CN102127427B - Blue-light-emitting fluorescent material and preparation method thereof - Google Patents
Blue-light-emitting fluorescent material and preparation method thereof Download PDFInfo
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- CN102127427B CN102127427B CN201110004478.8A CN201110004478A CN102127427B CN 102127427 B CN102127427 B CN 102127427B CN 201110004478 A CN201110004478 A CN 201110004478A CN 102127427 B CN102127427 B CN 102127427B
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- fluorescent material
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- phenanthroline
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- oxygen
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Abstract
The invention discloses a blue-light-emitting fluorescent material and a preparation method thereof. The invention is characterized in that the fluorescent material is a cadmium compound of orotic acid, which is prepared by carrying out chemical reaction on orotic acid with carboxylic acid, phenanthroline and cadmium ions with optical activity; the molecular formula of the fluorescent material is C44H52N12O28Cd2, the crystal system is triclinic, and the space group is P-1; and the cell parameters are as follows: a=9.5220 Angstroms, b=11.8790 Angstroms, c=12.6141 Angstroms, alpha=73.082 degrees, gamma=78.073 degrees, and beta=81.100 degrees. The cadmium ions are in a pentagonal bipyramidal coordination mode, two nitrogen coordinating atoms are from the phenanthroline, three oxygen coordinating atoms are from orotic acid, and two oxygen coordinating atoms are from water. The fluorescent material has the advantages of accurate space structure and accurate molecular formula, and contains abundant Cd(II) ions with optical activity and carboxylic acid with strong coordinating capacity, thereby being beneficial to electron transition and energy transmission. The fluorescent material has favorable photoelectric activity and favorable blue light emission performance.
Description
Technical field
The present invention relates to a kind of fluorescent material, especially relate to a kind of fluorescent material with blue luminescent properties and preparation method thereof.
Background technology
Fluorescent material typically refers to be accepted after outside energy, energy absorption can be stored, and in dark place, is converted into luminous energy.It was come out the earliest in 1938.The people such as early stage Stokes have synthesized the fluorescent material such as calcium wolframate and for luminescent lamp.Within 1948, developed phosphate phosphor, the early stage fluorescent material of this light-emitting phosphor Performance Ratio has had remarkable improvement.60～seventies of 20th century fluorescent material be widely applied.The organic ligand that has optically active metal ion or contain conjugation primitive is incorporated in fluorescent material, can greatly improves the luminescent properties of fluorescent material.Have compared with the compound of hyperfluorescenceZeng Yongminggaoyingguang luminous power and have very important potential using value, can develop as new function material, as luminous fuel, laser fuel, sensitizing fuel, fluorescent probe etc.
Along with deepening continuously that fluorescent material is studied, people have developed three primary colours indigo plant, red, green fluorescence powder.Compared with red, green fluorescence emissive material, the development of organic blue electroluminescent material is a weak link, also more rare, at luminous efficiency, stability, moulding property, also has some problems.At present, can adopt fluorochrome doping to realize blue emission, but the general stability of fluorochrome is not high enough, film-forming properties is poor, does not mate, is easily separated with matrix energy level.According to the retrieval, have at present about various blue fluorescent materials and preparation method thereof, mainly contain the following: as U.S. Pat 4128498 discloses Chlorosilicate phosphor powder, its chemical formula is Sr
4-x-ybe
xsi
3o
8cl
4: yEu
2+, this fluorescent material can effectively be excited and launch bluish-green utilizing emitted light by ultraviolet ray, vacuum ultraviolet ray and negative ray.The compound that has used the virose Be of tool in the preparation process of this fluorescent material, is unfavorable for environmental protection and health.Chinese patent CN1408811A discloses a kind of chromatic plasma plane and has shown by aluminoborate blue fluorescent powder and manufacture method thereof, but this fluorescent material only has absorption more by force in shortwave ultraviolet region, and a little less than the absorption of long wave ultraviolet region.Chinese patent CN1415695A discloses a kind of preparation method of blue aluminate fluorescent powder of vacuum ultraviolet ray activation, and this aluminate fluorescent powder stability is bad, and the ultraviolet region of its maximum excitation peak in shortwave.Chinese patent CN119011A discloses blue colour fluorescent powder BaMgAl
14o
23: Eu is also aluminate substrate, and stability is not so good, and maximum excitation peak is also in vacuum ultraviolet.Chinese patent CN1128785A discloses blue fluorescent powder for fluorescent lamp with three primary colors, and its chemical constitution is europkium-activated calcium chlorophosphate strontium barium, very weak owing to absorbing in long wave ultraviolet region, is not suitable as equally ultraviolet and activates photic colour developing fluorescent material.
Recent study finds to have d
10metal complexes has received people's very big concern and by a large amount of synthetic and research, has also become one of forward position study hotspot of coordination chemistry simultaneously owing to having novel structure and optical activity.Carboxylic-acid part receives much attention in ligand polymer is constructed always, and such ligand moiety is taken off proton, makes part show various coordination mode flexibly, obtains the compound of different structure.Therefore in blue organic luminous material, utilize d preparing
10the metal ion of metal complexes and designing and to synthesize efficient blue organic luminous material very challenging containing the adjustability of Carboxylic acid ligand.
Vitamin B13 has asymmetry, when forming title complex, vitamin B13 forms an electronegative part by the H taking off on carboxylic acid, thereby plays the effect of balancing charge, can be used as the good chelating ligand of metal ion, thereby regulate and control the space dimensionality of its coordinated network.
Summary of the invention
Primary technical problem to be solved by this invention is for prior art, and a kind of fluorescent material with blue luminescent properties and preparation method thereof is provided.
The present invention solves the problems of the technologies described above the technical scheme of taking to be: a kind of fluorescent material with blue luminescent properties, this fluorescent material is a kind of vitamin B13 cadmic compound with certain space structure, its molecular formula is C44H52N12O28Cd2, crystallographic system is three oblique, spacer is P-1, unit cell parameters a=9.5220
b=11.8790
c=12.6141
α=73.082 °, γ=78.073 °, β=81.100 °, cadmium ion is pentagonal bipyramid coordination mode, and two nitrogen ligating atoms come from phenanthroline, and three oxygen ligating atoms come from vitamin B13, and two oxygen ligating atoms are from water.
The preparation method that this has the fluorescent material of blue luminescent properties, comprises the following steps:
1) vitamin B13, Cadmium Sulphate and 1,10-phenanthroline are added in container 5～7:6～8:2～4 in molar ratio, then according to the weight of all substances in container, add the ethanol of 5～10mL/g and the water of 10～30mL/g, stir it is mixed;
2) under the condition of stirring at room, dropwise add triethylamine, regulate pH value to 5～8, room temperature obtains colourless bulk crystals after placing 12～48h;
3) by the colourless bulk crystals distilled water flushing making, obtain vitamin B13 cadmic compound after natural air drying, its molecular formula is C
44h
52n
12o
28cd
2.
The material of more than participating in reaction is analytical pure.
Compared with prior art, the invention has the advantages that: by having vitamin B13 and the phenanthroline of stronger coordination ability and having optically active cadmium ion, carry out chemical reaction and make novel cadmium vitamin B13 compound, this compound has space structure (Fig. 1) and accurately molecular formula accurately as blue light emissive material; There is carboxylic acid drawing electron group, be conducive to intramolecular electric charge transfer, transition and transmission ofenergy, thereby make compound there is good photoelectric activity.Prepared material has good blue emission performance and film forming properties, as fluorescent material, has potential application prospect.Adopt method of the present invention can obtain 40%～80% productive rate.
Accompanying drawing explanation
Fig. 1 is the structural unit figure of cadmic compound of the present invention;
Fig. 2 is cadmic compound fluorescence emission spectrum of the present invention.
Embodiment
Below in conjunction with accompanying drawing, embodiment is described in further detail the present invention.
Embodiment 1:
In 50mL beaker, add vitamin B13 (0.5mmol, 0.85g), Cadmium Sulphate (0.6mmol, 0.462g), phenanthroline (0.2mmol, 0.04g), add 10mL ethanol and 20mL water, under the condition of stirring at room, dropwise add triethylamine, regulate pH value to 5, room temperature is placed 12h, obtains colourless bulk crystals.
Embodiment 2:
In 50mL beaker, add vitamin B13 (0.6mmol, 1.02g), Cadmium Sulphate (0.7mmol, 0.539g), phenanthroline (0.3mmol, 0.06g), add 10mL ethanol and 20mL water, under the condition of stirring at room, dropwise add triethylamine, regulate pH value to 6, room temperature is placed 24h, obtains colourless bulk crystals.
Embodiment 3:
In 50mL beaker, add vitamin B13 (0.7mmol, 1.19g), Cadmium Sulphate (0.8mmol, 0.616g), phenanthroline (0.4mmol, 0.08g), add 10mL ethanol and 20mL water, under the condition of stirring at room, dropwise add triethylamine, regulate pH value to 7, room temperature is placed 48h, obtains colourless bulk crystals.
By the colourless bulk crystals distilled water flushing making in above-described embodiment, natural air drying; After measured, the molecular formula of this vitamin B13 cadmic compound is C
44h
52n
12o
28cd
2.Crystallographic system is three oblique, and spacer is P-1, unit cell parameters a=9.5220
b=11.8790
c=12.6141
α=73.082 °, γ=78.073 °, β=81.100 °, cadmium ion is pentagonal bipyramid coordination mode, and two nitrogen ligating atoms come from phenanthroline, and three oxygen ligating atoms come from vitamin B13, and two oxygen ligating atoms are from water.Its crystalline structure figure as shown in Figure 1.
By prepared vitamin B13 cadmic compound C
44h
52n
12o
28cd
2carry out fluorescence property test, this compound demonstrates good blue light emitting performance (as Fig. 2).
Claims (3)
1. have a fluorescent material for blue luminescent properties, it is characterized in that this fluorescent material is a kind of vitamin B13 cadmic compound with certain space structure, its molecular formula is C
44h
52n
12o
28cd
2, crystallographic system is three oblique, spacer is P-1, unit cell parameters a=9.5220
b=11.8790
c=12.6141
α=73.082 °, γ=78.073 °, β=81.100 °, cadmium ion is pentagonal bipyramid coordination mode, and two nitrogen ligating atoms come from phenanthroline, and three oxygen ligating atoms come from vitamin B13, and two oxygen ligating atoms are from water.
2. there is a preparation method for the fluorescent material of blue luminescent properties, it is characterized in that comprising the following steps:
1) vitamin B13, Cadmium Sulphate and 1,10-phenanthroline are added in container 5～7:6～8:2～4 in molar ratio, then according to the weight of all substances in container, add the ethanol of 5～10mL/g and the water of 10～30mL/g, stir it is mixed;
2) under the condition of stirring at room, dropwise add triethylamine, regulate pH value to 5～8, room temperature obtains colourless bulk crystals after placing 12～48h;
3) by the colourless bulk crystals distilled water flushing making, obtain vitamin B13 cadmic compound after natural air drying, its molecular formula is C
44h
52n
12o
28cd
2, crystallographic system is three oblique, spacer is P-1, unit cell parameters a=9.5220
b=11.8790
c=12.6141
α=73.082 °, γ=78.073 °, β=81.100 °, cadmium ion is pentagonal bipyramid coordination mode, and two nitrogen ligating atoms come from phenanthroline, and three oxygen ligating atoms come from vitamin B13, and two oxygen ligating atoms are from water.
3. the preparation method of the fluorescent material with blue luminescent properties according to claim 2, is characterized in that the material of participating in reaction is analytical pure.
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| CN102391856A (en) * | 2011-09-23 | 2012-03-28 | 宁波大学 | Blue fluorescent material and preparation method thereof |
| CN106243136B (en) * | 2016-07-26 | 2018-06-15 | 宁波大学 | A kind of purple fluorescence material and preparation method thereof |
| CN106929007B (en) * | 2017-03-10 | 2019-01-22 | 宁波大学 | A kind of cyanic colours fluorescent material and preparation method thereof |
| CN106893582B (en) * | 2017-03-10 | 2019-03-15 | 宁波大学 | A kind of broadband fluorescent material and preparation method thereof |
| CN106833624B (en) * | 2017-03-10 | 2018-11-27 | 宁波大学 | A kind of bluish violet fluorescent material and preparation method thereof |
| CN107266374B (en) * | 2017-06-12 | 2019-06-04 | 宁波大学 | A kind of monokaryon zinc super molecular complex and preparation method thereof |
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Non-Patent Citations (6)
| Title |
|---|
| #351 * |
| ilel等.An unprecedented coordination mode of the orotate ligand in novel polynuclear cadmium(II)–orotate complexes.《Polyhedron》.2010,第29卷1815-1821,第1818页右栏第4段,1819页图3,1816页表1. * |
| Okan Zafer Yeş |
| Okan Zafer Ye& * |
| 二核、四核镉簇合物的合成与结构表征;卢越等;《第十六届全国金属有机化学学术讨论会论文集》;20101022;第110页第2段，图1 * |
| 卢越等.二核、四核镉簇合物的合成与结构表征.《第十六届全国金属有机化学学术讨论会论文集》.2010,第110页第2段，图1. |
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