CN107337688B - A kind of europium organic backbone complex and preparation method thereof - Google Patents
A kind of europium organic backbone complex and preparation method thereof Download PDFInfo
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- CN107337688B CN107337688B CN201710564099.1A CN201710564099A CN107337688B CN 107337688 B CN107337688 B CN 107337688B CN 201710564099 A CN201710564099 A CN 201710564099A CN 107337688 B CN107337688 B CN 107337688B
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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
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/13—Crystalline forms, e.g. polymorphs
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- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/182—Metal complexes of the rare earth metals, i.e. Sc, Y or lanthanide
Abstract
The invention discloses a kind of europium organic backbone complex and preparation method thereof, the chemical formulas of complex are as follows: [Eu (L) (DMF)2]n, wherein H3L is 5- (4 '-formic acid benzene oxygen) methylresorcinol dioctyl phthalate, DMF N, N '-dimethyl formamide.The complex can be made by dimethylformamide thermal method: the H for being 1:1.5 by the ratio between amount of substance3L ligand and EuCl3It is added in the DMF of certain volume, after being stirred at room temperature 30 minutes, 120 DEG C of reaction 72h of temperature is kept in closed reactor.Room temperature is cooling, obtains colourless bulk crystals, washs, vacuum drying, yield 76%.Complex of the present invention can send out feature feux rouges stronger when being excited with the light of 395nm wavelength, and CIE chromaticity coordinates is (0.5859,0.3178), its fluorescence lifetime is 2.535ns, and quantum yield is up to 93.0%, therefore the complex can be used as potential optical material.
Description
Technical field
The present invention relates to rare earth metal complexs, and in particular to a kind of europium organic backbone complex, especially one kind are based on
The europium complex and its system with luminosity that europium (III) ion and 5- (4 '-formic acid benzene oxygen) methylresorcinol dioctyl phthalate are constructed
Preparation Method.
Background technique
Rare earth metal complex due to multifrequency natures such as light, electricity, magnetic, shine, catalysis, the fields table such as biological medicine
Reveal wide application prospect, wherein organolanthanide complexes are as embedded photoluminescent material with traditional phosphor phase
Than due to unique texture possessed by rare earth ion itself and property, making it after cooperating with organic ligand, there is luminous intensity
Height, fluorescence color is pure, required excitation energy is low, fluorescence efficiency is high, is soluble in the advantages that organic media, thus is considered as most
There is a kind of luminescent material of application prospect.
Organic polycarboxylic acid ligand has stronger coordination ability, is widely used in preparing organolanthanide complexes.5-
(4 '-formic acid benzene oxygen) methylresorcinol dioctyl phthalate has good photo and thermal stability and hair as a kind of flexible organic carboxyl acid ligand
Optical property, especially when its with d10 electronic structure transition metal ions or rare earth ion be coordinated and to form complex
Afterwards, there is high application value in optical material field.Up to the present, it is based on 5- (4 '-formic acid benzene oxygen) methylresorcinol two
The rare earth metal complex that formic acid is constructed yet there are no report.
Summary of the invention
The purpose of the present invention is to provide a kind of europium organic backbone complex that can be used as optical material and its preparation sides
Method.
A kind of europium organic backbone complex provided by the invention, molecular formula are as follows: [Eu (L) (DMF) 2] n, wherein H3L be
5- (4 '-formic acid benzene oxygen) methylresorcinol dioctyl phthalate, DMF N, N '-dimethyl formamide；Structural formula are as follows:
The crystal of the complex belongs to monoclinic system, space group C2/c, cell parameter: α=γ=90 °, β=99.05 (6) °.The complex
The coordination mode of middle europium ion is nine coordinations, and each Eu (III) ion and nine oxygen are coordinated, and two of them oxygen (O1, O2) comes from
One chelating L3-Ligand, five oxygen (O4, O5, O6, O6A, O7) come from four bridging L3-Ligand, other two oxygen (O8, O9) come
The DMF molecule being coordinated from two end groups, i.e. the complex is to be connected adjacent ligand anion by coordinate bond, finally
Constitute tridimensional network.The range of Eu-O bond distance isX-ray powder diffraction confirms crystalloids
Product stable homogeneous.Under room temperature, the solid complexes are excited with the excitation wavelength of 395nm, the results show that complex exists
Occur Eu (III) ion characteristic emission peak due to caused by f-f transition at 592nm, 617nm, 651nm, 695nm, belongs to respectively
For Eu (III) ion5D0→7F1,5D0→7F2,5D0→7F3,5D0→7F4Characteristic transition.Wherein 617nm be Eu (III) from
Son5D0→7F2Maximum transition emission peak illustrates that ligand is higher to the energy transfer efficiency of rare earth ion.Pass through ultraviolet light irradiation
Digital photograph, complex can be observed and show the stronger feux rouges feature of Eu (III).Europium complex of the invention may be used as
Optical material.
The present invention provides a kind of preparation method of europium organic backbone complex, includes the following steps:
It (1) is the H of 1:1~1.5 by molar ratio3L ligand and EuCl3The polytetrafluoroethylene (PTFE) of the DMF solvent containing certain volume is added
Guan Zhong is stirred at room temperature 20~40 minutes；
(2) this polyfluortetraethylene pipe is placed in stainless steel cauldron and is sealed, be warming up to 120 DEG C of reaction 72h, dropped naturally
Temperature, it is overnight that colourless bulk crystals are precipitated, it washs, vacuum drying.
The H3L ligand and EuCl3Molar ratio be preferably 1:1.5.
It is described that be stirred at room temperature the time be preferably 30 minutes.
Advantages of the present invention and effect:
Rare Earth Europium organic backbone complex of the invention is to synthesize to obtain by dimethylformamide thermal method, preparation side
Method is simple, at low cost, and yield is high, and crystal quality is good.
Europium organic backbone complex provided by the invention is based on a kind of flexible ligand 5- (4 '-formic acid benzene oxygen) methylresorcinol
What dioctyl phthalate was constructed, the solid fluorescence emission spectrum of complex is shown under room temperature, when excitation wavelength is 395nm, cooperation
Object shows the stronger feux rouges feature of Eu (III), and chromaticity coordinates is (0.5859,0.3178), and test shows its fluorescence quantum yield
It is 93.0%, fluorescence lifetime 2.535ns.Europium organic backbone complex of the invention may be used as optical material.
Detailed description of the invention
The crystal structure figure of europium organic backbone complex prepared by Fig. 1 embodiment 1.
X-ray powder diffraction figure (experiment and the theoretical mould of europium organic backbone complex prepared by Fig. 2 embodiment 1 in 298K
Quasi- figure).
Europium organic backbone complex and 5- (4 '-formic acid benzene oxygen) methylresorcinol dioctyl phthalate ligand prepared by Fig. 3 embodiment 1 exists
The fluorescence spectra of 298K.
The feature feux rouges that europium organic backbone complex prepared by Fig. 4 embodiment 1 issues under ultraviolet light.
The fluorescence decay curve of europium organic backbone complex prepared by Fig. 5 embodiment 1.
Specific embodiment
Embodiment 1
Weigh 0.1mmol H3L and 0.15mmolEuCl3It is added in the polyfluortetraethylene pipe of 15ml, and 5ml DMF is added,
It is stirred at room temperature 30 minutes.This polyfluortetraethylene pipe is sealed in stainless steel cauldron, controlled at 120 DEG C of heating 72h, certainly
So cooling, it is overnight that colourless bulk crystals are precipitated, it washs, vacuum drying, the yield of gained europium organic backbone complex is 76%.
The structure determination of europium organic backbone complex:
The monocrystalline for choosing suitable size under the microscope, by using X-ray diffraction, with Bruker Smart Apex II
Detector passes through the Mo-K alpha ray of graphite monochromator monochromatization, and scanning mode ω, the temperature for collecting data is 293K.It is all to spread out
Data are penetrated after SAINT is restored, carry out semiempirical absorption correction using SADABS program.Crystal structure is direct by SHELXL-97
Method solves.Detailed axonometry data are shown in Table 1；Crystal structure is shown in Fig. 1, it is seen that each Eu (III) is all made of nine coordination modes,
With L3-It is coordinated using chelating, bridging and chelating-bridging mode, is coordinated, is consequently formed three-dimensional netted using end group with DMF
Structure；X-ray powder diffraction as shown in Fig. 2, experimental diffraction map is consistent with the powder diffraction spectrum simulated according to crystal structure,
Show that crystal prototype object is mutually uniform.
The crystallographic data of 1 complex of table
The luminosity of europium organic backbone complex:
The solid fluorescence emission spectrum (Fig. 3) of ligands and complexes is determined at room temperature.It is seen that
Under the excitation of 405nm wavelength, there is Eu (III) ion due to f-f transition at 592nm, 617nm, 651nm, 695nm in complex
Caused characteristic emission peak is attributed to Eu (III) ion respectively5D0→7F1,5D0→7F2,5D0→7F3,5D0→7F4Feature
Transition.Wherein Eu (III) ion at 617nm5D0→7F2Transition emission peak intensity is maximum, illustrate ligand to rare earth ion energy
It is higher to measure transmission efficiency.By ultraviolet light irradiation, it can be observed that complex shows the stronger feux rouges feature of Eu (III) (figure
4), chromaticity coordinates is (0.5859,0.3178).The fluorescence quantum yield and fluorescence lifetime of complex are tested, fluorescence is obtained
Quantum yield is 93.0%, and fluorescence lifetime 2.535ns, fluorescence decay curve is shown in Fig. 5.
Embodiment 2
Weigh 0.1mmol H3L and 0.15mmolEuCl3It is added in the polyfluortetraethylene pipe of 15ml, and 5ml H is added2O,
It is stirred at room temperature 30 minutes.This polyfluortetraethylene pipe is sealed in stainless steel cauldron, after heating 72h at 120 DEG C, is dropped naturally
Temperature, it is overnight to fail to precipitate crystal, obtain a large amount of white powders.
Embodiment 3
Weigh 0.1mmol H3L and 0.15mmolEuCl3It is added in the polyfluortetraethylene pipe of 15ml, and 5ml volume ratio is added
For the H of 1:12The mixed solvent of O and DMF is stirred at room temperature 30 minutes.This polyfluortetraethylene pipe is sealed in stainless steel cauldron
In, after heating 72h at 120 DEG C, Temperature fall is overnight that colourless bulk crystals are precipitated, wash, vacuum drying, gained crystal compared with
Small, shape is poor, and yield is about 14%.
Embodiment 4
Weigh 0.1mmol H3L and 0.15mmolEuCl3It is added in the polyfluortetraethylene pipe of 15ml, and 5ml volume ratio is added
For the H of 1:42The mixed solvent of O and DMF is stirred at room temperature 30 minutes.This polyfluortetraethylene pipe is sealed in stainless steel cauldron
In, after heating 72h at 120 DEG C, Temperature fall is overnight that colourless bulk crystals are precipitated, wash, vacuum drying, gained crystal compared with
Good, yield is about 46%.
Claims (5)
1. a kind of europium organic backbone complex, which is characterized in that molecular formula are as follows: [Eu (L) (DMF) 2] n, wherein H3L is 5- (4 '-
Formic acid benzene oxygen) methylresorcinol dioctyl phthalate, DMF N, N '-dimethyl formamide；Structural formula are as follows:
2. a kind of preparation method of europium organic backbone complex as described in claim 1, which is characterized in that including walking as follows
It is rapid:
It (1) is the H of 1:1~1.5 by molar ratio3L ligand and EuCl3The polyfluortetraethylene pipe of the DMF solvent containing certain volume is added
In, it is stirred at room temperature 20~40 minutes；
(2) this polyfluortetraethylene pipe is placed in stainless steel cauldron and is sealed, be warming up to 120 DEG C of reaction 72h, Temperature fall, every
Colourless bulk crystals are precipitated in night, wash, vacuum drying.
3. a kind of preparation method of europium organic backbone complex as claimed in claim 2, which is characterized in that the H3L ligand with
EuCl3Molar ratio be 1:1.5.
4. a kind of preparation method of europium organic backbone complex as claimed in claim 2, which is characterized in that described to be stirred at room temperature
Time is 30 minutes.
5. a kind of application of the europium organic backbone complex as described in claim 1 as optical material.
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