CN102503967B - One class single-substrate white rare earth compound and Synthesis and application thereof - Google Patents
One class single-substrate white rare earth compound and Synthesis and application thereof Download PDFInfo
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- CN102503967B CN102503967B CN201110348288.8A CN201110348288A CN102503967B CN 102503967 B CN102503967 B CN 102503967B CN 201110348288 A CN201110348288 A CN 201110348288A CN 102503967 B CN102503967 B CN 102503967B
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Abstract
The present invention relates to class single-substrate white rare earth compound and a Synthesis and application thereof, [Ln
2(3-tzba)
2(3-Htzba)
4(H
2o)
8] 4H
2o and Synthesis and application thereof, wherein, Ln=Sm, Dy; 3-H
2tzba=3-(5-tetrazole)-phenylformic acid, is 3-tzba after complete dehydrogenation
2 –.Two kinds of compounds are all adopt hydro-thermal reaction to be prepared.Under the UV-irradiation of different wave length, two kinds of compounds such as to send from redness to mazarine, from yellow to blueness respectively at the fluorescence of serial different wave length.Under the UV-irradiation of suitable wavelength, two kinds of compounds all can launch the fluorescence close to pure white (Sm metallic compound) or pure white (Dy metallic compound).This compounds has that synthesis is simple, non-impurity-doped, single component, directly emit white light, the luminous feature such as adjustable, can be applicable to the coating of various object, distinctive mark and the field such as luminescence display and LED illumination.
Description
Technical field
The present invention relates to a class single-substrate white rare earth compound [Ln
2(3-tzba)
2(3-Htzba)
2(H
2o)
8] 4H
2the Synthesis and application of O, wherein Ln=Sm, Dy; 3-H
2tzba=3-(5-tetrazole)-phenylformic acid, is 3-tzba after complete dehydrogenation
2 –.
Background technology
Green illumination is an importance of the Implement of sustainable development strategy, formally listed China's state plan in 1996, its most basic requirement is high-quality lamp source, and the light namely sent is panchromatic light, so-called panchromatic light, namely spectrum continuous distribution is in human visible range.Have the plurality of advantages such as energy saving standard due to green illumination, white light LEDs is just paid close attention to day by day widely in the application in display and lighting field.The problem such as the high and device of color balance difference, cost is complicated that utilizes many components fluorescent material or multi-colored led assembling white light LEDs often to there will be.For avoiding these problems, single-matrix white luminescent material has become a current study hotspot, and about the report of single-matrix white luminescent material also considerably less.On purpose design and synthesis single-matrix white luminescent material is still a sciences problems.
Rare earth metal can send stronger fluorescence, and its fluorescence shows the advantages such as very narrow line spectrum, very wide wavelength (covering from ultraviolet to infrared band), longer fluorescence lifetime, thus can be developed into as light power and energy and fluorescent material.Such as can be used for making light power and energy device and coating etc., and also play a significant role in photodiode, trace analysis, anti-fake material, bioprobe and molecular recognition etc.But because the transition of rare earth metal f – f configuration is that spectrum selects rate to prohibit, it will be caused luminous by direct excitation rare-earth metal, be almost impossible.For this reason, suitable chromophoric group must be found, it can have stronger receptivity, and the energy efficient absorbed can be passed to the excited state of rare earth metal and cause luminescence, this the transmission ofenergy of chromophore absorption to rare earth metal, the phenomenon that rare earth metal illumination effect is strengthened, is called " antenna effect ", this chromophoric group is called sensitizing agent.We select 3-(5-tetrazole)-phenylformic acid (H
2tzba, is tzba after dehydrogenation
2 –), because of himself characteristic likely as the sensitizing agent of fluorescence radiation: (1) exists electron-conjugated system and strong π – π * absorption jump, show abundant electrodes transfer behaviour, itself can launch stronger fluorescence, has good application prospect at Material Fields such as luminescence, magnetic and semi-conductors; (2) triplet energies is suitable, close to or the energy of first excited state a little more than many rare earth metals.Therefore, with the optical excitation of suitable wavelength, it can show as self luminescence or as fluorescence radiation sensitizing agent, induces rare earth metal excited state and cause luminescence, realizing the adjustability of material emission, the single-matrix white luminescent material of preparation high-quality.
Summary of the invention:
Object of the present invention selects 3-(5-tetrazole)-phenylformic acid to prepare single-substrate white rare earth compound as the sensitizing agent of fluorescence radiation with regard to being, its technical scheme is as follows:
The technical solution used in the present invention is as follows:
1. a class single-substrate white rare earth compound, is characterized in that: this compound is [Ln
2(3-tzba)
2(3-Htzba)
2(H
2o)
8] 4H
2o, molecular formula is C
32h
42n
16o
20ln
2, wherein Ln=Sm or Dy, 3-tzba are that 3-(5-tetrazole)-phenylformic acid after deprotonation bears divalent ion; As Ln=Sm, the cell parameter of compound crystal is: spacer is P – 1,
a=117.12 (2) °, b=98.12 (4) °, g=99.36 (3) °, Z=1, unit-cell volume
as Ln=Dy, the cell parameter of compound crystal is spacer is P – 1,
a=117.229 (9) °, b=98.13 (2) °, g=99.496 (15) °, Z=1, unit-cell volume
2. a preparation method for the single-substrate white rare earth compound of item 1, is characterized in that: employing reaction in－situ, Hydrothermal Synthesis two-step reaction are prepared.
3. the preparation method of the single-substrate white rare earth compound as described in item 2, it is characterized in that, reaction in－situ is wherein: the mol ratio of raw material 3-cyanobenzoic acid sodium, sodium azide and zinc chloride is 1:1 ~ 2:1 ~ 2, and adopt water as solvent, hydro-thermal reaction is warming up to 120 ~ 150 DEG C; Constant temperature 3 days, after be down to room temperature and obtain leucocompound crystal [Zn (3-tzba)]
n.
4. the preparation method of the single-substrate white rare earth compound as described in item 2, is characterized in that, Hydrothermal Synthesis is wherein: use 1molL
– 1dissolve with hydrochloric acid solution [Zn (3-tzba)]
nclear crystal, obtains white precipitate after filtration, is 3-H
2tzba part; Mixing LnCl
3nH
2o, Ln=Sm or Dy, raw material and 3-H
2tzba part, mol ratio is 1:1 ~ 2, adds a small amount of 2,2 '-dipyridyl, adopt water as solvent, stirring at normal temperature 0.5 ~ 1 hour, hydro-thermal reaction is warming up to 150 ~ 170 DEG C, constant temperature 2 ~ 4 days, after be down to room temperature.
5. a purposes for the single-substrate white rare earth compound of item 1, is characterized in that wherein [Ln
2(3-tzba)
2(3-Htzba)
2(H
2o)
8] 4H
2o, Ln=Sm, under the UV-irradiation of different wave length, the fluorescence of a series of different wave length from redness to mazarine can be sent, launch close to lily fluorescence when irradiating with about 315nm incident light, can use as single-substrate white LED illumination, also can be applicable to the fields such as the coating of various object, distinctive mark and luminescence display.
6. a purposes for the single-substrate white rare earth compound of item 1, is characterized in that: [Ln
2(3-tzba)
2(3-Htzba)
2(H
2o)
8] 4H
2o, Ln=Dy, under the UV-irradiation of different wave length, the fluorescence of a series of different wave length from yellow to blueness can be sent, lily fluorescence is launched when irradiating with about 315nm incident light, can use as single-substrate white LED illumination, also can be applicable to the fields such as the coating of various object, distinctive mark and luminescence display.
We select 3-cyanobenzoic acid sodium, sodium azide and zinc chloride to be raw material, and mol ratio is 1:2:2, adopt water as solvent, and Situ Hydrothermal reaction is warming up to 140 DEG C, constant temperature 3 days, after be down to room temperature and obtain clear crystal [Zn (3-tzba)]
n; Use 1molL
– 1dissolve with hydrochloric acid solution crystal, solution occurs muddy, obtains white precipitate after filtration, is 3-H
2tzba part; By LnCl
3nH
2o (Ln=Sm, Dy) and 3-H
2tzba part mixes, and mol ratio is 1:1, adds a small amount of 2,2 '-dipyridyl, and adopt water as solvent, stirring at normal temperature 0.5 hour, hydro-thermal reaction is warming up to 170 DEG C, constant temperature 3 days, after be down to room temperature and obtain bulk-shaped monocrystal.
We record two the heterogeneous tetrazole of the isomorphous-5-(3-phenylformic acid) rare earth compound [Ln
2(3-tzba)
2(3-Htzba)
2(H
2o)
8] 4H
2the crystalline structure of O (Ln=Sm, Dy), overall structure can be described as passes through 3-tzba
2 –carboxyl bridging two Ln (III) ions of part form double-core isolated structures, and Ln (III) ion has the coordination environment of eight-coordinate.Their structural parameter are as follows: [Sm
2(3-tzba)
4(OH)
2(H
2o)
6] 4H
2o: spacer is P – 1, and cell parameter is
a=117.12 (2) °, b=98.12 (4) °, g=99.36 (3) °, Z=1, unit-cell volume
[Dy
2(3-tzba)
4(OH)
2(H
2o)
6] 4H
2o: spacer is P – 1, and cell parameter is
a=117.229 (9) °, b=98.13 (2) °, g=99.496 (15) °, Z=1, unit-cell volume
The single-substrate white rare earth compound that two kinds of luminescences provided by the invention are adjustable, the light that the serial different wave length such as can to realize from redness to mazarine, from yellow to blueness changes.This compounds has that synthesis is simple, non-impurity-doped, single component, directly emit white light, the luminous feature such as adjustable, can be applicable to the coating of various object, distinctive mark and the field such as luminescence display and LED illumination.
Accompanying drawing explanation
Fig. 1 is for implementing [Sm
2(3-tzba)
2(3-Htzba)
2(H
2o)
8] 4H
2the room temperature fluorescence spectrogram of O compound.
Fig. 2 is for implementing [Dy
2(3-tzba)
2(3-Htzba)
2(H
2o)
8] 4H
2the room temperature fluorescence spectrogram of O compound.
Embodiment
1, the preparation of compound
Take tricyano Sodium Benzoate (0.5mol), sodium azide (1mol) and zinc chloride (1mol), add 8mL water as solvent, load in the tetrafluoroethylene reactor of the 25mL of sealing, be warming up to 140 DEG C, constant temperature 3 days, after be down to room temperature, clear crystal [Zn (3-tzba)] can be obtained
n; Use 1molL
– 1dissolve with hydrochloric acid solution crystal, solution occurs muddy, obtains white precipitate after filtration, is 3-H
2tzba part; Take LnCl
3nH
2o (Ln=Sm, Dy) (0.4mol), 3-H
2tzba powder (0.4mol) and 2,2 '-dipyridyl (about 0.5mol) mixes, and add 8 ~ 10mL water as solvent, stirring at normal temperature 0.5 hour, hydro-thermal reaction is warming up to 170 DEG C, constant temperature 3 days, after be down to room temperature and obtain bulk-shaped monocrystal.Analyze through X-ray single crystal diffraction, determine that this crystal is [Ln
2(3-tzba)
2(3-Htzba)
2(H
2o)
8] 4H
2o.
2, fluorometric investigation
The grinding of the crystal of preparation is evenly obtained pressed powder, and EdinburghF920 fluorescence spectrophotometer is carried out luminescence can test, and result shows: for [Sm
2(3-tzba)
2(3-Htzba)
2(H
2o)
8] 4H
2, when excitation wavelength is 305nm, there is sharp-pointed fluorescence peak in 597 and 643nm position, send stronger red fluorescence in O compound; When excitation wavelength increases gradually, 597 and the fluorescence peak of 643nm position start to weaken, there is relatively wide fluorescence peak near 425nm and strengthen gradually; When wavelength increases to 350nm, compound fluorescence peak mainly, near about 425nm, launches blue-fluorescence.Wherein, when excitation wavelength increases to about 315nm, compound is launched close to lily fluorescence.
Identical test condition, for [Dy
2(3-tzba)
2(3-Htzba)
2(H
2o)
8] 4H
2o compound, excitation wavelength increases to 345nm by 304nm, and compound is launched the yellow fluorescence to blue a series of different colours.Wherein, when excitation wavelength is about 315nm, compound launches lily fluorescence.
Claims (4)
1. a class single-substrate white rare earth compound, is characterized in that: this compound is [Ln
2(3-tzba)
2(3-Htzba)
2(H
2o)
8] 4H
2o, molecular formula is C
32h
42n
16o
20ln
2, wherein Ln=Sm or Dy, 3-tzba are that 3-(5-tetrazole)-phenylformic acid after deprotonation bears divalent ion; As Ln=Sm, the cell parameter of compound crystal is: spacer is P – 1,
α=117.12 (2) °, β=98.12 (4) °, γ=99.36 (3) °, Z=1, unit-cell volume
as Ln=Dy, the cell parameter of compound crystal is: spacer is P – 1,
α=117.229 (9) °, β=98.13 (2) °, γ=99.496 (15) °, Z=1, unit-cell volume
2. a preparation method for the single-substrate white rare earth compound of claim 1, is characterized in that: employing reaction in－situ, Hydrothermal Synthesis two-step reaction are prepared.
3. a purposes for the single-substrate white rare earth compound of claim 1, is characterized in that wherein [Ln
2(3-tzba)
2(3-Htzba)
2(H
2o)
8] 4H
2o, Ln=Sm, under the UV-irradiation of different wave length, can send the fluorescence of a series of different wave length from redness to mazarine, can use, also can be applicable to the coating of various object, distinctive mark and luminescence display field as single-substrate white LED illumination.
4. a purposes for the single-substrate white rare earth compound of claim 1, is characterized in that: [Ln
2(3-tzba)
2(3-Htzba)
2(H
2o)
8] 4H
2o, Ln=Dy, under the UV-irradiation of different wave length, can send the fluorescence of a series of different wave length from yellow to blueness, can use, also can be applicable to the coating of various object, distinctive mark and luminescence display field as single-substrate white LED illumination.
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| CN201110030396.0 | 2011-01-28 | ||
| CN2011100303960 | 2011-01-28 | ||
| CN201110348288.8A CN102503967B (en) | 2011-01-28 | 2011-11-07 | One class single-substrate white rare earth compound and Synthesis and application thereof |
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| CN102503967B true CN102503967B (en) | 2016-03-02 |
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| CN101560383A (en) * | 2008-04-18 | 2009-10-21 | 中国科学院福建物质结构研究所 | Synthesis and application of blue luminescent organometallic composition |
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2011
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| CN101560383A (en) * | 2008-04-18 | 2009-10-21 | 中国科学院福建物质结构研究所 | Synthesis and application of blue luminescent organometallic composition |
| CN101560218A (en) * | 2008-04-18 | 2009-10-21 | 中国科学院福建物质结构研究所 | Organometallic complex of nonlinear optical and ferroelectric material, synthesis and application thereof |
| CN101993691A (en) * | 2009-08-25 | 2011-03-30 | 中国科学院福建物质结构研究所 | Metal coordination polymer fluorescence luminescent material and synthesis and application thereof |
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| "Zinc(II) and Cadmium(II) Coordination Polymers Based on 3-(5H-Tetrazolyl)benzoate Ligand with Different Coordination Modes:Hydrothermal Syntheses, Crystal Structures and Ligand-Centered Luminescence";Feng Chen et al.;《European Journal of Inorganic Chemistry》;20100921;第2010卷(第31期);第4982-4990页 * |
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