.03mmol/mL,0.04mmol/mL,0.05mmol/mL,0.06mmol/mL,0.07mmol/mL,0.08mmol/mL,0.09mmol/mL,0.1mmol/mL, etc.
In some embodiments of the invention, the concentration of the ppip in the hydrothermal reaction system is 0.005 to 0.06mmol/mL, preferably 0.005 to 0.02mmol/mL, including but not limited to 0.005mmol/mL,0.007mmol/mL,0.01mmol/mL,0.02mmol/mL,0.03mmol/mL,0.04mmol/mL,0.05mmol/mL,0.06mmol/mL, and the like.
In some examples of the invention, the hydrothermal reaction is carried out under basic conditions. Preferably, the pH of the alkaline conditions is from 8 to 13, preferably from 10 to 13, more preferably from 11 to 13, still more preferably from 11.5 to 12.5, including but not limited to 8,8.5,9,9.5, 10, 10.5, 11, 11.2, 11.4, 11.6, 11.8, 12, 12.2, 12.4, 12.6, 12.8, 13, etc.
In some embodiments of the invention, the hydrothermal reaction system contains a base at a concentration of 0.02 to 0.1wt%, preferably 0.02 to 0.05wt%, including but not limited to 0.02wt%,0.04wt%,0.05wt%,0.06wt%,0.08wt%,0.1wt%. The alkali includes but is not limited to any one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, potassium carbonate, potassium bicarbonate and ammonia water, and other alkaline substances can be adopted according to actual situations.
In some examples of the invention, the temperature of the hydrothermal reaction is 160 to 220 ℃, preferably 180 to 200 ℃, including but not limited to 160, 170, 180, 190, 200, 210, 220 ℃ and the like. The invention carries out high-temperature and high-pressure hydrothermal reaction in a closed system, and can hydrolyze benzonitrile in situ to obtain benzoate radical anion PhCOO – Thereby obtaining the target product. If the raw materials are directly mixed without adopting high temperature and high pressure, the cyanobenzene cannot be hydrolyzed in situ to obtain benzoate anions, so that the target product cannot be obtained.
In some examples of the present invention, the hydrothermal reaction time is 30 to 100 hours, preferably 48 to 96 hours, including but not limited to 30, 36, 40, 48, 50, 55, 60, 65, 70, 72, 84, 96 hours, etc. The synthesis method has short reaction time, can be completed in about 3 days generally, and has short time and high yield.
In a third aspect, the present invention provides a pigment composition, which comprises the fluorescent rare earth complex, and any one or more of a mineral pigment, a plant pigment and a chemical pigment. The fluorescent rare earth complexes of the invention are of low color, e.g. [ Eu ] 2 (ppip) 2 (PhCOO) 6 ]Is light yellow, does not affect the color of the pigment after being mixed with the pigment, but still presents remarkable fluorescent color under the irradiation of ultraviolet light and blue-violet light due to the excellent fluorescent characteristic of the fluorescent rare earth complex (such as [ Eu ] for example 2 (ppip) 2 (PhCOO) 6 ]Red) and can be used as a pigment, in particular to a 'invisible' fluorescent material of a pigment for repairing cultural relics, and the problem of identifying and repairing the cultural relics can be solved.
In some embodiments of the present invention, the fluorescent rare earth complex is incorporated in the pigment composition in an amount of 0.02 to 0.2wt%, preferably 0.02 to 0.06wt%, including but not limited to 0.02wt%,0.03wt%,0.04wt%,0.05wt%,0.06wt%,0.08wt%,0.1wt%,0.15wt%,0.2wt%. The fluorescent rare earth complex can realize the fluorescent recognition function under the condition of extremely low doping amount, and cannot influence the color of the pigment under the condition of low doping amount.
In some examples of the invention, the mineral pigment comprises any one or more of cinnabar, lime, realgar, lime green, ochre, clam powder, lead powder, mud gold, mud silver and titanium dioxide; the plant pigment comprises any one or more of cyanine, gamboge, rouge and carmine; the chemical pigment comprises any one or more of sky blue, chrome yellow, scarlet, dark red and eosin.
The fourth aspect of the invention provides the application of the fluorescent rare earth complex in fluorescence identification. The fluorescent rare earth complex of the invention presents specific color under the irradiation of ultraviolet light and blue-violet light, and can be applied to fluorescent identification.
The fifth aspect of the invention is to provide the application of the fluorescent rare earth complex in cultural relic identification and repair. For example, the method can be applied to the identification modification of Chinese painting cultural relics.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a novel fluorescent rare earth complex, which has excellent fluorescence characteristic, can emit bright fluorescence under the irradiation of ultraviolet light and blue-violet light, and has high fluorescence quantum yield.
Meanwhile, the invention develops a unique application of the fluorescent rare earth complex, and because the fluorescent rare earth complex has excellent fluorescence characteristic and light color, the color of the pigment is not influenced after a small amount of fluorescent rare earth complex is mixed with the pigment, but the fluorescent rare earth complex still presents obvious specific color under the irradiation of ultraviolet light and blue-violet light, so that the fluorescent rare earth complex can be used as an invisible fluorescent material for cultural relic restoration, and the problem of recognizable restoration of the cultural relic can be solved.
The fluorescent rare earth complex has higher fluorescence quantum yield than other rare earth complex fluorescent materials, and the rare earth complex material with low fluorescence quantum yield can achieve similar effect only by using larger amount, while the fluorescent rare earth complex can achieve the invisible and fluorescent recognition effect in the cultural relic repair pigment only by trace amount, thereby having more advantages in cost. On the other hand, the addition usage amount of the rare earth complex fluorescent material in the cultural relic repair material exceeds a certain limit, and the cultural relic repair material can be influenced to a certain extent.
Drawings
FIG. 1 shows [ Eu ] in example 1 2 (ppip) 2 (PhCOO) 6 ]The molecular structure of (1).
FIG. 2 shows [ Eu ] in example 1 2 (ppip) 2 (PhCOO) 6 ]A two-dimensional supramolecular network in the b-axis direction of (a).
FIG. 3 shows [ Eu ] in example 1 2 (ppip) 2 (PhCOO) 6 ]Is a perspective view of the supramolecular network along the c-axis direction.
FIG. 4 shows [ Eu ] in example 1 2 (ppip) 2 (PhCOO) 6 ]Simulation of (a) and PXRD pattern of the actual synthesized product.
FIG. 5 shows [ Eu ] in example 1 2 (ppip) 2 (PhCOO) 6 ]Infrared spectrum of (D).
FIG. 6 shows [ Eu ] in example 1 2 (ppip) 2 (PhCOO) 6 ]Thermogravimetric curve of (c).
FIG. 7 shows [ Eu ] in example 1 2 (ppip) 2 (PhCOO) 6 ]Photoluminescence spectrum in solid state.
FIG. 8 shows the control of [ Eu ] under (a) room light (LED lamp) and (b) UV lamp (365 nm) in example 1 2 (ppip) 2 (PhCOO) 6 ]Is shown in the figure.
FIG. 9 is a photograph of 5 pigment compositions of example 2 under natural light and an ultraviolet lamp.
FIG. 10 is the fluorescence spectra of 5 pigment compositions of example 2.
FIG. 11 shows [ Eu ] 2 (ppip) 2 (PhCOO) 6 ]、[Eu 2 (pip) 2 (PhCOO) 6 ]And [ Eu ] 2 (papip) 2 (PhCOO) 6 ]Comparative solid fluorescence spectra of (a).
Detailed Description
The technical solution of the present invention is further described below with reference to specific examples. The starting materials used in the following examples were obtained from conventional commercial sources, except that ppip (1, 2-diphenylimidazo [4,5-f ] [1,10] phenanthroline), pip (2-phenylimidazo [4,5-f ] [1,10] phenanthroline), papip (1-p-aminophenyl-2-phenylimidazo [4,5-f ] [1,10] phenanthroline) were synthesized by literature references; the adopted process adopts the conventional process in the field if no special specification exists; in the following examples or comparative examples, the room temperature mentioned means 20. + -. 5 ℃.
Example 1
This example provides a fluorescent rare earth complex [ Eu ] 2 (ppip) 2 (PhCOO) 6 ]Which has the following repeating structural unit: [ Eu ] as a source of electric potential 2 (ppip) 2 (PhCOO) 6 ]。
[Eu 2 (ppip) 2 (PhCOO) 6 ]The preparation method comprises the following steps:
weighing Eu (NO) 3 ) 3 ·6H 2 O (0.20mmol, 89mg) and ligand ppip (0.10mmol, 37mg) in a polytetrafluoroethylene-lined stainless steel reaction kettle, adding deionized water (10 ml), benzonitrile (50. Mu.L) and 40% NaOH (10. Mu.L), setting a temperature-programmed oven to heat at 190 ℃ for 72h, and then at 5 ℃ h -1 Is cooled to room temperature. The resulting crystals were filtered to obtain pale yellow flaky crystals, washed with distilled water and dried. The yield was 77%.
[Eu 2 (ppip) 2 (PhCOO) 6 ]And (3) characterization:
1) Crystal structure
[Eu 2 (ppip) 2 (PhCOO) 6 ]The crystal structure of (A) is shown in FIGS. 1-3, FIG. 1 is the molecular structure (labeled partial atom) of the fluorescent rare earth complex, FIG. 2 is the two-dimensional supramolecular network in the b-axis direction, and FIG. 3 is the two-dimensional supramolecular network in the b-axis directionPerspective view of supramolecular network along the c-axis direction.
In the fluorescent rare earth complex, each positive trivalent Eu ion is simultaneously combined with ppip ligand and benzoate ligand to form [ Eu 2 (ppip) 2 (PhCOO) 6 ]A repeating structural unit.
2) Crystal powder X-ray diffraction (PXRD)
According to [ Eu ] 2 (ppip) 2 (PhCOO) 6 ]The crystal structure of (a) is subjected to a simulated PXRD pattern, and is aligned with [ Eu 2 (ppip) 2 (PhCOO) 6 ]PXRD testing was performed to obtain a PXRD pattern for the simulated and actual synthetic product as shown in figure 4. FIG. 4 illustrates the successful synthesis of a product [ Eu ] having a target structure by the above-described method 2 (ppip) 2 (PhCOO) 6 ]。
3) Infrared spectroscopy
[Eu 2 (ppip) 2 (PhCOO) 6 ]The infrared spectrum of the sample is shown in FIG. 5. At 1412cm -1 And 1626cm -1 The strong absorption peak is related to the symmetric and asymmetric stretching vibration of carboxyl, 1571cm -1 The absorption peak can be assigned as C = N, and the C-H bond on the aromatic ring vibrates telescopically with 3060cm -1 The absorption peaks at (a) correspond to (b).
4) Heat weight change
[Eu 2 (ppip) 2 (PhCOO) 6 ]The thermogravimetric curve of (a) is shown in fig. 6. Before 300 ℃, the complex remains stable, the organic ligand is thermally decomposed after 300 ℃, resulting in rapid mass loss, and finally, the structure of the complex completely collapses, the mass fraction of the residual metal oxide being about 18%, in accordance with the composition.
5) Solid state fluorescence spectroscopy
[Eu 2 (ppip) 2 (PhCOO) 6 ]Photoluminescence spectrum (365 nm excitation) and excitation spectrum (inset, emission detection wavelength 620 nm) in solid state are shown in FIG. 7, from which [ Eu ] can be seen 2 (ppip) 2 (PhCOO) 6 ]Emitting red light under ultraviolet irradiation.
6) Fluorescence quantum yield
[Eu 2 (ppip) 2 (PhCOO) 6 ]Amount of fluorescence ofThe measurement result of the quantum yield was 84.23%, and the fluorescence quantum yield was very high.
7) Lifetime of fluorescence
[Eu 2 (ppip) 2 (PhCOO) 6 ]The fluorescence lifetime measurement of (365 nm excitation, 615nm emission) was 1.110ms.
8) Appearance form
FIG. 8 shows [ Eu ] under (a) room light (LED lamp) and (b) ultraviolet lamp (365 nm) 2 (ppip) 2 (PhCOO) 6 ]A photograph of the crystal. Can observe [ Eu ] under indoor light 2 (ppip) 2 (PhCOO) 6 ]Is light yellow crystal, and emits intense red light under the irradiation of an ultraviolet lamp.
Example 2
This example will describe [ Eu ] of example 1 2 (ppip) 2 (PhCOO) 6 ]Mixing with Realgar as Chinese painting pigment, and making into invisible fluorescent material.
Specifically, 2mg of Eu is added to 10mL of colloidoalum solution 2 (ppip) 2 (PhCOO) 6 ](abbreviated as "Eu") to obtain a suspension A. With no addition of [ Eu ] 2 (ppip) 2 (PhCOO) 6 ]10mL of collodion water is used as the component B. And (3) preparing 5 pigment composition samples by using the A liquid, the B liquid and realgar according to the composition shown in the table 1, and inspecting the performance and the fluorescence spectrum of the pigment composition under natural light and an ultraviolet lamp.
TABLE 1 pigment composition sample compositions
| Sample number | Realgar/g | A/μL | B/μL | Eu wt％ |
| ① | 0.1 | 0 | 300 | 0 |
| ② | 0.1 | 50 | 250 | 0.01 |
| ③ | 0.1 | 100 | 200 | 0.02 |
| ④ | 0.1 | 200 | 100 | 0.04 |
| ⑤ | 0.1 | 300 | 0 | 0.06 |
A photograph of 5 pigment compositions under natural light and UV light is shown in FIG. 9. FIG. 9 shows that [ Eu ] 2 (ppip) 2 (PhCOO) 6 ]After being combined with realgar, the color of realgar is not affected, and the realgar can be prepared under the condition of low mixing amount (0.02 wt percent)Can emit fluorescence under the irradiation of an ultraviolet lamp.
The fluorescence spectra (excitation wavelength: 365 nm) of the pigment compositions (1) to (5) are shown in FIG. 10, in which [ Eu ] 2 (ppip) 2 (PhCOO) 6 ]The doping amount of the compound (A) is gradually increased according to the arrow direction. FIG. 10 further reflects [ Eu 2 (ppip) 2 (PhCOO) 6 ]The fluorescent light can be emitted under the irradiation of an ultraviolet lamp under the condition of low doping amount, and the fluorescent intensity is enhanced along with the increase of the doping amount.
As can be seen from FIGS. 9 and 10, [ Eu ] 2 (ppip) 2 (PhCOO) 6 ]Can be mixed with pigment without influencing the color of the pigment, but emits bright red fluorescence under an ultraviolet lamp, so that the invisible fluorescent material can be used for repairing cultural relics, and the problem of recognizable repair of the cultural relics can be solved.
Comparative example 1
This comparative example provides two fluorescent rare earth complexes [ Eu ] 2 (pip) 2 (PhCOO) 6 ]、[Eu 2 (papip) 2 (PhCOO) 6 ]The only difference from example 1 is that the ligand ppip is
Replacement by the same molar amount of pip
Or papip
Is prepared from [ Eu 2 (pip) 2 (PhCOO) 6 ]、[Eu 2 (papip) 2 (PhCOO) 6 ]With [ Eu ] of example 1 2 (ppip) 2 (PhCOO) 6 ]The solid state fluorescence spectra of (2) were compared, as shown in FIG. 11. Three compounds were measured on the same fluorescence spectrometer, all conditions were: an excitation unit Slit (EX Slit) is 2.5nm, an emission unit Slit (EM Slit) is 2.5nm, and a photoelectric tube negative high Voltage (PMT Voltage) 550V.
As can be seen from the figure, [ Eu ] 2 (pip) 2 (PhCOO) 6 ]、[Eu 2 (papip) 2 (PhCOO) 6 ]And [ Eu ] of example 1 2 (ppip) 2 (PhCOO) 6 ]The fluorescence intensity sequence of the three fluorescent rare earth complexes under the same condition is as follows: [ Eu ] as a source of electric potential 2 (ppip) 2 (PhCOO) 6 ]>>[Eu 2 (pip) 2 (PhCOO) 6 ]>>[Eu 2 (papip) 2 (PhCOO) 6 ]Wherein [ Eu ] of example 1 2 (ppip) 2 (PhCOO) 6 ]Has obviously higher fluorescence intensity.
It can be seen that the ligand has a great influence on the fluorescence intensity of the fluorescent rare earth complex, and although the structure of pip and papip is similar to that of ppip and has a phenanthroline structure, the fluorescence property of the rare earth complex is obviously reduced by replacing the ppip ligand with other ligands containing phenanthroline structures.
Comparative example 2
This comparative example provides a fluorescent rare earth complex [ Eu ] 2 (ppip) 2 (PhCH 2 COO) 6 ]The only difference from example 1 is the addition of benzoate PhCOO – Substitution to phenylacetate PhCH 2 COO – Accordingly, benzonitrile is replaced with equimolar amounts of phenylacetonitrile during the preparation.
Tested, [ Eu ] 2 (ppip) 2 (PhCH 2 COO) 6 ]The fluorescence quantum yield of (1) is only 62.71%, compared with [ Eu ] of example 2 (ppip) 2 (PhCOO) 6 ]The fluorescence yield (84.23%) is significantly reduced.
Comparative example 3
The only difference between this comparative example and example 1 in the synthesis is that: the benzonitrile from example 1 was replaced with the same molar amount of benzoic acid.
As a result, the comparative example could not obtain the target product [ Eu ] under the same synthesis conditions 2 (ppip) 2 (PhCOO) 6 ]。
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Claims (10)
1. A fluorescent rare earth complex, which is characterized in that: having the following repeating structural unit: [ Ln 2 (ppip) 2 (PhCOO) 6 ]Wherein Ln is rare earth ion, ppip is 1, 2-diphenyl imidazo [4,5-f][1,10]Phenanthroline
2. The fluorescent rare earth complex of claim 1, wherein: and the Ln is selected from any one of Eu, tb, sm, la and Gd.
3. A method for preparing a fluorescent rare earth complex according to claim 1 or 2, characterized in that: the method comprises the following steps:
and carrying out hydrothermal reaction on rare earth ions, ppip and benzonitrile to obtain the fluorescent rare earth complex.
4. The method according to claim 3, wherein: the molar ratio of the rare earth ions to the ppip is 1-4: 1.
5. the method according to claim 3, wherein: the hydrothermal reaction is carried out under alkaline conditions.
6. The method according to claim 5, wherein: the pH value under the alkaline condition is 8-13.
7. The method according to claim 3, wherein: the temperature of the hydrothermal reaction is 160-220 ℃.
8. A pigment composition characterized by: the pigment composition comprises the fluorescent rare earth complex of claim 1 or 2 and any one or more of mineral pigments, plant pigments and chemical pigments.
9. Use of the fluorescent rare earth complex of claim 1 or 2 for fluorescence recognition.
10. The use of the fluorescent rare earth complex of claim 1 or 2 in cultural relics identification and repair.
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