CN106317092A - Europium complex of pyromellitic acid ligand as well as preparation method and application thereof - Google Patents

Europium complex of pyromellitic acid ligand as well as preparation method and application thereof Download PDF

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CN106317092A
CN106317092A CN201610691960.6A CN201610691960A CN106317092A CN 106317092 A CN106317092 A CN 106317092A CN 201610691960 A CN201610691960 A CN 201610691960A CN 106317092 A CN106317092 A CN 106317092A
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europium complex
pyromellitic acid
preparation
europium
ion
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CN106317092B (en
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王军杰
石云峰
张道军
张有娟
张仁春
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Anyang Normal University
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Anyang Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
    • C07F5/003—Compounds containing elements of Groups 3 or 13 of the Periodic System without C-Metal linkages
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • 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 invention aims at providing an europium complex of a pyromellitic acid ligand, as well as a preparation method and an application of the europium complex of the pyromellitic acid ligand. The molecular formula of the europium complex is {[Eu(L)(FA)][(CH3)2NH2](H3O)}n, wherein L is an anion ligand of a pyromellitic acid, the structural formula is shown in the description, and the FA is formyl. The europium complex has a three dimensional topological structure {4<4>.6<10>.8}{4<4>.6<2>}, and has a stable optical property at room temperature.

Description

Europium complex, its preparation method and the application of a kind of Pyromellitic Acid part
Technical field
The invention belongs to rare earth metal complex technical field, the europium being specifically related to a kind of Pyromellitic Acid part coordinates Thing, its preparation method and application.
Background technology
Rare earth element is owing to itself having [Xe] 4f of uniqueness(0-1)5d(1-10)6s(2)Electron structure, there is general unit The spectral quality that element is incomparable, the rare earth luminous category almost covering whole solid luminescence, and there is abundant electricity Sub-energy level and long-life excited state, up to more than 20 ten thousand, energy level transition passage, diversified radiation absorption can be produced and send out Penetrate, constitute luminous widely and laser material.Along with Rare Earth Separation, the progress of purification technique, and the promotion of correlation technique, dilute Research and the application of soil luminescent material are significantly developed [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].The luminescence of rare earth compound is 4f based on them Electronics transition within f-f configuration or between f-d configuration.There is rare earth atom or the ion of the 4f shell of underfill, its light Composing about 30000 observable spectral lines, they can be launched from ultraviolet light, the various wavelength of visible ray to infrared light district Electromagnetic radiation.Energy level that rare earth ion is abundant and the transition characteristic of 4f electronics, make rare earth become huge luminous treasure-house, therefrom More novel luminescent material can be excavated out.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].In conjunction with joining The characteristics design of body and europium ion synthesizes the luminescent material of suitable europium complex and will inject for luminescent material scientific domain new Vigor.
Summary of the invention
It is an object of the invention to provide europium complex, its preparation method and the application of a kind of Pyromellitic Acid part, institute State europium complex and there is 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
The europium complex of a kind of Pyromellitic Acid part, the molecular formula of described 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 formyl.
Further, the crystal of described europium complex belongs to rhombic system, and space group is Pbca, and cell parameter is: a= 11.525 (2), b=13.547 (3), c=22.854 (5),α = 90 °, β=90 °,γ = 90°；Described The basic structure of europium complex is three-dimensional { 44.610.8}{44.62Topological structure.
The preparation method of the europium complex of above-mentioned Pyromellitic Acid part, is initially charged Pyromellitic Acid and Eu (NO3)2· 6H2O, adds the mixed solvent being made up of DMF and distilled water, and ultrasonic dissolution is uniform, regulates pH to 3 ~ 4, Then constant temperature 40 ~ 60 hours in the drying baker of 80 ~ 100 ° of C, through washing with acetone, are drying to obtain.
Specifically, described Pyromellitic Acid and Eu (NO3)2·6H2The mol ratio of O is 1 ~ 2:1.
Specifically, in described mixed solvent, DMF is 1 ~ 2:1 with the volume ratio of distilled water.
The europium complex of above-mentioned Pyromellitic Acid part is as the application of fluorescent material.
Beneficial effects of the present invention is as follows:
The present invention uses low-temperature solvent full-boiled process to synthesize, and the method is different from the methods such as high temperature hydro-thermal conventional in document report, gram The shortcomings such as high, dangerous big, low, the repeatable difference of productivity of temperature are taken.Preparation method technique of the present invention is simple, mild condition, Yield is higher, favorable repeatability, and described europium complex has stable optical property at normal temperatures, has Sensitive Detection aluminum Ion A l3+Ability, for material science development inject new vitality.
Accompanying drawing explanation
Fig. 1 is the coordination environment figure of europium (Eu) ion in described europium complex；
Fig. 2 is the two-dimensional structure schematic diagram in the three-dimensional network of described europium complex and three-dimensional network；
Fig. 3 is the three-dimensional { 4 of described europium complex4.610.8}{44.62Topological structure schematic diagram；
Fig. 4 is the XRD figure of described europium complex；
Fig. 5 is the solid ultraviolet-visible light spectrogram of described europium complex；
Fig. 6 is the solid fluorescence figure of described europium complex；
Fig. 7 is that described europium complex fluorescence intensity in various cationic solutions compares figure (at 422nm)；
Fig. 8 is that described europium complex fluorescence intensity in different mixed-cation solution compares figure (at 422nm).
Detailed description of the invention
In order to make the technical purpose of the present invention, technical scheme and beneficial effect clearer, below in conjunction with the accompanying drawings and specifically Technical scheme is further illustrated by embodiment, but described embodiment is intended to explain the present invention, and can not manage Solving is limitation of the present invention, and unreceipted concrete technology or condition person in embodiment, described by the document in this area Technology or condition or carry out according to product description.
Embodiment 1
The preparation process of described europium complex is as follows:
First in vial, add 0.1 mmol Pyromellitic Acid (Jinan Heng Hua Science and Technology Ltd.) and 0.05 mmol Eu (NO3)2·6H2O(europium nitrate, Jinan Heng Hua Science and Technology Ltd.), then with liquid-transfering gun by 2 mL mixed solvent (volume ratios DMF and the mixed solvent of distilled water for 1:1) add in this vial, ultrasonic dissolution is uniform, and adds Enter nitric acid 0.1 mL that mass fraction is 65% and regulate reactant liquor pH to 3 ~ 4, after being sealed by vial, be transferred to the dry of 100 ° of C In dry case, the heating environment in drying baker is more uniform, the present invention without vacuum condition, constant temperature 48 hours, to be cooled arrive After room temperature, observe and obtain faint yellow bulk crystals, with washing with acetone, be drying to obtain.
The productivity of gained europium complex is 70%, and molecular formula is: { [Eu (L) (FA)] [(CH3)2NH2](H3O)}n；
Main infrared absorption peak is 3441 cm1, 1640 cm1, 1545 cm1, 1520 cm1, 1481 cm1, 1321 cm1, 1252 cm1, 1121 cm1, 1086 cm1, 1025 cm1, 861 cm1, 823 cm1, 756 cm1, 788 cm1, 679 cm1, 619 cm1, 536 cm1, 507 cm1, 415 cm1。
The structure determination of gained europium complex:
Choose the monocrystalline of the suitable size of gained europium complex under the microscope, visit in Bruker APEX II CCD face under room temperature On diffractometer, with the Mo-K through graphite monochromator monochromatizationαRay (λ=0.71073), diffraction data is collected in ω mode. All diffraction datas use SADABS program to carry out semiempirical absorption correction.Cell parameter method of least square determines.Data are also Former and structure elucidation uses SAINT and SHELXTL program to complete respectively.Crystal structure direct method solves, the position of metallic atom Put by direct methodE-map determines, other non-hydrogen atoms then utilize difference Fourier function method and method of least square true Fixed, then carry out anisotropy refine, finally determine hydrogen atom position with theoretical hydrogenation method, partial solvent utilizes Q peak to be hydrogenated with.In detail The axonometry data of thin gained europium complex are shown in Table 1, XRD figure as shown in Figure 4, the characteristic peak of laboratory sample and analogue spectrums Characteristic peak fit like a glove, structure chart such as Fig. 1, in gained europium complex, the coordination environment of each europium ion is identical, nine coordination Europium ion, wherein seven coordination sites and L(i.e. Pyromellitic Acid anion ligand) by chelating-chelating-chelating-monodentate bridging Coordination mode is coordinated, and forms the two-dimensional structure figure (upside being positioned in Fig. 2) in Fig. 2, remains two coordination sites and FA(FA I.e. formyl part) it is coordinated by the coordination mode of bridging, the two-dimensional structure bridged in adjacent two Fig. 2 (is positioned at Fig. 2 In upside), the three dimensional structure (downside being positioned in Fig. 2) in pie graph 2, be consequently formed the three-dimensional { 4 shown in Fig. 34.610.8} {44.62Topological structure.Wherein, FA i.e. formyl part, it derives from the fabricated in situ of DMF DMF (at pH It is in the strong acidic environment of 3 ~ 4, the amido link easy fracture in DMF, and and water molecules, wherein formoxyl combines hydroxyl formation Formic acid, and remainder combines hydrogen evolution dimethylamine).Free hydrogen ion and the dimethylamine of protonation can neutralize anion Skeleton, and be stable in the presence of in three dimensional structure by hydrogen bond action.
Table 1 europium complex { [Eu (L) (FA)] [(CH3)2NH2](H3O)}nCrystallographic data
As shown in Table 1, the molecular formula of gained europium complex is C13H14EuNO11, its crystal belongs to rhombic system, and space group is Pbca, Cell parameter is: a=11.525 (2), b=13.547 (3), c=22.854 (5),α = 90 °, β= 90 °,γ = 90°。
The ultraviolet-ray visible absorbing property testing of gained europium complex:
After the ground process of europium complex sample being dried, carry out solid uv-visible absorption spectra test, outside solid violet-can See that spectrogram is shown in Fig. 5, at 218nm, 252 nm and 338 nm, demonstrate characteristic absorption.
The photoluminescent property of gained europium complex measures:
After the ground process of europium complex sample being dried, carrying out fluorometric investigation, solid fluorescence spectrogram as shown in Figure 6, at Ex is Excite at 370 nm, be 422 nm at Em, at 486 nm and 505 nm, all obtain emission peak.
Embodiment 2
The preparation process of described europium complex is as follows:
First in vial, add 0.05 mmol Pyromellitic Acid (Jinan Heng Hua Science and Technology Ltd.) and 0.05 mmol Eu (NO3)2·6H2O(europium nitrate, Jinan Heng Hua Science and Technology Ltd.), then with liquid-transfering gun by 2 mL mixed solvent (volume ratios DMF and the mixed solvent of distilled water for 2:1) add in this vial, ultrasonic dissolution is uniform, and adds Enter nitric acid 0.1 mL that mass fraction is 65% and regulate reactant liquor pH to 3 ~ 4, after being sealed by vial, be transferred to the dry of 80 ° of C In dry case, the heating environment in drying baker is more uniform, the present invention without vacuum condition, constant temperature 60 hours, to be cooled arrive After room temperature, observe and obtain faint yellow bulk crystals, with washing with acetone, be drying to obtain.The productivity of gained europium complex is 55%.
Application test 1
The embodiment of the present invention 1 gained europium complex (the most following sample) is carried out cationic fluorescent chemical sensitisation as luminescent material Application test.
Test method
Following concentration is 7 × 10-4The various nitrate M (NO of mol/L3)xN,N-dimethylformamide (DMF) solution: M =lithium ion 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 ion Co2+, nickel ion Ni2+, copper ion Cu2+, zinc ion Zn2+, strontium ion Sr2 +, silver ion Ag+, cesium ion Cs+, barium ions Ba2+, every kind of nitrate solution all takes 4 mL and adds 4 mg samples, for ensureing It is uniformly dispersed, ultrasonic Treatment 30 minutes, carried out by fluorescence analyser (Cary Eclipse EL06053221) the most respectively Fluorometric investigation.Result is as shown in Figure 7, it can be seen that the fluorescence of europium complex is had little to no effect by major part cation, ferrous Ion Fe2+, iron ion Fe3+, copper ion Cu2+The fluorescence making europium complex weakens significantly, and aluminium ion Al3+Make europium complex glimmering Light almost cancellation completely.And as shown in Figure 8, even in the environment of hybrid metal ion (hybrid metal solion with The test method of above-mentioned independent metal ion solution is identical: adding two kinds of nitrate in the DMF solution of 4mL, one of which is Aluminium salt, another kind is optional, and the concentration of two kinds of nitrate is 7 × 10-4Mol/L, is subsequently adding 4mg sample, obtains mixing gold Belong to solion, carry out testing), aluminium ion Al3+Still the almost cancellation completely of europium complex fluorescence is made, so described europium is joined Compound has Sensitive Detection aluminium ion Al3+Ability, can use as fluorescent material.
It should be noted last that: above-described embodiment is merely to illustrate and unrestricted technical scheme, any right The equivalent that the present invention is carried out and amendment or local without departing from spirit and scope of the invention are replaced, and it all should be contained at this Within bright protective scope of the claims.

Claims (6)

1. the europium complex of a Pyromellitic Acid part, it is characterised in that the molecular formula of described 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 formyl.
The europium complex of Pyromellitic Acid part the most according to claim 1, it is characterised in that the crystalline substance of described europium complex Body belongs to rhombic system, and space group is Pbca, and cell parameter is: a=11.525 (2), b=13.547 (3), and c= 22.854 (5),α = 90 °, β=90 °,γ = 90°。
The preparation method of the europium complex of Pyromellitic Acid part the most according to claim 1, it is characterised in that be initially charged Pyromellitic Acid and Eu (NO3)2·6H2O, adds the mixed solvent being made up of DMF and distilled water, ultrasonic It is uniformly dissolved, regulates pH to 3 ~ 4, then constant temperature 40 ~ 60 hours in the drying baker of 80 ~ 100 ° of C, through washing with acetone, be dried i.e. ?.
The preparation method of the europium complex of Pyromellitic Acid part the most according to claim 3, it is characterised in that described all Benzene tetracarboxylic acid and Eu (NO3)2·6H2The mol ratio of O is 1 ~ 2:1.
5. according to the preparation method of the europium complex of the Pyromellitic Acid part described in claim 3 or 4, it is characterised in that institute The volume ratio stating N,N-dimethylformamide and water is 1 ~ 2:1.
The europium complex of Pyromellitic Acid part the most according to claim 1 is as the application of fluorescent material.
CN201610691960.6A 2016-08-19 2016-08-19 A kind of europium complex, preparation method and the application of Pyromellitic Acid ligand Expired - Fee Related CN106317092B (en)

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CN107586390A (en) * 2017-07-14 2018-01-16 河南城建学院 A kind of calcium metal-organic framework materials and preparation method thereof and fluorescence property
CN107987282A (en) * 2017-12-12 2018-05-04 南开大学 A kind of hydrostable lanthanide series metal-organic framework materials and preparation and application

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Publication number Priority date Publication date Assignee Title
CN106588964A (en) * 2016-12-02 2017-04-26 浙江大学 Rare earth coordination complex nano materials as well as preparation method and application thereof
CN106588964B (en) * 2016-12-02 2019-01-29 浙江大学 A kind of rare earth compounding nano material and its preparation method and application
CN107586390A (en) * 2017-07-14 2018-01-16 河南城建学院 A kind of calcium metal-organic framework materials and preparation method thereof and fluorescence property
CN107987282A (en) * 2017-12-12 2018-05-04 南开大学 A kind of hydrostable lanthanide series metal-organic framework materials and preparation and application
CN107987282B (en) * 2017-12-12 2020-07-24 南开大学 Water-stable lanthanide metal-organic framework material, preparation and application thereof

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