CN102127426A - Fluorescent material with purple luminescence property and preparation method thereof - Google Patents
Fluorescent material with purple luminescence property and preparation method thereof Download PDFInfo
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- CN102127426A CN102127426A CN2011100043107A CN201110004310A CN102127426A CN 102127426 A CN102127426 A CN 102127426A CN 2011100043107 A CN2011100043107 A CN 2011100043107A CN 201110004310 A CN201110004310 A CN 201110004310A CN 102127426 A CN102127426 A CN 102127426A
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- fluorescent material
- carboxylic acid
- cadmium
- quinoline carboxylic
- phenanthroline
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Abstract
The invention discloses a fluorescent material with purple luminescence property and a preparation method thereof. The invention is characterized in that: quinoline carboxylic acid with a conjugated large pi bond, phenanthroline and cadmium ions with optical activity are subjected to chemical reaction to form the fluorescent material of a cadmium quinoline carboxylic acid compound; the fluorescent material is the cadmium quinoline carboxylic acid compound with a certain space structure, and has the molecular formula of C88H64N8012Cd2, a monoclinic crystal system, a space group of P21/c, and the cell parameters as follows: a=14.8760, b=13.8406, c=17.8687, alpha=gamma=90 degrees, and beta=96.034 degrees; the cadmium ions are in a distorted octahedral coordination mode; two nitrogen coordination atoms are from 1,10-phenanthroline; three oxygen coordination atoms are from three different quinoline carboxylic acid ligands; and an oxygen coordination atom is from a coordinated water molecule. The compound contains rich Cd (II) ions and the conjugated large pi bond with high optical activity, facilitates electron transition and energy transfer, has good photoelectric activity and shows good purple luminescence property.
Description
Technical field
The present invention relates to a kind of fluorescent material, especially relate to a kind of fluorescent material and preparation method thereof with violet light performance.
Background technology
The radiation that fluorescence is discharged when being the material low-energy state identical from the excited state inactivation to multiplicity.The most basic condition that compound can produce fluorescence is that its energy of being absorbed when the constant transition of multiplicity takes place is less than the most weak chemical bond energy needed of fracture.In the structure of compound, must have fluorophor as=C=O ,-N=O ,-N=N ,=C=N-,=C=S etc.When these groups were conjugated system a part of of molecule, then this compound may produce fluorescence.
Fluorescent material can roughly be divided into following three classes by 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.As oxine is a coordination reagent commonly used in analysis, Φ
fBe worth extremely lowly, almost can think not fluoresce.At itself and Al
3+The oxine aluminium (Alq) that forms after the coordination just has good fluorescence property, has become the star molecule in the electroluminescent at present.In addition, oxine can also form the luminescent ligand compound with metal ions such as Be, Ga, In, Sc, Th, Zn, Zr.This is because after forming title complex, the structure of the part more rigidity that becomes, thus significantly reduce the radiationless transition probability and make radiative transistion probability be significantly improved.Some Schiff bases part and the formed title complex of Hete rocyclic derivatives molecule also can form good luminescent ligand compound.
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 widespread use.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 all is to realize round photoluminescence, has obtained great advance in recent years, has developed the fluorescent material of many novel systems, has 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 fluorescent material with violet light performance also has many work that have much room for improvement to do, and for example: luminous efficiency is low, poor heat stability etc., also needs to develop more novel system, so that improve its performance.
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
Primary technical problem to be solved by this invention is at prior art, and a kind of good fluorescent material with violet light performance and preparation method thereof that has 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 violet light performance, this fluorescent material are a kind of cadmium quinoline carboxylic acid compounds with certain space structure, and its molecular formula is C
88H
64N
8O
12Cd
2, crystallographic system is a monocline, spacer is P21/c, unit cell parameters a=14.8706
B=13.8406
C=17.8687
α=γ=90 °, β=96.034 °, cadmium ion is distortion octahedral coordination pattern, two nitrogen ligating atoms come from 1, the 10-phenanthroline, three oxygen ligating atoms come from three different quinoline carboxylic acid's parts, and an oxygen ligating atom comes from a coordinated water molecule.
Above-mentioned Preparation of Fluorescent Material method may further comprise the steps:
(1) add quinoline carboxylic acid, cadmium acetate, 1 at 1～3: 1～5: 2～3: 1～5 in molar ratio in reactor, 10-phenanthroline, potassium hydroxide add the water of 5～30mL/g then according to the weight of all substances in the container, stir it is mixed;
(2) baking oven is put in the reactor sealing, at 60-130 ℃ of heating 24-48h; Naturally cool to room temperature then, open reactor and get colourless bulk crystals;
The colourless bulk crystals distilled water flushing that (3) will make obtains cadmium quinoline carboxylic acid compound behind the natural air drying, its molecular formula is C
88H
64N
8O
12Cd
2
The material of participating in reaction is analytical pure.
Compared with prior art, the invention has the advantages that: will have the quinoline carboxylic acid and the phenanthroline of the big π key of conjugation and have optically active cadmium ion and carry out chemical reaction and make novel cadmium quinoline carboxylic acid compound, this compound has space structure (Fig. 1) and molecular formula accurately accurately as the purple light emissive material; Contain and enrich optically active Cd (II) ion and the big π key of conjugation, help transition of electron and transmission ofenergy, thereby make compound have good photoelectric activity.Prepared material has good purple light emitting performance, has the potential application prospect as fluorescent material.Adopt method of the present invention then can obtain the productive rate of 60-85%.
Description of drawings
Fig. 1 is the structural unit figure of cadmium quinoline carboxylic acid purple fluorescence material of the present invention;
Fig. 2 is the fluorescence emission spectrum of cadmium quinoline carboxylic acid purple fluorescence material 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 quinoline carboxylic acid (0.0123g, 0.05mmol), cadmium acetate (0.0133g, 0.05mmol), 1,10-phenanthroline (0.0198g, 0.10mmol), potassium hydroxide (0.0028g, 0.05mmol), add an amount of water 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 quinoline carboxylic acid (0.0123g, 0.05mmol), cadmium acetate (0.0399g, 0.15mmol), 1,10-phenanthroline (0.0198g, 0.10mmol), potassium hydroxide (0.0028g, 0.05mmol), add an amount of water 15mL, stirring mixes it.Baking oven is put in the reactor sealing, 100 ℃ of heating 36h; 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 quinoline carboxylic acid (0.0123g, 0.05mmol), cadmium acetate (0.0665g, 0.25mmol), 1,10-phenanthroline (0.0198g, 0.10mmol), potassium hydroxide (0.0028g, 0.05mmol), add an amount of water 20mL, stirring mixes it.Baking oven is put in the reactor sealing, 120 ℃ of heating 48h; Naturally cool to room temperature then, open reactor and get colourless bulk crystals.
With the colourless bulk crystals distilled water flushing that makes in the foregoing description, natural air drying; After measured, the molecular formula of this cadmium quinoline carboxylic acid compound is C
88H
64N
8O
12Cd
2Crystallographic system is a monocline, and spacer is P21/c, unit cell parameters a=14.8706
B=13.8406
C=17.8687
α=γ=90 °, β=96.034 °, cadmium ion is distortion octahedral coordination pattern, two nitrogen ligating atoms come from 1, the 10-phenanthroline, three oxygen ligating atoms come from three different quinoline carboxylic acid's parts, and an oxygen ligating atom comes from a coordinated water molecule.Its crystalline structure figure as shown in Figure 1.
With prepared cadmium quinoline carboxylic acid Compound C
88H
64N
8O
12Cd
2Carry out the fluorescence property test, this compound exhibits goes out good purple light emitting performance (as Fig. 2).
Claims (3)
1. the fluorescent material with violet light performance is characterized in that this fluorescent material is a kind of cadmium quinoline carboxylic acid compound with certain space structure, and its molecular formula is C
88H
64N
8O
12Cd
2, crystallographic system is a monocline, spacer is P21/c, unit cell parameters a=14.8706
B=13.8406
C=17.8687
α=γ=90 °, β=96.034 °, cadmium ion is distortion octahedral coordination pattern, two nitrogen ligating atoms come from 1, the 10-phenanthroline, three oxygen ligating atoms come from three different quinoline carboxylic acid's parts, and an oxygen ligating atom comes from a coordinated water molecule.
2. Preparation of Fluorescent Material method with violet light performance is characterized in that may further comprise the steps:
(1) add quinoline carboxylic acid, cadmium acetate, 1 at 1～3: 1～5: 2～3: 1～5 in molar ratio in reactor, 10-phenanthroline, potassium hydroxide add the water of 5～30mL/g then according to the weight of all substances in the container, stir it is mixed;
(2) baking oven is put in the reactor sealing, at 60-130 ℃ of heating 24-48h; Naturally cool to room temperature then, open reactor and get colourless bulk crystals;
The colourless bulk crystals distilled water flushing that (3) will make obtains cadmium quinoline carboxylic acid compound behind the natural air drying, its molecular formula is C
88H
64N
8O
12Cd
2
3. the Preparation of Fluorescent Material method with violet light performance according to claim 2 is characterized in that the material of participating in reaction is analytical pure.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329610A (en) * | 2011-09-23 | 2012-01-25 | 宁波大学 | Purple fluorescent material and a preparation method thereof |
| CN103833779A (en) * | 2014-04-03 | 2014-06-04 | 哈尔滨工业大学 | Two-dimensional cadmium coordination polymer with conjugated pi bond-containing aromatic carboxylic acid 3-quinolinedicarboxylic acid ligands and synthesis method for two-dimensional cadmium coordination polymer |
| CN104119862A (en) * | 2014-08-01 | 2014-10-29 | 宁波大学 | Complex with purple fluorescence emission property and preparation method of complex |
| CN104744499A (en) * | 2015-02-27 | 2015-07-01 | 广东工业大学 | Trifluoromethyl quinoline-containing cadmium complex tetramer as well as preparation method and application thereof |
| CN104789212A (en) * | 2015-04-21 | 2015-07-22 | 徐伟鹏 | White light fluorescent powder for LED and preparation method thereof |
| CN106929007A (en) * | 2017-03-10 | 2017-07-07 | 宁波大学 | A kind of cyanic colours fluorescent material and preparation method thereof |
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| GB1313720A (en) * | 1970-12-15 | 1973-04-18 | Boehringer Mannheim Gmbh | Crystalline trisodium d-fructose-1,6-diphosphoric acid octahydrate |
| CN101701021A (en) * | 2009-11-02 | 2010-05-05 | 南昌航空大学 | Rare earth lanthanum chelidonamic acid complex and preparation method thereof |
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2011
- 2011-01-11 CN CN2011100043107A patent/CN102127426A/en active Pending
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| GB1313720A (en) * | 1970-12-15 | 1973-04-18 | Boehringer Mannheim Gmbh | Crystalline trisodium d-fructose-1,6-diphosphoric acid octahydrate |
| CN101701021A (en) * | 2009-11-02 | 2010-05-05 | 南昌航空大学 | Rare earth lanthanum chelidonamic acid complex and preparation method thereof |
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), pages 473 - 482 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102329610A (en) * | 2011-09-23 | 2012-01-25 | 宁波大学 | Purple fluorescent material and a preparation method thereof |
| CN102329610B (en) * | 2011-09-23 | 2013-07-10 | 宁波大学 | Purple fluorescent material and a preparation method thereof |
| CN103833779A (en) * | 2014-04-03 | 2014-06-04 | 哈尔滨工业大学 | Two-dimensional cadmium coordination polymer with conjugated pi bond-containing aromatic carboxylic acid 3-quinolinedicarboxylic acid ligands and synthesis method for two-dimensional cadmium coordination polymer |
| CN103833779B (en) * | 2014-04-03 | 2016-08-17 | 哈尔滨工业大学 | Aromatic carboxylic acids 3-quinolinecarboxylic acid part two dimension cadmium coordination polymer containing conjugatedπbond |
| CN104119862A (en) * | 2014-08-01 | 2014-10-29 | 宁波大学 | Complex with purple fluorescence emission property and preparation method of complex |
| CN104119862B (en) * | 2014-08-01 | 2016-03-30 | 宁波大学 | A kind of have title complex of purple fluorescence emitting performance and preparation method thereof |
| CN104744499A (en) * | 2015-02-27 | 2015-07-01 | 广东工业大学 | Trifluoromethyl quinoline-containing cadmium complex tetramer as well as preparation method and application thereof |
| CN104789212A (en) * | 2015-04-21 | 2015-07-22 | 徐伟鹏 | White light fluorescent powder for LED and preparation method thereof |
| CN106929007A (en) * | 2017-03-10 | 2017-07-07 | 宁波大学 | A kind of cyanic colours fluorescent 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 |
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Application publication date: 20110720 |