CN103694993A - Beta-diketone rare earth complex red fluorescent material - Google Patents
Beta-diketone rare earth complex red fluorescent material Download PDFInfo
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- CN103694993A CN103694993A CN201310755651.7A CN201310755651A CN103694993A CN 103694993 A CN103694993 A CN 103694993A CN 201310755651 A CN201310755651 A CN 201310755651A CN 103694993 A CN103694993 A CN 103694993A
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Abstract
The invention relates to a beta-diketone rare earth complex red fluorescent material as well as a preparation and an application thereof. The rare earth complex is a luminous material with excellent performance and has a molecular structure of Eu(BTA)3(DFA), wherein BTA is benzoyltrifluoroacetone; DFA is 4,5-diazafluoren. The luminous material is prepared by carrying out a coordination reaction among europium nitrate, BTA and DFA. The specific preparation method comprises the following steps: reacting the europium nitrate, BTA and DFA in a mixed solution of acetonitrile and water according to a stoichiometric ratio of 1:3:1, adding a proper amount of sodium hydroxide to remove a proton of BTA, performing reduction vaporization, washing and drying to obtain a target product. The complex is high in dissolution performance, high in luminous efficiency and high in heat stability and can be applied to the field of photoluminescence or electroluminescence.
Description
Technical field
The present invention relates to rare earth luminescent material field, particularly relate to rare-earth complexes luminous material field.
Background technology
China has the abundantest in the world rare earth resources, and A wide selection of colours and designs, and this application that is rare earth luminescent material provides huge guarantee.At present, the research and development of rare earth luminescent material has covered whole luminous field, and has formed certain commercial production scale and market, and rare earth luminescent material has become the leading of current luminescent material.The rare-earth products of active development high-tech content, is converted into science and technology competition advantage by the rare earth resources advantage of China, and for the industrial transformation and the upgrading that promote China, and it is all significant to promote international competitiveness.
Rare earth ion, due to its special electron structure, shows the character of a lot of uniquenesses, thereby is all widely used in optical, electrical, magnetic field, is described as the treasure-house of novel material.Material is one of three large pillars of society development in science and technology, and luminescent material is a kind of important functional materials wherein.The transition of the energy level that rare earth ion is abundant and 4f layer electronics, makes rare earth ion become huge luminous treasure-house.Design and synthesize the rare earth compounding with high luminous performance is the target that investigators pursue always, because the distinctive 4f layer of rare earth ion electronics is subject to outer 5S
25P
6the shielding effect of layer electronics, makes rare earth ion be subject to the impact of Ligand Field very little, so luminescence rare earth ion generally has narrow band fluorescent emission, purity of color is high, luminous by force, luminescent lifetime is long.Yet the specific absorbance of rare earth ion is very little, need to by means of " antenna effect " of part, carry out the transmission of energy, the feature that effectively strengthens rare earth ion is luminous.Normally used anion ligand has carboxylic-acid part and beta-diketon class part, and as the neutral ligand of the second assistant ligand, is generally the heterocyclic ligand of nitrogenous, phosphorus, Sauerstoffatom.
Rare earth ion is high coordination of metal ion, and modal ligancy is 8-10, and therefore often having solvent coordination meets coordination structure, and such as water or ethanol etc., and the existence of these solvent molecules can greatly affect the luminescent properties of complex material.In addition on the one hand, luminescent material can have specific requirement to its thermostability when reality is used, and when being applied to organic electroluminescent (OEL), with regard to requiring rare earth luminescent material can stand the temperature of vacuum evaporation, does not decompose.
At present, luminous efficiency and the thermal stability of rare-earth complexes luminous material are not high enough, and this remains restriction, and it obtains the key issue of application at key areas such as organic electroluminescents.Therefore research and develop all good rare-earth complexes luminous materials of luminous efficiency and thermostability, for related industrieies such as exploitation OEL, all have important practical significance.
Summary of the invention
The object of the present invention is to provide a kind of beta-diketon rare earth compounding red fluorescence material with high luminescent properties and thermostability and preparation method thereof.This rare earth luminescent material is directly under solution reaction condition, and by part benzoyltrifluoroacetone, 4,5-diaza fluorenes and europium nitrate reaction obtain, and its simple synthetic method is easily gone, production cost is low.In this rare earth compounding red fluorescence material, due to the cooperate optimization effect of part, realized the high efficiency energy transmission between part and rare earth ion, thereby made material present very high luminous efficiency; And the combination of rare earth ion and stable aromaticity part, make described rare earth compounding possess good thermostability simultaneously.Therefore, this rare-earth complexes luminous material can be used as candidate material and is applied to photoluminescence or electroluminescent field.
One of technical scheme of the present invention, is to provide a kind of beta-diketon rare earth compounding red fluorescence material, carries out coordination reaction obtain with europium nitrate and part, and its molecular structural formula is Eu (BTA)
3(DFA), in formula, BTA is beta-diketonate ligand benzoyltrifluoroacetone, and DFA is neutral heterocyclic ligand 4,5-diaza fluorenes; Described rare earth (Eu
3+) structural formula (I) of title complex is as follows:
Described beta-diketon rare earth compounding red fluorescence material belongs to triclinic(crystalline)system, P-1 (NO.2) spacer, and unit cell parameters a=9.9416 (5), b=14.3928 (9),
α=80.406 (5), β=87.925 (4), γ=75.887 (5) °,
z=2, D
c=1.612g/cm
3, single crystal is that water white transparency is block; Title complex is eight-coordinate structure, central ion Eu
3+six Sauerstoffatoms and 4 with benzoyltrifluoroacetone part, two nitrogen-atoms coordinations of 5-diaza fluorenes part, rare earth ion is in coordination polyhedron center, rigidity phenyl ring and the aromatic heterocycle of surrounding, strengthened rigidity and the stability of agent structure, be also conducive to compound and by " antenna effect ", realize high efficiency luminous.
Described beta-diketon rare earth compounding red fluorescence material, under the ultraviolet excitation of different wave length, all be take the 610nm ruddiness strong as maximum emission peak sends, and can be used as red photoluminescent material, or as the luminescent layer material in multilayer electroluminescent device.
Two of technical scheme of the present invention, is to provide a kind of preparation method of described beta-diketon rare earth compounding red fluorescence material, and the method is that the solution coordination reaction by europium nitrate and part obtains.Its specific embodiments is divided into four steps:
(1) under room temperature, europium nitrate and benzoyltrifluoroacetone are dissolved in acetonitrile completely, both mol ratios are 1: 3, are fully uniformly mixed, and obtain colorless cleared solution A;
(2) under room temperature, in A solution, dropwise add sodium hydroxide solution, fully stir simultaneously, finally make sodium hydroxide and benzene
The mol ratio of formyl trifluoroacetone is 1: 1, obtains colorless cleared solution B;
(3) under room temperature, 4,5-diaza fluorenes is dissolved in acetonitrile completely, wherein 4, the mol ratio of 5-diaza fluorenes and europium nitrate is 1: 1, fully, after stirring and dissolving, obtains light settled solution C;
(4) under room temperature, C solution is dropwise added in B solution, stirs simultaneously and make it sufficient reacting, obtain settled solution, then, by gained solution rotary evaporation under reduced pressure, obtain white, crystalline, powder, through water washing and be drying to obtain rare-earth complexes luminous material product.
Beneficial effect of the present invention, first be provided beta-diketon rare earth compounding red fluorescence material, wherein combine well the beta-diketon class part of anionic and neutral heterocycle pyridine, luminous efficiency and the thermostability of material by " synergistic effect " of two kinds of parts, have effectively been improved, material presents strong narrow band emission characteristic under the exciting of UV-light, for the further application of luminescent material in fields such as organic electroluminescents provides technical support.
Secondly beneficial effect of the present invention is described beta-diketon rare earth compounding red fluorescence material Eu (BTA)
3(DFA) preparation method, has simple process, and equipment used is simple, and raw material is simple and easy to get, and production cost is low, and high productivity obtains the advantage of a large amount of products in a short period of time.
Accompanying drawing explanation
Fig. 1 is beta-diketon rare earth compounding red fluorescence material Eu of the present invention (BTA)
3(DFA) the single crystal structure figure of molecule;
Fig. 2 is according to the Eu in embodiment 1 (BTA)
3(DFA) the X-ray powder diffraction figure of luminescent material and monocrystalline simulated diffraction figure, X-coordinate represents diffraction angle scale, ordinate zou represents intensity scale.
Fig. 3 is rare earth luminescent material Eu (BTA)
3(DFA) Fourier infrared spectrum figure, X-coordinate represents wave number, ordinate zou represents transmitance.
Fig. 4 is rare earth luminescent material Eu (BTA)
3(DFA) UV, visible light absorbs collection of illustrative plates, and X-coordinate represents wavelength, and ordinate zou represents absorbancy.
Fig. 5 is rare earth luminescent material Eu (BTA)
3(DFA) excitation spectrum, supervisory wavelength is 610nm, and X-coordinate is wavelength, and ordinate zou is intensity.
Fig. 6 is rare earth luminescent material Eu (BTA)
3(DFA) emmission spectrum, excitation wavelength is 370nm, and X-coordinate is wavelength, and ordinate zou is intensity.
Fig. 7 is rare earth luminescent material Eu (BTA)
3(DFA) thermal analysis curve, X-coordinate represents temperature, ordinate zou represents respectively weight percentage (left side) and hot-fluid (right side).
Embodiment
The present invention is a kind of beta-diketon rare earth compounding red fluorescence material and preparation method thereof, clear and definite title complex Eu (BTA)
3(DFA) molecular structure, and the thermostability of material and luminescent properties.Embodiment is as follows:
Embodiment 1
Rare earth compounding polycrystal powder Eu (BTA)
3(DFA) preparation:
A. take the Eu (NO of 1mmol
3)
36H
2o and 3mmol benzoyltrifluoroacetone, add 15ml acetonitrile to dissolve, and dropwise add the sodium hydroxide solution of 6ml0.5mol/L, fully stirs, and obtains settled solution 1;
B. take 1mmol4,5-diaza fluorenes, adds 7ml acetonitrile to dissolve, and obtains colorless cleared solution 2;
D. by solution 3 through reduction vaporization, washing, dry, obtain Powdered rare-earth complexes luminous material Eu (BTA)
3(DFA), productive rate 83%.
To rare earth compounding Eu (BTA)
3(DFA) pure phase powder carries out a series of performance test.To rare earth Eu of the present invention
3+luminescent material polycrystal powder has carried out steady-state fluorescence test, and result shows that this material, under different excitation wavelength effects, can launch strong ruddiness, and chromaticity coordinates value is (0.6612,0.3367).Thermogravimetric analysis test shows that this material has good thermostability, and its initial decomposition temperature reaches 240 degrees Celsius, sees shown in accompanying drawing 7.
Rare earth compounding Eu (BTA)
3(DFA) acquisition of monocrystalline and sign:
The rare earth compounding Eu (BTA) taking a morsel
3(DFA) solid product, dissolves with acetonitrile, obtains saturated solution A, adds successively deionized water, deionized water and acetonitrile damping fluid, solution A in test tube.Treat standing a couple of days, obtain water white transparency bulk crystals, select single crystal that a size is 0.32x0.23x0.20mm for X ray single crystal diffraction, resolve and obtain Eu (BTA)
3(DFA) molecular structure.The molecular structure of this compound is illustrated in accompanying drawing 1.
Claims (3)
1. a beta-diketon rare earth compounding red fluorescence material, is characterized in that: the structural formula of described rare earth compounding is Eu (BTA)
3(DFA), the BTA in formula is beta-diketonate ligand benzoyltrifluoroacetone, and DFA is neutral assistant ligand 4,5-diaza fluorenes, and its molecular structure is suc as formula (I):
Described beta-diketon rare earth compounding red fluorescence material belongs to triclinic(crystalline)system, P-1 (NO.2) spacer, and unit cell parameters a=9.9416 (5), b=14.3928 (9),
α=80.406 (5), β=87.925 (4), γ=75.887 (5) °,
z=2, D
c=1.612g/cm
3, single crystal is that water white transparency is block; Title complex is by six Sauerstoffatoms of a rare earth ion and three benzoyltrifluoroacetone parts and one 4, and two nitrogen-atoms of 5-diaza fluorenes part form eight-coordinate structures.Rare earth ion is positioned at the center of coordination polyhedron, by part chromophoric group, absorb UV-light, then, by intramolecular energy transfer excitation center rare earth ion, the feature that realizes rare earth ion is luminous, rigidity phenyl ring and the aromatic heterocycle on part simultaneously, has strengthened rigidity and the stability of agent structure.
2. the preparation method of beta-diketon rare earth compounding red fluorescence material according to claim 1, the method comprises the following steps:
(1) under room temperature, europium nitrate and benzoyltrifluoroacetone are dissolved in acetonitrile completely, both mol ratios are 1: 3, are fully uniformly mixed, and obtain colorless cleared solution A;
(2) under room temperature, in A solution, dropwise add sodium hydroxide solution, fully stir simultaneously, finally making the mol ratio of sodium hydroxide and benzoyltrifluoroacetone is 1: 1, obtains colorless cleared solution B;
(3) under room temperature, 4,5-diaza fluorenes is dissolved in acetonitrile completely, wherein 4, the mol ratio of 5-diaza fluorenes and europium nitrate is 1: 1, fully, after stirring and dissolving, obtains light settled solution C;
(4) under room temperature, C solution is dropwise added in B solution, stirs simultaneously and make it sufficient reacting, obtain settled solution, then, by gained solution rotary evaporation under reduced pressure, obtain white, crystalline, powder, through water washing and be drying to obtain rare-earth complexes luminous material product.
3. the application of beta-diketon rare earth compounding red fluorescence material according to claim 1, is characterized in that thermostability and luminescent properties that described luminescent material has had; Material be take the 610nm ruddiness strong as maximum emission peak sends, and is applied to red photoluminescent material, or as the luminescent layer luminescent material in multilayer electroluminescent device.
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| CN113336779A (en) * | 2021-06-04 | 2021-09-03 | 中国计量大学 | Rare earth luminescent material, preparation method thereof and fluorescent sensing application |
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| CN102503965A (en) * | 2010-12-31 | 2012-06-20 | 南京大学 | Rare earth complex with light conversion function and preparation method thereof |
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2013
- 2013-12-31 CN CN201310755651.7A patent/CN103694993B/en not_active Expired - Fee Related
Patent Citations (6)
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| EP0446846A2 (en) * | 1990-03-13 | 1991-09-18 | Eastman Kodak Company | Thermally-transferable fluorescent europium complexes |
| EP1496097A1 (en) * | 2003-07-11 | 2005-01-12 | Orient Chemical Industries, Ltd. | Luminous organic compound and manufacturing method |
| JP2005111704A (en) * | 2003-10-03 | 2005-04-28 | Dainippon Ink & Chem Inc | Identification mark, its judging method and system and label and transfer foil for forming it |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113336779A (en) * | 2021-06-04 | 2021-09-03 | 中国计量大学 | Rare earth luminescent material, preparation method thereof and fluorescent sensing application |
| CN113336779B (en) * | 2021-06-04 | 2022-06-28 | 中国计量大学 | Rare earth luminescent material, preparation method thereof and fluorescent sensing application |
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