CN102241974A - Near blue fluorescent material and preparation method thereof - Google Patents
Near blue fluorescent material and preparation method thereof Download PDFInfo
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- CN102241974A CN102241974A CN2011101140496A CN201110114049A CN102241974A CN 102241974 A CN102241974 A CN 102241974A CN 2011101140496 A CN2011101140496 A CN 2011101140496A CN 201110114049 A CN201110114049 A CN 201110114049A CN 102241974 A CN102241974 A CN 102241974A
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Abstract
The invention discloses a near blue fluorescent material and a preparation method thereof. The material is prepared through chemical reactions of quinoline carboxylic acid and 4,4'-bipyridine with conjugated extended pi bonds, and zinc ions with optical activity. The fluorescent material is a zinc quinoline carboxylic crystal with a molecular formula of C84H56N8O8Zn2. The crystal belongs to a crystal system of triclinic system, and a space group of P-1. Cell parameters of the crystal are that: alpha= 91.357 DEG, gamma=106.573 DEG, and beta=101.953DEG. The zinc ions have two coordination modes, one is a square pyramid coordination mode, wherein two nitrogen coordinating atoms come from two different 4,4'-bipyridines, and three oxygen coordinating atoms come from two different quinoline carboxylic acid ligands; the other is a octahedral coordination mode, wherein two nitrogen coordinating atoms come from two different 4,4'-bipyridines, and four oxygen coordinating atoms come from two different quinoline carboxylic acid ligands. The material is advantaged in that: the fluorescent material contains abundant optically active Zn (II) ions and conjugated extended bonds, and has good near blue light emission performance.
Description
Technical field
The present invention relates to a kind of fluorescent material, be specifically related to a kind of nearly blue fluorescent material and preparation method thereof.
Background technology
Fluorescent material typically refers to after having accepted outside energy, energy absorption can be stored, and is converted into the material of luminous energy in the place of dark.The organic ligand that has optically active metal ion or contain the conjugation primitive is incorporated in the fluorescent material, can greatly improves the luminescent properties of fluorescent material.The organic ligand that employing contains different conjugation primitives cooperates with metal ion, and sensitizing agent can be prepared the fluorescent material of various optical effects, and it is widely used in decorating, false proof, sign, medical treatment, numerous areas such as commodity inspection.
Fluorescent material can roughly be divided into following three classes by material structure: the aromatic fused ring compound that (a) has rigid structure; (b) has the intramolecular charge transfer compounds of conjugated structure; (c) some a metal-organic complex.Many ligand moleculars are not luminous or luminous very weak under free state, are transformed into strong luminophore behind the formation title complex.Also having a class title complex luminescence mechanism is to come from metal ion to have cut off the photic transfer transport in the ligand molecular and strengthened the fluorescent radiation transition.Therefore, non-luminous part can be as the analytical reagent or the probe molecule of specific ion under some free state.It is because they can be in order to survey some crucial ionic concn in the body fluid that the research of this quasi-molecule is just becoming one of focus, for biology with medically solve many key issues condition easily is provided.If they are carried out certain chemically modified, can be prepared into and have specific optionally functional membrane.
Phosphor material powder was come out the earliest in 1938.People such as early stage Stokes have synthesized fluorescent material such as calcium wolframate and have been used for luminescent lamp.Developed phosphate phosphor in 1948, this light-emitting phosphor performance has had remarkable improvement than early stage fluorescent material.60～seventies of 20th century fluorescent material obtained general application.Along with deepening continuously that fluorescent material is studied, people have developed three primary colors fluorescent powder.Rare earth element is introduced in the fluorescent material as activator, the luminescent properties of fluorescent material is significantly improved.The rare-earth trichromatic luminescent lamp in Europe in 1997 accounts for half of head light total amount according to statistics.The eighties in 20th century, ultrafine powder grows up gradually, becomes the emphasis of various countries' research day by day.So-called ultrafine powder is meant yardstick between molecule, atom and bulk material, comprises multiple particulate materials such as metal, nonmetal, organic and inorganic and biology, also claims nano-particle material.Fluorescent material mainly contains sulfide-based fluorescent material in the market, aluminate fluorescent powder, phosphate-based fluorescent material, fluorescent RE powder etc.From luminous wave band, mainly contain near ultraviolet excitated redness, green and blue colour fluorescent powder.
Generally speaking, the luminous three primary colors fluorescent powder of near ultraviolet had been obtained great advance round realizing photoluminescence in recent years, had developed the fluorescent material of many novel systems, had improved the fluorescent material performance of previous exploitation.Especially develop and improved near ultraviolet fluorescent powder, make its performance more can be implemented in application on the light emitting devices.Emerged in large numbers many novel systems at present, wherein oxynitride system and molybdenum (tungsten) silicate system etc. is very promising rouge and powder.Green powder had also been developed some novel systems in recent years.But the shortage of blue colour fluorescent powder hampers the development of practical panchromatic demonstration always, so seek the direction that the blue-light-emitting substrate material of high-level efficiency, high stability, high color purity is research always.
The metal organic micromolecule compound that Recent study finds to have optically active metal ion and the organic ligand assembling that contains the conjugation primitive demonstrates good luminous property.Such research has significant novelty: organic composition and inorganic components can be carried out autotelic screening and regulation and control, by the size of screening metal ion or conjugation primitive, realize the regulation and control to emission wavelength; In addition, can on molecular level, the design to material synthesize, help the relation of research structure and performance, explore the luminescence mechanism of material, thereby provide theoretical foundation for designing advanced luminescent material.
Summary of the invention
Technical problem to be solved by this invention is at prior art, and a kind of fluorescent material with good nearly blue emission performance 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 nearly blue fluorescent material, this fluorescent material are a kind of zinc quinoline carboxylic acid crystal, and its molecular formula is C
84H
56N
8O
8Zn
2, crystallographic system is three oblique, spacer is P-1, unit cell parameters
α=91.357 °, γ=106.573 °, β=101.953 °, zine ion has two kinds of coordination modes: a kind of is the tetragonal pyramid coordination mode, two nitrogen ligating atoms come from two different 4,4 '-dipyridyl, three oxygen ligating atoms come from two different quinoline carboxylic acid's parts; Another kind of is the octahedral coordination pattern, and two nitrogen ligating atoms come from two 4,4 ' different-dipyridyls, and four oxygen ligating atoms come from two different quinoline carboxylic acid's parts.
A kind of preparation method of nearly blue fluorescent material may further comprise the steps:
(1) by mass ratio 5～45: to reactor in add quinoline carboxylic acid, zinc acetate, 4 at 5～120: 5～110: 1～15,4 '-dipyridyl and potassium hydroxide, according to the ratio adding an amount of water of above-mentioned substance total mass in 0.04～1.2mL/mg, stirring mixes it then;
(2) baking oven is put in the reactor sealing, 60-130 ℃ of heating 24-72h; Naturally cool to room temperature then, open reactor and get colourless bulk crystals;
The colourless bulk crystals distilled water flushing that (3) will make, natural air drying; Obtain zinc quinoline carboxylic acid crystal, molecular formula is C
84H
56N
8O
8Zn
2
The material of participating in reaction is analytical pure.
Compared with prior art, the invention has the advantages that: the quinoline carboxylic acid and 4 that will have the big π key of conjugation, 4 '-dipyridyl with have optically active zine ion and carry out chemical reaction and make new zinc quinoline carboxylic acid crystal, this crystal has space structure (Fig. 1) and molecular formula accurately accurately as nearly blue light fluorescent material; Contain and enrich optically active Zn (II) ion and the big π key of conjugation, help transition of electron and transmission ofenergy, thereby make crystal have good photoelectric activity, have good nearly blue emission performance, have the potential application prospect as fluorescent material.Use method of the present invention to prepare zinc quinoline carboxylic acid crystal, productive rate can reach 60-80%.
Description of drawings
Fig. 1 is the structural unit figure of the nearly blue fluorescent material of zinc quinoline carboxylic acid of the present invention;
Fig. 2 is the fluorescence emission spectrum of the nearly blue fluorescent material of zinc quinoline carboxylic acid of the present invention.
Embodiment
Embodiment describes in further detail the present invention below in conjunction with accompanying drawing.
Embodiment 1:
In the 25mL of stainless steel cauldron polytetrafluoroethyllining lining, add the quinoline carboxylic acid (12.3mg, 0.05mmol), zinc acetate (10.5mg, 0.05mmol), 4, and 4 '-dipyridyl (9.8mg, 0.05mmol), potassium hydroxide (2.8mg, 0.05mmol), adding entry 10mL, stirring mixes it.
Baking oven is put in the reactor sealing, 60 ℃ of heating 24h; Naturally cool to room temperature then, open reactor and get colourless bulk crystals.
Embodiment 2:
In the 25mL of stainless steel cauldron polytetrafluoroethyllining lining, add the quinoline carboxylic acid (24.6mg, 0.10mmol), zinc acetate (101.0mg, 0.50mmol), 4, and 4 '-dipyridyl (99.0mg, 0.50mmol), potassium hydroxide (5.6mg, 0.10mmol), adding entry 15mL, stirring mixes it.
Baking oven is put in the reactor sealing, 100 ℃ of heating 48h; Naturally cool to room temperature then, open reactor and get colourless bulk crystals.
Embodiment 3:
In the 25mL of stainless steel cauldron polytetrafluoroethyllining lining, add the quinoline carboxylic acid (36.9mg, 0.15mmol), zinc acetate (31.5mg, 0.15mmol), 4, and 4 '-dipyridyl (19.8mg, 0.10mmol), potassium hydroxide (11.2mg, 0.20mmol), adding entry 20mL, stirring mixes it.
Baking oven is put in the reactor sealing, 120 ℃ of heating 72h; Naturally cool to room temperature then, open reactor and get colourless bulk crystals.
With the colourless bulk crystals distilled water flushing that makes, natural air drying; After measured, this zinc quinoline carboxylic acid crystalline molecular formula is C
84H
56N
8O
8Zn
2, crystallographic system is three oblique, spacer is P-1, unit cell parameters
α=91.357 °, γ=106.573 °, β=101.953 °, zine ion has two kinds of coordination modes: a kind of is the tetragonal pyramid coordination mode, two nitrogen ligating atoms come from two different 4,4 '-dipyridyl, three oxygen ligating atoms come from two different quinoline carboxylic acid's parts; Another kind of is the octahedral coordination pattern, and two nitrogen ligating atoms come from two 4,4 ' different-dipyridyls, and four oxygen ligating atoms come from two different quinoline carboxylic acid's parts.Its crystalline structure figure as shown in Figure 1.
With prepared zinc quinoline carboxylic acid crystal C
84H
56N
8O
8Zn
2Carry out the fluorescence property test, this crystal demonstrates good nearly blue light emitting performance (as Fig. 2).
Claims (3)
1. a nearly blue fluorescent material is characterized in that this fluorescent material is a kind of zinc quinoline carboxylic acid crystal, and its molecular formula is C
84H
56N
8O
8Zn
2, crystallographic system is three oblique, spacer is P-1, unit cell parameters
α=91.357 °, γ=106.573 °, β=101.953 °, zine ion has two kinds of coordination modes: a kind of is the tetragonal pyramid coordination mode, two nitrogen ligating atoms come from two different 4,4 '-dipyridyl, three oxygen ligating atoms come from two different quinoline carboxylic acid's parts; Another kind of is the octahedral coordination pattern, and two nitrogen ligating atoms come from two 4,4 ' different-dipyridyls, and four oxygen ligating atoms come from two different quinoline carboxylic acid's parts.
2. the preparation method of a nearly blue fluorescent material is characterized in that may further comprise the steps:
(1) by mass ratio 5～45: 5～120: 5～110: 1～15 adds the quinoline carboxylic acid in reactor, zinc acetate, 4,4 '-dipyridyl and potassium hydroxide, according to the ratio adding an amount of water of above-mentioned substance total mass in 0.04～1.2mL/mg, stirring mixes it then;
(2) baking oven is put in the reactor sealing, 60-130 ℃ of heating 24-72h; Naturally cool to room temperature then, open reactor and get colourless bulk crystals, productive rate 60-80%.；
The colourless bulk crystals distilled water flushing that (3) will make, natural air drying; Obtain zinc quinoline carboxylic acid crystal, molecular formula is C
84H
56N
8O
8Zn
2
3. the preparation method of nearly blue fluorescent material according to claim 2 is characterized in that the material of participating in reaction is analytical pure.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898447A (en) * | 2012-09-28 | 2013-01-30 | 宁波大学 | Three-dimensional ordered porous material of metal zinc complex and method for preparing same |
| CN104119863A (en) * | 2014-08-01 | 2014-10-29 | 宁波大学 | Green fluorescent material and preparation method thereof |
| CN104628747A (en) * | 2015-01-30 | 2015-05-20 | 郑州轻工业学院 | Green-fluorescence zinc N,N-bis(4-cyanophenyl) aminoacetate complex and preparation method thereof |
| CN104628746A (en) * | 2015-01-30 | 2015-05-20 | 郑州轻工业学院 | Blue fluorescence N,N-bis(4-cyanophenyl)glycine zinc complex and preparation method thereof |
| CN105623650A (en) * | 2016-03-22 | 2016-06-01 | 河南省医疗器械检验所 | Proton transfer blue luminescent material and preparation method thereof |
| CN106893582A (en) * | 2017-03-10 | 2017-06-27 | 宁波大学 | A kind of broadband fluorescent material and preparation method thereof |
| CN108299475A (en) * | 2018-02-06 | 2018-07-20 | 云南农业大学 | 3-dimensional metal based on 5- chlorothiophene -2- carboxylic acids and 4,4 '-bipyridyls-organic backbone crystalline material and preparation method |
| CN108976432A (en) * | 2018-07-16 | 2018-12-11 | 江西师范大学 | Lanthanide Coordination Polymers of alkali metal modified and its preparation method and application |
| CN109206444A (en) * | 2018-09-20 | 2019-01-15 | 苏州大学 | Photic contraction metal organic framework compound |
| CN112094283A (en) * | 2020-10-10 | 2020-12-18 | 宁波大学 | Zinc ammoniarinone complex blue fluorescent material and preparation method thereof |
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| US20090167158A1 (en) * | 2005-11-07 | 2009-07-02 | Poopathy Kathirgamanathan | Electroluminescent Devices |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20090167158A1 (en) * | 2005-11-07 | 2009-07-02 | Poopathy Kathirgamanathan | Electroluminescent Devices |
Non-Patent Citations (2)
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| MEI-QIN ZHA等: "Syntheses, structures, and fluorescence of two cadmium compounds [Cd2(pqc)4(phen)2(H2O)2]•2H2O and {[Cd(pqc)2(bpy)(H2O)2]•2H2O}n", 《JOURNAL OF COORDINATION CHEMISTRY》 * |
| MEI-QIN ZHA等: "Syntheses, structures, and fluorescence of two cadmium compounds [Cd2(pqc)4(phen)2(H2O)2]•2H2O and {[Cd(pqc)2(bpy)(H2O)2]•2H2O}n", 《JOURNAL OF COORDINATION CHEMISTRY》, vol. 64, no. 3, 10 January 2011 (2011-01-10) * |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898447A (en) * | 2012-09-28 | 2013-01-30 | 宁波大学 | Three-dimensional ordered porous material of metal zinc complex and method for preparing same |
| CN102898447B (en) * | 2012-09-28 | 2015-04-29 | 宁波大学 | Three-dimensional ordered porous material of metal zinc complex and method for preparing same |
| CN104119863A (en) * | 2014-08-01 | 2014-10-29 | 宁波大学 | Green fluorescent material and preparation method thereof |
| CN104119863B (en) * | 2014-08-01 | 2015-09-09 | 宁波大学 | A kind of green fluorescent material and preparation method thereof |
| CN104628747A (en) * | 2015-01-30 | 2015-05-20 | 郑州轻工业学院 | Green-fluorescence zinc N,N-bis(4-cyanophenyl) aminoacetate complex and preparation method thereof |
| CN104628746A (en) * | 2015-01-30 | 2015-05-20 | 郑州轻工业学院 | Blue fluorescence N,N-bis(4-cyanophenyl)glycine zinc complex and preparation method thereof |
| CN104628747B (en) * | 2015-01-30 | 2016-04-20 | 郑州轻工业学院 | A kind of green fluorescence N, N-bis-(4-cyano-phenyl) Padil Zn complex and preparation method thereof |
| CN105623650A (en) * | 2016-03-22 | 2016-06-01 | 河南省医疗器械检验所 | Proton transfer blue luminescent material and preparation method thereof |
| CN106893582A (en) * | 2017-03-10 | 2017-06-27 | 宁波大学 | A kind of broadband 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 |
| CN108299475A (en) * | 2018-02-06 | 2018-07-20 | 云南农业大学 | 3-dimensional metal based on 5- chlorothiophene -2- carboxylic acids and 4,4 '-bipyridyls-organic backbone crystalline material and preparation method |
| CN108976432A (en) * | 2018-07-16 | 2018-12-11 | 江西师范大学 | Lanthanide Coordination Polymers of alkali metal modified and its preparation method and application |
| CN108976432B (en) * | 2018-07-16 | 2021-09-07 | 江西师范大学 | Alkali metal modified lanthanide coordination polymer and preparation method and application thereof |
| CN109206444A (en) * | 2018-09-20 | 2019-01-15 | 苏州大学 | Photic contraction metal organic framework compound |
| CN112094283A (en) * | 2020-10-10 | 2020-12-18 | 宁波大学 | Zinc ammoniarinone complex blue fluorescent material and preparation method thereof |
| CN112094283B (en) * | 2020-10-10 | 2022-09-09 | 宁波大学 | Aninorinone zinc complex blue fluorescent material and preparation method thereof |
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