CN106317092B - A kind of europium complex, preparation method and the application of Pyromellitic Acid ligand - Google Patents
A kind of europium complex, preparation method and the application of Pyromellitic Acid ligand Download PDFInfo
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- CN106317092B CN106317092B CN201610691960.6A CN201610691960A CN106317092B CN 106317092 B CN106317092 B CN 106317092B CN 201610691960 A CN201610691960 A CN 201610691960A CN 106317092 B CN106317092 B CN 106317092B
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
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- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/64—Fluorescence; Phosphorescence
- G01N21/6428—Measuring fluorescence of fluorescent products of reactions or of fluorochrome labelled reactive substances, e.g. measuring quenching effects, using measuring "optrodes"
Abstract
The purpose of the present invention is to provide a kind of europium complex, preparation method and the application of Pyromellitic Acid ligand, the molecular formula of the europium complex is { [Eu (L) (FA)] [(CH3)2NH2](H3O)}n, wherein L is Pyromellitic Acid anion ligand, and structural formula is as follows：, FA is formate.Europium complex of the present invention has three-dimensional { 44.610.8}{44.62Topological structure, there is under room temperature stable optical property.
Description
Technical field
The invention belongs to rare earth metal complex technical fields, and in particular to a kind of europium cooperation of Pyromellitic Acid ligand
Object, preparation method and application.
Background technology
Rare earth element has unique [Xe] 4f due to itself(0-1)5d(1-10)6s(2)Electron structure, there is general member
The incomparable spectral quality of element, the rare earth luminous scope for almost covering entire solid luminescence, and with abundant electricity
Sub- energy level and long-life excitation state, up to more than 20 ten thousand, energy level transition channel, can generate diversified radiation absorption and hair
It penetrates, forms extensive luminous and laser material.It is dilute with Rare Earth Separation, the progress of purification technique and the promotion of the relevant technologies
The research and application of native luminescent material obtain significantly developing [Sun, J.；Song,B.；Ye,Z.；Yuan,
J.Inorg.Chem.2015,54,11660；Zhang,S.-Y.；Shi,W.；Cheng,P.；Zaworotko,
M.J.J.Am.Chem.Soc.2015,137,12203；Li,Y.；Yu,J.-W.；Liu,Z.-Y.；Yang,E.-C.；Zhao,X.-
J.Inorg.Chem.2015,54,153].Rare earth compound it is luminous be based on their 4f electronics within f-f configurations or f-
Transition between d configurations.The rare earth atom or ion of 4f shells with underfill, spectrum about 30000 observables
The spectral line arrived, they can emit the electromagnetic radiation of the various wavelength from ultraviolet light, visible ray to infrared light district.Rare earth ion is rich
Rich energy level and the transition characteristic of 4f electronics make rare earth become huge luminous treasure-house, can therefrom excavate out more novel hairs
Luminescent material.Europium (Eu) is one of Typical Representative therein [Han, Y.；Li,X.；Li,L.；Ma,C.；Shen,Z.；Song,Y.；
You,X.Inorg.Chem.2010,49,10781].The design of the characteristic of binding partner and europium ion synthesizes suitable europium complex
Luminescent material will be luminescent material scientific domain inject new vitality.
Invention content
The purpose of the present invention is to provide a kind of europium complex, preparation method and the application of Pyromellitic Acid ligand, institutes
Stating europium complex has three-dimensional { 44.610.8}{44.62Topological structure, there is under room temperature stable optical property.
The present invention adopts the following technical scheme that：
A kind of europium complex of Pyromellitic Acid ligand, the molecular formula of the europium complex is { [Eu (L) (FA)] [(CH3)2NH2](H3O)}n, wherein L is Pyromellitic Acid anion ligand, and structural formula is as follows：
FA is formate.
Further, the crystal category rhombic system of the europium complex, space group Pbca, cell parameter are： α=90 °, β=90 °, γ=90 °；The europium
The basic structure of complex is three-dimensional { 44.610.8}{44.62Topological structure.
The preparation method of the europium complex of above-mentioned Pyromellitic Acid ligand first adds in Pyromellitic Acid and Eu (NO3)3·
6H2O adds the mixed solvent being made of n,N-Dimethylformamide and distilled water, and ultrasonic dissolution is uniform, and adjusting pH to 3~
4, then constant temperature 40~60 hours in 80~100 DEG C of drying box, wash through acetone, are drying to obtain.
Specifically, the Pyromellitic Acid and Eu (NO3)3·6H2The molar ratio of O is 1~2：1.
Specifically, the volume ratio of the in the mixed solvent, n,N-Dimethylformamide and distilled water is 1~2：1.
Application of the europium complex of above-mentioned Pyromellitic Acid ligand as fluorescent material.
Beneficial effects of the present invention are as follows：
The present invention is synthesized using low-temperature solvent heat method, and this method is different from the side such as common high temperature hydro-thermal in document report
Method overcomes the shortcomings of temperature is high, danger is big, low yield, repeatability difference.Preparation method of the present invention is simple for process, condition
Mildly, yield is higher, favorable repeatability, and the europium complex has stable optical property at normal temperatures, has sensitive
Detect aluminium ion Al3+Ability, be materials science field development inject new vitality.
Description of the drawings
Fig. 1 is the coordination context diagram of europium (Eu) ion in the europium complex；
Fig. 2 is the two-dimensional structure schematic diagram in the three-dimensional network and three-dimensional network of the europium complex；
Fig. 3 is the three-dimensional { 4 of the europium complex4.610.8}{44.62Topological structure schematic diagram；
Fig. 4 is the XRD diagram of the europium complex；
Fig. 5 is the solid UV-visible spectrum of the europium complex；
Fig. 6 is the solid fluorescence figure of the europium complex；
Fig. 7 compares figure for fluorescence intensity of the europium complex in various cationic solutions (at 422nm)；
Fig. 8 compares figure for fluorescence intensity of the europium complex in different mixed-cation solution (at 422nm).
Specific embodiment
In order to make the technical purpose of the present invention, technical solution and advantageous effect clearer, below in conjunction with the accompanying drawings and specifically
Embodiment is further illustrated technical scheme of the present invention, but the embodiment is intended to explain the present invention, and cannot manage
It solves as limitation of the present invention, it is in the examples where no specific technique or condition is specified, described according to document in the art
Technology or condition are carried out according to product description.
Embodiment 1
The preparation process of the europium complex is as follows：
0.1mmol Pyromellitic Acids (Jinan Heng Hua Science and Technology Ltd.s) and 0.05mmol are added in first in vial
Eu(NO3)3·6H2O (europium nitrate, Jinan Heng Hua Science and Technology Ltd.s), then with liquid-transfering gun by 2mL mixed solvents (volume ratio 1:
1 n,N-Dimethylformamide and the mixed solvent of distilled water) it adds in the vial, ultrasonic dissolution is uniform, and adds in matter
It measures the nitric acid 0.1mL that score is 65% and adjusts reaction solution pH to 3~4, after vial is sealed, be transferred to 100 DEG C of drying
In case, the heating environment in drying box is more uniform, and the present invention is without vacuum condition, constant temperature 48 hours, to be cooled to room
Wen Hou, observation obtain faint yellow bulk crystals, are washed, be drying to obtain with acetone.
The yield of gained europium complex is 70%, and molecular formula is：{[Eu(L)(FA)][(CH3)2NH2](H3O)}n；
Main infrared absorption peak is 3441cm﹣ 1, 1640cm﹣ 1, 1545cm﹣ 1, 1520cm﹣ 1, 1481cm﹣ 1, 1321cm﹣ 1,
1252cm﹣ 1, 1121cm﹣ 1, 1086cm﹣ 1, 1025cm﹣ 1, 861cm﹣ 1, 823cm﹣ 1, 756cm﹣ 1, 788cm﹣ 1, 679cm﹣ 1, 619cm﹣ 1,
536cm﹣ 1, 507cm﹣ 1, 415cm﹣ 1。
The structure determination of gained europium complex：
The monocrystalline of the suitable size of gained europium complex is chosen under the microscope, at room temperature in Bruker APEX II CCD
Face is visited on diffractometer, with the Mo-K alpha rays through graphite monochromator monochromatizationDiffraction number is collected in a manner of ω
According to.All diffraction datas carry out semiempirical absorption correction using SADABS programs.Cell parameter is determined with least square method.Data
Reduction and structure elucidation are completed respectively using SAINT and SHELXTL programs.Crystal structure is solved with direct method, metallic atom
Position is determined by the E-map of direct method, and other non-hydrogen atoms are then true using difference Fourier function method and least square method
It is fixed, anisotropy refine is then carried out, finally determines hydrogen atom position with theoretical hydrogenation method, partial solvent adds hydrogen using Q peaks.In detail
The axonometry data of thin gained europium complex are shown in Table 1, and XRD diagram is as shown in figure 4, the characteristic peak and analogue spectrums of laboratory sample
Characteristic peak fit like a glove, structure chart such as Fig. 1, the coordination environment of each europium ion is identical in gained europium complex, nine coordinations
Europium ion, wherein seven coordination sites pass through chelating-chelating-chelating-monodentate bridging with L (i.e. Pyromellitic Acid anion ligand)
Coordination mode is coordinated, and forms the two-dimensional structure figure in Fig. 2 (being located at the upside in Fig. 2), remaining two coordination sites and FA (FA
That is formate ligand) it is coordinated by the coordination mode of bridging, the two-dimensional structure bridged in two adjacent Fig. 2 (is located at Fig. 2
In upside), form the three-dimensional structure (be located at downside in Fig. 2) in Fig. 2, three-dimensional { 4 shown in Fig. 3 be consequently formed4.610.8}
{44.62Topological structure.Wherein, FA, that is, formate ligand, the fabricated in situ from n,N-Dimethylformamide DMF is (in pH
For in 3~4 strong acidic environment, the amido bond easy fracture in DMF, and and water molecules, wherein formoxyl combination hydroxyl shape
Formic acid, and remainder combination hydrogen forms dimethylamine).Free hydrogen ion and the dimethylamine of protonation can neutralize it is cloudy from
Sub- skeleton, and pass through hydrogen bond action and be stable in the presence of in three-dimensional structure.
1 europium complex of table { [Eu (L) (FA)] [(CH3)2NH2](H3O)}nCrystallographic data
As shown in Table 1, the molecular formula of gained europium complex is C13H14EuNO11, crystal category rhombic system, space group is
Pbca, cell parameter are：α=90 °, β=
90 °, γ=90 °.
The ultraviolet-ray visible absorbing property of gained europium complex measures：
After the dry ground processing of europium complex sample, solid uv-visible absorption spectra test, solid violet are carried out
Outside-visible ray spectrogram is shown in Fig. 5, and characteristic absorption is shown at 218nm, 252nm and 338nm.
The photoluminescent property of gained europium complex measures：
After the dry ground processing of europium complex sample, carry out fluorometric investigation, solid fluorescence spectrogram as shown in fig. 6,
Ex is excites at 370nm, in Em all to obtain emission peak at 422nm, 486nm and 505nm.
Embodiment 2
The preparation process of the europium complex is as follows：
First in vial add in 0.05mmol Pyromellitic Acids (Jinan Heng Hua Science and Technology Ltd.s) and
0.05mmol Eu(NO3)3·6H2O (europium nitrate, Jinan Heng Hua Science and Technology Ltd.s), then with liquid-transfering gun by 2mL mixed solvents
(volume ratio 2:1 n,N-Dimethylformamide and the mixed solvent of distilled water) it adds in the vial, ultrasonic dissolution is equal
It is even, and add in the nitric acid 0.1mL that mass fraction is 65% and adjust reaction solution pH to 3~4, after vial is sealed, it is transferred to
In 80 DEG C of drying box, the heating environment in drying box is more uniform, and the present invention is without vacuum condition, constant temperature 60 hours,
It is to be cooled to after room temperature, observation obtains faint yellow bulk crystals, is washed, is drying to obtain with acetone.The yield of gained europium complex
It is 55%.
Application test 1
Cationic fluorescent chemistry is carried out using 1 gained europium complex of the embodiment of the present invention (i.e. following samples) as luminescent material
Application in Sensing is tested.
Test method
Following concentration are 7 × 10-4The various nitrate M (NO of mol/L3)xN,N-dimethylformamide (DMF) it is molten
Liquid：M=lithium ions Li+, sodium ion Na+, magnesium ion Mg2+, aluminium ion Al3+, potassium ion K+, calcium ion Ca2+, chromium ion Cr3+, manganese
Ion Mn2+, iron ion Fe3+, ferrous ion Fe2+, cobalt ions Co2+, nickel ion Ni2+, copper ion Cu2+, zinc ion Zn2+, strontium from
Sub- Sr2+, silver ion Ag+, cesium ion Cs+, barium ions Ba2+, each nitrate solution takes 4mL and respectively adds in 4mg samples, to protect
Card is uniformly dispersed, ultrasonication 30 minutes, then respectively by fluorescence analyser (CaryEclipse EL06053221) into
Row fluorometric investigation.The results are shown in Figure 7, it can be seen that most of cation has little effect the fluorescence of europium complex, sub-
Iron ion Fe2+, iron ion Fe3+, copper ion Cu2+The fluorescence of europium complex is made to weaken significantly, and aluminium ion Al3+Make europium complex
Fluorescence is almost quenched.Even and as shown in figure 8, in the environment of mixed metal ion (mixed metal solion
It is identical with the test method of above-mentioned independent metal ion solution：Two kinds of nitrate, one of which are added in the DMF solution of 4mL
It is another optional for aluminium salt, and the concentration of two kinds of nitrate is 7 × 10-4Then mol/L adds in 4mg samples, is mixed
Metal ion solution is tested), aluminium ion Al3+Still europium complex fluorescence is made almost to be quenched, so the europium
Complex has Sensitive Detection aluminium ion Al3+Ability, can be used as fluorescent material.
It should be noted last that：Technical scheme of the present invention that the above embodiments are only illustrative and not limiting is any right
The equivalent replacement and do not depart from the modification of spirit and scope of the invention or part replacement that the present invention carries out, should all cover in this hair
Within bright protective scope of the claims.
Claims (5)
1. a kind of europium complex of Pyromellitic Acid ligand, which is characterized in that the molecular formula of the europium complex is { [Eu (L)
(FA)][(CH3)2NH2](H3O)}n, wherein L is Pyromellitic Acid anion ligand, and structural formula is as follows：
, FA is formate；The crystal category rhombic system of the europium complex, space group Pbca,
Cell parameter is：A=11.525 (2), b=13.547 (3), c=22.854 (5),α = 90 °, β=
90 °,γ = 90°。
2. the preparation method of the europium complex of Pyromellitic Acid ligand according to claim 1, which is characterized in that first add in
Pyromellitic Acid and Eu (NO3)3·6H2O adds the mixed solvent being made of n,N-Dimethylformamide and distilled water, ultrasound
It is uniformly dissolved, adjusts pH to 3 ~ 4, then constant temperature 40 ~ 60 hours in 80 ~ 100 °C of drying box, are washed through acetone, and drying is
.
3. the preparation method of the europium complex of Pyromellitic Acid ligand according to claim 2, which is characterized in that described equal
Benzene tetracarboxylic acid and Eu (NO3)3·6H2The molar ratio of O is 1 ~ 2：1.
4. the preparation method of the europium complex of the Pyromellitic Acid ligand according to Claims 2 or 3, which is characterized in that institute
The volume ratio for stating N,N-dimethylformamide and water is 1 ~ 2：1.
5. application of the europium complex of Pyromellitic Acid ligand according to claim 1 as fluorescent material.
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