CN104130771B - A kind of three core Rare Earth Europium Complex luminescent materials and its preparation method and application - Google Patents
A kind of three core Rare Earth Europium Complex luminescent materials and its preparation method and application Download PDFInfo
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- CN104130771B CN104130771B CN201410316865.9A CN201410316865A CN104130771B CN 104130771 B CN104130771 B CN 104130771B CN 201410316865 A CN201410316865 A CN 201410316865A CN 104130771 B CN104130771 B CN 104130771B
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Abstract
Three core Rare Earth Europium Complex luminescent materials provided by the invention and its preparation method and application, the luminescent material that described three core Rare Earth Europium Complexes are a kind of Heat stability is goods, luminous efficiency is high, by complex Eu in early stage (beta-diketon)3.2H2O and the reaction of three arm terpyridyl derivatives (tristpy) obtain after distilled water and ethanol washing vacuum drying; For milk yellow pressed powder, its simple synthetic method is easily gone, production cost is low. Flat panel display device for development superior performance of future generation is significant. The solubility property of this three core Rare Earth Europium Complex complex is good, luminous efficiency is high, heat endurance might as well, can be used as the potential material in luminescence generated by light or electroluminescent field.
Description
Technical field
The present invention relates to rare earth luminescent material field, particularly a kind of three arm terpyridyl (tristpy) conductsThree core Rare Earth Europium Complex luminescent materials and preparation and the application of neutral ligand.
Background technology
Rare earth luminescent material has that emission band is sharp-pointed, half-peak width (being generally less than 10nm), interior quantum effectThe series of advantages such as rate is high, fluorescence lifetime is long and heat resistance is superior is luminous organic material field alwaysStudy hotspot. China has abundant rare earth resources, and A wide selection of colours and designs, this application that is rare earth luminescent materialGood guarantee is provided. At present, the research and development of rare earth luminescent material has covered whole luminous field,And having formed certain commercial production scale and market, rare earth luminescent material has become the master of current luminescent materialLead. Therefore, the rare-earth products of active development high-tech content, is converted into science and technology by the rare earth resources advantage of ChinaCompetitive advantage, for the industrial transformation and the upgrading that promote China, and lifting international competitiveness all has important meaningJustice.
Material is one of three large pillars of society development in science and technology, and luminescent material is a kind of important merit whereinCan material. The transition of the energy level that rare earth ion is abundant and 4f layer electronics, becomes rare earth ion huge luminousTreasure-house. Design and synthesize the rare earth compounding with excellent luminescent properties is that various countries researchers pursue alwaysTarget, because the distinctive 4f layer of rare earth ion electronics is subject to outer 5S25P6The shielding action of layer electronics, makes rareSoil ion is subject to the impact of Ligand Field very little, so luminescence rare earth ion generally has narrow band fluorescent emission, colour puritySpend high, luminous strong, the advantage such as luminescent lifetime is long. But the absorptivity of rare earth ion is very little, need to be by means of" antenna effect " of part carried out the transmission of energy, and the feature that could effectively strengthen rare earth ion is luminous.
According to energy level matching principle, the part that rare earth ion is conventional is divided into two kinds of anion ligand and neutral ligands.Wherein anion ligand mainly comprises beta-diketon class part and carboxylic acids part; Neutral ligand mainly contain ferrosin,The heterocyclic ligands such as second bipyridine, triphenylphosphine oxide derivative. Numerous neutral ligands of finding report are mainly at presentPlay the requirement that meets rare-earth ion coordination number, the energy transfer function between part and rare earth ion is risenHave little effect. Luminous efficiency and the thermal stability of Rare Earth Europium Complex luminescent material are not high enough, and this remains systemApproximately it obtains the key issue of application at key areas such as organic electroluminescents.
Summary of the invention
For above shortcomings in prior art, the object of the invention is to solve prior art europium complex and send outThe problem that the luminous efficiency of luminescent material and thermal stability are not high enough, provides one to have high luminescent properties and Gao ReThree core Rare Earth Europium Complex luminescent material and application thereof of stability.
Another object of the present invention is to provide that a kind of production cost is low, the preparation of easy operating three core rare-earth europium coordinateThe method of thing luminescent material.
Realize goal of the invention, the present invention adopts following technical scheme: a kind of three core Rare Earth Europium Complex luminescent materials,The general structure of this three core Rare Earth Europium Complex luminescent material is as shown in (I):
Wherein, R be H or-CH3；R1For-CH3、-CF3, phenyl or naphthyl; R2For-CH3, thienyl,Phenyl or naphthyl.
The preparation method of above-mentioned three core Rare Earth Europium Complex luminescent materials, comprises the following steps:
1) be in molar ratio the europium complex Eu (beta-diketon) shown in the ratio modus ponens (II) of 1～10:13.2H2OMix with three arm terpyridyls (tristpy) shown in formula (III), add good solvent, stir, make dissolution of solid,Reactant is warming up to 40～90 DEG C, sustained response 3～12 hours.
2) by step 1) products therefrom is cooled to room temperature, removes precipitation, and solvent evaporated obtains solute, successivelyWith distilled water and ethanol washing solute, by little the solute vacuum drying 12～24 under 60 DEG C of conditions after washingTime, obtain three above-mentioned core Rare Earth Europium Complex luminescent materials.
Compared to existing technology, the present invention has following beneficial effect:
1, this three core Rare Earth Europium Complex luminescent material mostly is milk yellow powder, and this luminescent material molecule has threeArm configuration, by three identical europium complex unit Eu (beta-diketon)3(TPY) form each Eu (β-bis-Ketone)3(TPY) unit is by an Eu3+With six oxygen atoms from three beta-diketonate ligands and three from threeThe nitrogen-atoms of pyridine forms nine coordination structures, Eu3+Be positioned at coordination polyhedrom center, on part, contain rigidity phenyl ringAnd aromatic heterocycle, strengthen rigidity and the stability of agent structure, be also conducive to compound simultaneously by " antennaEffect " realize high efficiency luminous. Described luminescent material is under the ultraviolet excitation of certain wavelength, all with 613Nm is that maximum emission peak sends strong ruddiness, can be used as red photoluminescent material, or causes as multilayer electricityLuminescent layer material in luminescent device.
2,, in the present invention, neutral ligand tristpy can while and three Eu3+Coordination, so just makes sameThe centre of luminescence in light emitting molecule is increased to 3 by 1 in conventional monokaryon europium complex, joins thereby improvedBody is to the energy transfer efficiency of rare-earth europium central ion, therefore the present invention's three core Rare Earth Europium Complexes and conventional listCore Rare Earth Europium Complex is compared, and luminescent properties is more superior. Therefore the present invention's three core Rare Earth Europium Complex luminescent materialsHave that good stability, dissolubility are good, good film-forming property, long service life and luminous efficiency high, favourableBe prepared into large-area display device in processing, application prospect is very wide; Particularly can be used as luminescence generated by light orThe potential material in electroluminescent field.
3, the present invention prepares three core Rare Earth Europium Complex luminescent material methods, step 1) in three arm terpyridyls(tristpy) contain three terpyridyl unit, can carry out coordination with three rare-earth europium ions simultaneously. NeutralPart tristpy has very strong coordination ability, under room temperature, can carry out effective coordination with rare-earth europium ion. TristpyEnergy level and europium ion5D0Energy level matches, and therefore tristpy part can pass the energy absorbing effectivelyPass europium ion, thereby improved the luminous efficiency of this three core Rare Earth Europium Complex material. In addition, rare earth ionOrganically combine with stable armaticity part tristpy, make the heat endurance of this three core Rare Earth Europium Complex greatlyImprove.
The present invention is under solution reaction condition, by complex Eu in early stage (beta-diketon)3.2H2O and three arm terpyridylsDerivative (tristpy) reaction preparation. Therefore, the present invention has simple, and the feature that manufacturing cost is low is rightFlat panel display device in development superior performance of future generation is significant.
Brief description of the drawings
Fig. 1 is infrared spectrogram (the KBr pressure of three core Rare Earth Europium Complexes of the embodiment of the present invention 1 gainedSheet).
Fig. 2 is the uv absorption spectra of three core Rare Earth Europium Complexes of the embodiment of the present invention 1 gained.
Fig. 3 is the fluorescent exciting spectrogram (transmitted wave of three core Rare Earth Europium Complexes of the embodiment of the present invention 1 gainedLong: 613nm, slit 5nm, solid state powder).
Fig. 4 is the fluorescence emission spectrogram (excitation wave of three core Rare Earth Europium Complexes of the embodiment of the present invention 1 gainedLong: 368nm, slit 5nm, solid state powder).
Fig. 5 is the thermogravimetric curve (N of three core Rare Earth Europium Complexes of the embodiment of the present invention 1 gained2Protection, rises15 DEG C/min of temperature speed).
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present inventionBe not limited to this.
Embodiment 1:
1) get material tristpy shown in the europium complex shown in the formula (IV) of 0.3mmol and 0.1mmol formula (V)Be placed in a 100ml there-necked flask with magneton stirring and reflux, then add 60ml oxolane(THF), the concentration 1 × 10 of THF solution-5Mol/L, stirs and allows dissolution of solid, and now solution is light yellow,Be warming up to 70 DEG C, reflux 6 hours.
2) by step 1) products therefrom is cooled to room temperature, removes precipitation, and evaporate to dryness THF obtains solute, thenSuccessively with distilled water and ethanol washing solute, by little the solute vacuum drying 24 under 60 DEG C of conditions after washingTime, obtain three core Rare Earth Europium Complex Eu shown in formula (VI)3(TTA)9(tristpy), milk yellow pressed powder,Productive rate 97%.
Three prepared core Rare Earth Europium Complexes are soluble in common organic solvent, as acetone, oxolane, trichlorineMethane or DMF etc., hence one can see that, and this complex has good filming performance.
This three core Rare Earth Europium Complex infrared spectrogram as shown in Figure 1, has occurred that one is joined near being positioned at 581nmThe new vibration peak not having in body tristpy, this belongs to the stretching vibration peak of N → Eu in three core europium complexes,Show part tritpy and europium ion success coordination. Uv absorption spectra as shown in Figure 2, as shown in Figure 2 shouldThree core europium complexes, 250～400nm region in ultra-violet absorption spectrum has very strong extinction ability. Fluorescence swashsAs shown in Figure 3, in 200～450nm region, three core europium complex excitation peak intensity are higher for luminous spectrogram, in addition,In excitation spectrum, do not see obvious europium ion characteristic emission peak, this shows that part tristpy is to the centre of luminescenceAbility transmission between europium ion is very effective.
Fluorescence emission spectrogram as shown in Figure 4. As can be seen from Figure 4, this three core Rare Earth Europium Complex performanceFor pure red emission, its half-peak breadth is about 10nm, and in fluorescence radiation spectrum (PL) without partEmission peak appearance, this shows that be completely by organic ligand to the energy transmission centre of luminescence europium ion. HeatWeight-loss curve as shown in Figure 5, as can be seen from Figure 5, the corresponding temperature of the mass loss of this complex 5%Degree is 206 DEG C, has good heat resistance.
As can be seen from the above results, this trinuclear complex has good solubility property, and filming performance is photicLuminescent properties and thermal stability are to prepare the required potential luminescent material of large-area displays device.
Embodiment 2:
1) get material tristpy shown in the europium complex shown in the formula (VII) of 0.3mmol and 0.1mmol formula (V)Be placed in a 100ml there-necked flask with magneton stirring and reflux, then add 60ml oxolane(THF), stir and allow dissolution of solid, now solution is light yellow, is warming up to 70 DEG C, refluxes 4 hours;
2) by step 1) products therefrom is cooled to room temperature, removes precipitation, and rotary evaporation is removed THF and is obtained moltenMatter, then successively with distilled water and ethanol washing solute, by dry the vacuum under 60 DEG C of conditions of the solute after washingDry 12 hours, obtain three core Rare Earth Europium Complex Eu shown in formula (VIII)3(DBM)9(tristpy), light yellowPressed powder, productive rate 91%.
Three prepared core Rare Earth Europium Complexes are soluble in common organic solvent, as chloroform, carrene,Acetone, oxolane or DMF etc., hence one can see that, and this three core Rare Earth Europium Complex has good film formingEnergy.
Finally explanation, above embodiment is only unrestricted in order to technical scheme of the present invention to be described, although ginsengAccording to preferred embodiment, the present invention is had been described in detail, those of ordinary skill in the art should be appreciated that passableTechnical scheme of the present invention is modified or is equal to replacement, and do not depart from technical solution of the present invention aim andScope, it all should be encompassed in the middle of claim scope of the present invention.
Claims (2)
1. a preparation method for three core Rare Earth Europium Complex luminescent materials, is characterized in that, comprises the following steps:
1) in molar ratio for the ratio of 3:1 is got europium complex Eu (beta-diketon)3.2H2O mixes with three arm terpyridyls, addsGood solvent, stirs, and makes dissolution of solid, reactant is warming up to 40～90 DEG C, sustained response 3～12 hours;
2) by step 1) products therefrom is cooled to room temperature, removes precipitation, and solvent evaporated obtains solute; Use successively distilled water andEthanol washing solute, by the solute after washing, under 40～90 DEG C of conditions, vacuum drying 12～24 hours, is tied as followsThree core Rare Earth Europium Complex luminescent materials of structure general formula;
Described europium complex Eu (beta-diketon)3.2H2O has following general structure:
Described three arm terpyridyls have following general structure:
Wherein, R be H or-CH3；R1For-CH3、-CF3, phenyl or naphthyl; R2For-CH3, thienyl, phenyl or naphthaleneBase; Described good solvent is oxolane, acetone, DMF, carrene or chloroform.
2. the preparation method of three core Rare Earth Europium Complex luminescent materials as claimed in claim 1, is characterized in that described step1 temperature is preferably 70 DEG C.
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| CN105086996B (en) * | 2015-08-26 | 2018-05-15 | 重庆理工大学 | A kind of tripolyphosphazene crosslinking rare-earth complexes luminous material and preparation method thereof |
| CN106432341B (en) * | 2016-09-12 | 2018-05-15 | 重庆理工大学 | Hyperbranched tripolyphosphazene terpyridyl and preparation and the recognition methods to metal ion |
| CN109438941B (en) * | 2018-10-31 | 2021-01-26 | 重庆理工大学 | Preparation method and application of biodegradable rare earth fluorescent film |
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| CN110551292A (en) * | 2019-09-18 | 2019-12-10 | 贵州师范大学 | preparation method of rare earth luminescent material with adjustable light color |
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| CN111606934A (en) * | 2020-06-06 | 2020-09-01 | 桂林理工大学 | Preparation, structure and fluorescence application of bteb bridged binuclear europium complex |
| CN113896904B (en) * | 2021-11-16 | 2023-03-24 | 曲阜师范大学 | Quaternary supermolecule anti-counterfeiting system of cucurbituril [8] -diarylethene derivative-terpyridyl imidazole-europium and preparation method thereof |
| CN115466404B (en) * | 2022-09-16 | 2023-07-07 | 贵州师范大学 | Preparation and application of homonuclear rare earth coordination polymer white light material |
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