CN104178131A - Mixed cuprous complex luminescent material containing oxazolyl pyridine ligand - Google Patents
Mixed cuprous complex luminescent material containing oxazolyl pyridine ligand Download PDFInfo
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- CN104178131A CN104178131A CN201410341572.6A CN201410341572A CN104178131A CN 104178131 A CN104178131 A CN 104178131A CN 201410341572 A CN201410341572 A CN 201410341572A CN 104178131 A CN104178131 A CN 104178131A
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- luminescent material
- pbo
- xantphos
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Abstract
The invention discloses a mixed cuprous complex luminescent material with yellowish green phosphorescence and a preparation method thereof. The phosphorescence complex is prepared by complexing cuprous salt and ligands. The molecular structure is Cu(Xantphos)(4-PBO)(CH3CN)(PF6), wherein the Xantphos and 4-PBO are electrically-neutral ligands 4,5-bisdiphenylphosphino-9,9-dimethylxanthene and 4-(2-benzooxazolyl)pyridine. The complex has the advantages of easy purification of small molecules and high luminescence efficiency, and can be easily dissolved by organic solvents. The material is prepared by directly mixing and reacting Cu(CH3CN)4PF6 with the two ligand solutions by multiple steps; and the method has the advantages of simple technique, simple equipment, accessible raw materials, low cost and the like. The material can be used as a photoluminescent yellow-light material, and can also be used as a luminescent layer phosphorescence material in an electroluminescent device composed of a multilayer organic material.
Description
Technical field
The present invention relates to luminescent material technical field, relate to embedded photoluminescent material field and electroluminescent material field, particularly relate to field of organic electroluminescent materials.
Background technology
Luminescent material comprises photoluminescence and the large class Application Areas of electroluminescent two.Photoluminescence refers to that object is subject to the irradiation of external light source, thereby obtain power generation, excites and be finally directed at luminous phenomenon.Uv-radiation, visible ray and ir radiation etc. all can cause photoluminescence.Embedded photoluminescent material can be used for the scintillator in fluorometric analysis, traffic sign, tracking monitor, agricultural light conversion film, nuclear detection technology, the aspects such as fluorescence optical collector in solar energy converting technology.Electroluminescent (electroluminescent, be called for short EL), refers to that luminescent material is under electric field action, is subject to electric current and exciting of electric field and luminous phenomenon is a kind of luminescence process that electric energy is directly converted to luminous energy.The material with this performance, can be made into automatically controlled luminescent device, for example photodiode (LED) and Organic Light Emitting Diode (Organic Light-Emitting Diode is called for short OLED).And LED and the large series products of OLED two all have very tempting application prospect in advanced flat pannel display and solid-state energy-saving illumination field, and demonstrated its good industrialized development impetus at present.
Can produce electroluminescent solid material has a variety ofly, mainly comprises inorganic semiconductor material, organic small molecule material, macromolecular material and title complex small molecule material.Due to OLED there is energy-conservation, frivolous, free from glare, without ultraviolet ray, without infrared rays, driving voltage is low, the time of response is short, cold property is good, luminous efficiency is high, manufacturing process is simple, all solid state shock resistance is good, almost do not have visible angle problem, can on the substrate of unlike material, manufacture, can make can bending the many merits such as product, enjoy in recent years attracting attention of scientific and technological circle and industrial community.And along with social development, OLED technology (or by) colour TV, mobile phone, various indicating meter, various illumination with or the fields such as display terminal of the military equipment such as decorative lamp, aircraft obtain using more and more widely.
The principle of work of OLED device is under the effect of extra electric field, and hole and electronics from positive and negative electrode injection device, are compounded to form exciton at luminescent layer respectively, luminous by the attenuation of exciton.And according to spin Statistics, singlet state exciton and triplet exciton respectively account for 25% and 75%, so luminescent layer that utilizes merely fluorescent material to make, by the input energy that can only utilize at most 25%, other most of energy can bring serious pyrogenic effect, not only wastes energy but also is unfavorable for the long-time steady operation of device.The fluorescent material of singlet state exciton energy is different from utilizing, transition metal complex phosphor material is owing to having very strong spin-orbit coupling, can make full use of all input energy that comprise triplet state and triplet state, fundamentally broken through 25% energy limited existing in a very long time, increased substantially the efficiency of OLED device, that is to say, utilize transition metal complex phosphor material can make the internal quantum of OLED device reach 100%.Therefore in the luminescent material research based on OLED device, it is particularly important that the research and development of phosphor material seem.
The phosphorescent substance that OLED product adopts is at present the title complex containing precious metals such as iridium, rheniums, and they have shown good use properties and market manifestation.But such precious metals complex exists cost expensive, especially the problem of environmental risk.Therefore, research and development for base metal Cu (I) complex phosphorescence material at present receive much concern, Cu (I) title complex is very cheap, without environmental risk, Cu (I) complex luminescent material of therefore researching and developing novel excellent property is significant and good market application foreground.
More specifically analyze, OLED on sale is the title complex of precious metal iridium and platinum etc. with yellow phosphorescence material at present, although they are existing performance preferably in performance, its expensive price also has influence on applying of OLED the finished product and market manifestation.With Cu (I) title complex as yellow phosphorescence material long-standing (N.Armaroli, G.Accorsi, F.Cardinali, A.Listorti, Top.Curr.Chem.2007,280,69-115.), the Cu of this cheapness (I) complex luminescent material can be prepared easily by Cu (I) ion and suitable organic ligand, just in its luminous intensity of OLED operating temperature range, does not still reach application demand.Therefore Cu (I) the title complex yellow phosphorescence material of development of new cheapness has great actual application value.
Summary of the invention
The object of this invention is to provide cuprous complex luminescent material of the inclined to one side green phosphorescent mixed matching of a kind of new Huang and preparation method thereof.By the solution coordination reaction of Cu (I) ion and organic ligand, convenient and prepared at an easy rate good Cu (I) complex luminescent material of luminescent properties, it is yellow, and green phosphorescent luminous intensity is very large partially, and its decay of luminescence feature meets the requirement of OLED device to material phosphorescence luminescent lifetime very much, be applied to the reduction that OLED luminescent layer material is conducive to product cost.
One of technical scheme of the present invention, is to provide the cuprous complex luminescent material of the inclined to one side green phosphorescent mixed matching of a kind of new Huang, by Cu (CH
3cN)
4pF
6carry out coordination reaction with part and obtain, its molecular structure is (4-PBO) (CH of Cu (Xantphos)
3cN) (PF
6), in formula, Xantphos and 4-PBO are respectively electric neutrality part 4, two diphenylphosphine-9 of 5-, 9-dimethyl oxa-anthracene and 4-(2-benzoxazole) pyridine.
Described part 4-(2-benzoxazole) pyridine, is the combination of benzoxazole and pyridine, and its molecular structure is suc as formula (I):
N in described part in benzoxazole structure and O atom have neither part nor lot in coordination, and N atom in pyridine structure and cuprous ion form coordinate bond.
Described luminescent material is rhombic system, P2
12
12
1(No.19) spacer, unit cell parameters
α=90 °, β=90 °, γ=90 °,
z=4, D
c=1.294 g/cm
3, crystal color is yellow, profile is block; Title complex shows as ionic complex, and counter anion is wherein hexafluoro-phosphate radical, and positively charged ion is the coordination cation being formed by cuprous ion and X ligand antphos, 4-PBO complexing; Cu in this coordination cation (I) adopts CuN
2p
2tetrahedral coordination pattern, wherein two N come from respectively pyridine groups and a ligand solvent acetonitrile molecule in 4-PBO part, and two P come from the Xantphos part of another bidentate chelating; Its molecular structure is suc as formula (II):
Described luminescent material is applied to gold-tinted phosphor material, this material is subject to the UV-light of very wide wavelength region (300-500nm) or exciting of visible ray, can send the inclined to one side green light of very strong Huang, its maximum emission wavelength is 545nm, chromaticity coordinates value is (0.3978,0.5339), luminescent lifetime is 6 microseconds.
Luminescent layer phosphor material in the electroluminescent device that described yellow phosphorescence luminescent material forms as multilayer organic materials.
Two of technical scheme of the present invention, is to provide (4-PBO) (CH of a kind of Huang cuprous title complex Cu of inclined to one side green phosphorescent mixed matching (Xantphos)
3cN) (PF
6) preparation method of luminescent material.This preparation method is by Cu (CH
3cN)
4pF
6with two kinds of parts in solution, mix there is coordination reaction, thereby then solvent is removed, separate out the crystal of product and realize.Its specific embodiments is divided into four steps:
(1) under room temperature by Cu (CH
3cN)
4pF
6powder complete solubilizing reaction in acetonitrile with 4-PBO;
(2) under room temperature, the powder of X ligand antphos is dissolved in methylene dichloride completely;
(3) described two kinds of solution are mixed, and stirring makes it fully to occur coordination reaction;
(4) by reacting liquid filtering, and gained filtrate is being vacuumized to the steaming of condition backspin, removing desolventizing and obtain yellow fine crystals product.
In preparation method of the present invention, the mol ratio Cu (CH of described three kinds of reactants
3cN)
4pF
6: Xantphos: 4-PBO is 1: 1: 1.
First beneficial effect of the present invention is (4-PBO) (CH of the provided Huang cuprous title complex Cu of inclined to one side green phosphorescent mixed matching (Xantphos)
3cN) (PF
6) luminescent material, it is luminous that the benzoxazole group of wherein introducing is conducive to molecular-excited state, metal Cu effectively promotes intersystem crossing to the existence of the electric charge transition (MLCT) of part, and on the other hand large two phosphine chelating ligand Xantphos to cause Cu (I) to exist around larger sterically hindered, and whole coordination structure has more rigidity, thereby non-radiative decay that can Inhibitory molecules excited state, thereby the phosphorescent emissions performance that had of this molecular material.This complex material had both possessed cheap and had been easy to the advantage of purifying, and had good solvability, for the further application of luminescent material provides technical support.
Secondly beneficial effect of the present invention is (4-PBO) (CH of the yellow cuprous title complex Cu of green phosphorescent mixed matching (Xantphos) partially of preparation
3cN) (PF
6) method of luminescent material, thering is simple process, equipment used is simple, and raw material is simple and easy to get, and production cost is low, can obtain in a short period of time having the very advantages such as product of high yield.
Accompanying drawing explanation
Fig. 1. phosphorescent complexes Cu (Xantphos) is (CH (4-PBO)
3cN) (PF
6) the single crystal structure figure of molecule.
Fig. 2. phosphorescent complexes Cu (Xantphos) is (CH (4-PBO)
3cN) (PF
6) molecule is in unit cell and peripheral space accumulation graph.
Fig. 3. phosphorescent complexes Cu (Xantphos) is (CH (4-PBO)
3cN) (PF
6) X-ray powder diffraction: (a) be the spectrogram calculate obtaining according to single crystal structure data in embodiment 2; (b) be the collection of illustrative plates of gained powder in the embodiment of the present invention 1.
Fig. 4. phosphorescent complexes Cu (Xantphos) is (CH (4-PBO)
3cN) (PF
6) ultraviolet-ray visible absorbing (UV-Vis) spectrogram.
Fig. 5. title complex Cu (Xantphos) is (CH (4-PBO)
3cN) (PF
6) crystallite sample under 545 nanometer supervisory wavelength, measure excite spectrogram.
Fig. 6. title complex Cu (Xantphos) is (CH (4-PBO)
3cN) (PF
6) the light emission spectrogram of crystallite sample under 410 nano wave length optical excitation.
Embodiment
The performance of implementation procedure of the present invention and material is illustrated by embodiment:
Embodiment 1
The preparation of a large amount of crystallite samples: take 112mg Cu (CH
3cN)
4pF
6be dissolved in 10mL acetonitrile with the 4-PBO part of 59mg, the Xantphos part that takes 174mg is dissolved in (mol ratio of described three kinds of reactants is 1: 1: 1) in 5mL methylene dichloride, these two kinds of solution are mixed, and stirring makes it fully to occur coordination reaction, finally gained yellow solution is filtered, and revolve to steam and remove all solvents, vacuum-drying, obtain yellow crystals powder and be product, productive rate 99% (in Cu).
Embodiment 2
Synthetic Cu (I) title complex Cu (Xantphos) is (CH (4-PBO)
3cN) (PF
6) monocrystalline: take 37mg Cu (CH
3cN)
4pF
6after being dissolved in 5mL methylene dichloride with the Xantphos part of 58mg, again the 2-PBO part of 20mg is once added in above-mentioned solution, stirring makes it to dissolve rear filtration completely, covers Virahol and impel product crystallization on filtrate, separates out a large amount of yellow bulk crystals after standing a couple of days.Select the block transparent crystals of yellow of 0.35mm * 0.28mm * 0.23mm size for the structured testing of X-ray single crystal diffraction.The molecular structure of this compound is illustrated in accompanying drawing 1, and its structure cell packed structures is illustrated in accompanying drawing 2.
To (4-PBO) (CH of title complex Cu (Xantphos)
3cN) (PF
6) pure phase crystal prototype carried out a series of performance tests.Material crystals of the present invention has been carried out to steady-state fluorescence test, result shows that this material, under different excitation wavelength effects, can launch the inclined to one side green light of strong Huang, and chromaticity coordinates value is (0.3978,0.5339), concrete excitation spectrum and emmission spectrum are as shown in accompanying drawing 5 and accompanying drawing 6.And the transient state fluorometric investigation of this material is shown, its luminescent lifetime is 6 microseconds, belongs to phosphorescent emissions.Visible, this material can be applicable to the yellow phosphorescence material that multi-wavelength excites, and is also suitable for very much the yellow phosphorescence material of OLED luminescent layer.
Claims (5)
1. the cuprous complex luminescent material of the inclined to one side green phosphorescent mixed matching of Huang, is characterized in that: the structural formula of luminescent material is (4-PBO) (CH of Cu (Xantphos)
3cN) (PF
6), in formula, Xantphos is that electric neutrality contains P part 4, two diphenylphosphine-9 of 5-, 9-dimethyl oxa-anthracene; In formula, 4-PBO is electric neutrality heterocyclic ligand 4-(2-benzoxazole) pyridine, and this part is the combination of benzoxazole and pyridine, and its molecular structure is suc as formula (I):
This luminescent material is rhombic system, P2
12
12
1(No.19) spacer, unit cell parameters
α=90 °, β=90 °, γ=90 °,
z=4, D
c=1.294g/cm
3, crystal color is yellow, profile is block; Title complex shows as ionic complex, and counter anion is wherein hexafluoro-phosphate radical, and positively charged ion is the coordination cation being formed by cuprous ion and X ligand antphos, 4-PBO complexing; Cu in this coordination cation (I) adopts CuN
2p
2tetrahedral coordination pattern, wherein two N come from respectively pyridine groups and a ligand solvent acetonitrile molecule in 4-PBO part, and two P come from the Xantphos part of another bidentate chelating; Its molecular structure is suc as formula (II):
2. the yellow preparation method of the cuprous complex luminescent material of green phosphorescent mixed matching partially according to claim 1, the method comprises the following steps:
(1) under room temperature by Cu (CH
3cN)
4pF
6powder complete solubilizing reaction in acetonitrile with 4-PBO;
(2) under room temperature, the powder of X ligand antphos is dissolved in methylene dichloride completely;
(3) described two kinds of solution are mixed, and stirring makes it fully to occur coordination reaction;
(4) by reacting liquid filtering, and gained filtrate is being vacuumized to the steaming of condition backspin, removing desolventizing and obtain yellow fine crystals product.
3. the yellow preparation method of the cuprous complex luminescent material of green phosphorescent mixed matching partially according to claim 2, is characterized in that: the mol ratio Cu (CH of described three kinds of reactants
3cN)
4pF
6: Xantphos: 4-PBO is 1: 1: 1.
4. the yellow application of the cuprous complex luminescent material of green phosphorescent mixed matching partially according to claim 1, is characterized in that described luminescent material is applied to gold-tinted embedded photoluminescent material.
5. the yellow application of the cuprous complex luminescent material of green phosphorescent mixed matching partially according to claim 1, is characterized in that described luminescent material is as the luminescent layer phosphor material in the electroluminescent device of multilayer organic materials composition.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104962281A (en) * | 2015-06-17 | 2015-10-07 | 中国计量学院 | Benzoxazolyl based CuN2P2 orange phosphorescent material |
| CN106967117A (en) * | 2017-03-21 | 2017-07-21 | 中国计量大学 | A kind of cuprous complex yellow phosphorescence luminescent materials of BINAP |
| CN108794534A (en) * | 2017-04-28 | 2018-11-13 | 中国计量大学 | A kind of cuprous complex orange phosphor luminescent material of BINAP and PBO mixtures |
| CN108795418A (en) * | 2017-04-28 | 2018-11-13 | 中国计量大学 | A kind of cuprous complex phosphorescence material of BINAP and aminopyridine mixture |
| CN108795417A (en) * | 2017-04-28 | 2018-11-13 | 中国计量大学 | A kind of cuprous complex yellow green phosphor material of chain structure |
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| CN102899029A (en) * | 2012-09-04 | 2013-01-30 | 中国计量学院 | Luminescent material of cuprous iodide complex and preparation method thereof |
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| DE102013100181A1 (en) * | 2013-01-09 | 2014-07-10 | Cynora Gmbh | Thermally activated fluorescence and singlet harvesting with rigid metal complexes for opto-electronic devices |
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2014
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Patent Citations (3)
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| CN102899029A (en) * | 2012-09-04 | 2013-01-30 | 中国计量学院 | Luminescent material of cuprous iodide complex and preparation method thereof |
| DE102013100181A1 (en) * | 2013-01-09 | 2014-07-10 | Cynora Gmbh | Thermally activated fluorescence and singlet harvesting with rigid metal complexes for opto-electronic devices |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104962281A (en) * | 2015-06-17 | 2015-10-07 | 中国计量学院 | Benzoxazolyl based CuN2P2 orange phosphorescent material |
| CN106967117A (en) * | 2017-03-21 | 2017-07-21 | 中国计量大学 | A kind of cuprous complex yellow phosphorescence luminescent materials of BINAP |
| CN108794534A (en) * | 2017-04-28 | 2018-11-13 | 中国计量大学 | A kind of cuprous complex orange phosphor luminescent material of BINAP and PBO mixtures |
| CN108795418A (en) * | 2017-04-28 | 2018-11-13 | 中国计量大学 | A kind of cuprous complex phosphorescence material of BINAP and aminopyridine mixture |
| CN108795417A (en) * | 2017-04-28 | 2018-11-13 | 中国计量大学 | A kind of cuprous complex yellow green phosphor material of chain structure |
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| Publication number | Publication date |
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| CN104178131B (en) | 2016-05-25 |
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