CN104140808A - Tetrahedral cuprous complex luminescent material containing oxazolyl pyridine ligands - Google Patents
Tetrahedral cuprous complex luminescent material containing oxazolyl pyridine ligands Download PDFInfo
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- CN104140808A CN104140808A CN201410270867.9A CN201410270867A CN104140808A CN 104140808 A CN104140808 A CN 104140808A CN 201410270867 A CN201410270867 A CN 201410270867A CN 104140808 A CN104140808 A CN 104140808A
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- luminescent material
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- pbo
- tetrahedral
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- NSTYHODPDRPTRO-UHFFFAOYSA-N c1ccc2[o]c(-c3ccncc3)nc2c1 Chemical compound c1ccc2[o]c(-c3ccncc3)nc2c1 NSTYHODPDRPTRO-UHFFFAOYSA-N 0.000 description 1
Abstract
The invention discloses a yellow phosphorescent tetrahedral cuprous complex luminescent material and preparation method thereof. The phosphorescent complex disclosed by the invention is obtained through the complexation of a cuprous salt and ligands and has the molecular structure of Cu(POP)(4-PBO)(CH3CN)(PF6), wherein POP and 4-PBO are electroneutral ligands, namely bis(2-diphenyl phosphorus phenyl) ether and 4-(2-benzoxazolyl)pyridine. The complex has the advantages of easiness in micromolecule purification and high luminescence efficiency and has the advantage of being easily dissolved by organic solvents; the material is directly obtained through the stepped mixing reaction of Cu(CH3CN)4PF6 and a solution of two ligands and has the advantages that the process is simple and convenient, the equipment is simple, the raw materials are easily obtained, the cost is low and the like; the material can serve as a photoluminescent yellow material and can also serve as a luminescent-layer phosphorescent material, consisting of multiple layers of organic materials, of an electroluminescent device.
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 a kind of new cuprous complex luminescent material of yellow phosphorescence tetrahedral 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, its yellow phosphorescence luminous intensity is very large, 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 a kind of new cuprous complex luminescent material of yellow phosphorescence tetrahedral, by Cu (CH
3cN)
4pF
6carry out coordination reaction with part and obtain, its molecular structure is (4-PBO) (CH of Cu (POP)
3cN) (PF
6), in formula, POP and 4-PBO are respectively two (the 2-diphenylphosphine phenyl) ether of electric neutrality part 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 oblique system, P2
1/ C (No.14) spacer, unit cell parameters
α=90 °, β=102.300 (7) °, γ=90 °,
z=4, D
c=1.402g/cm
3, crystal color is yellow; 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 part POP, 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 POP 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 (300-550nm) or exciting of visible ray, can send very strong sodium yellow, its maximum emission wavelength is 570nm, chromaticity coordinates value is (0.4731,0.5066), luminescent lifetime is 7 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 cuprous title complex Cu of yellow phosphorescence yellow phosphorescence tetrahedral (POP)
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 part POP 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: POP: 4-PBO is 1: 1: 1.
First beneficial effect of the present invention is (4-PBO) (CH of the provided cuprous title complex Cu of yellow phosphorescence tetrahedral (POP)
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 biphosphine ligand POP to cause Cu (I) to exist around larger sterically hindered, 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 preparation yellow phosphorescence Cu (I) title complex Cu (POP)
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 (POP) is (CH (4-PBO)
3cN) (PF
6) the single crystal structure figure of molecule.
Fig. 2. phosphorescent complexes Cu (POP) is (CH (4-PBO)
3cN) (PF
6) molecule is in unit cell and peripheral space accumulation graph.
Fig. 3. phosphorescent complexes Cu (POP) 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 (POP) is (CH (4-PBO)
3cN) (PF
6) Fourier transform infrared (FTIR) spectrogram.
Fig. 5. phosphorescent complexes Cu (POP) is (CH (4-PBO)
3cN) (PF
6) ultraviolet-ray visible absorbing (UV-Vis) spectrogram.
Fig. 6. title complex Cu (POP) is (CH (4-PBO)
3cN) (PF
6) crystallite sample under 570 nanometer supervisory wavelength, measure excite spectrogram.
Fig. 7. title complex Cu (POP) is (CH (4-PBO)
3cN) (PF
6) the light emission spectrogram of crystallite sample under 420 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 POP part that takes 162mg 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 98% (in Cu).
Embodiment 2
Synthetic Cu (I) title complex Cu (POP) is (CH (4-PBO)
3cN) (PF
6) monocrystalline: take 37mg Cu (CH
3cN)
4pF
6after being dissolved in 5mL methylene dichloride with 54mg POP part, 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 yellow crystals of 0.37mm * 0.33mm * 0.23mm size for x-ray crystal structure test.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 (POP)
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 strong gold-tinted, and chromaticity coordinates value is (0.4731,0.5066), concrete excitation spectrum and emmission spectrum are as shown in accompanying drawing 6 and accompanying drawing 7.And the transient state fluorometric investigation of this material is shown, its luminescent lifetime is 7 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 yellow phosphorescence tetrahedral, is characterized in that: the structural formula of luminescent material is (4-PBO) (CH of Cu (POP)
3cN) (PF
6), in formula, POP is that electric neutrality contains two (the 2-diphenylphosphine phenyl) ether of P part; 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 oblique system, P2
1/ C (No.14) spacer, unit cell parameters
α=90 °, β=102.300 (7) °, γ=90 °,
z=4, D
c=1.402g/cm
3, crystal color is yellow; 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 part POP, 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 POP part of another bidentate chelating; Its molecular structure is suc as formula (II):
2. the preparation method of the cuprous complex luminescent material of yellow phosphorescence tetrahedral 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 part POP 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 preparation method of the cuprous complex luminescent material of yellow phosphorescence tetrahedral according to claim 2, is characterized in that: the mol ratio Cu (CH of described three kinds of reactants
3cN)
4pF
6: POP: 4-PBO is 1: 1: 1.
4. the application of the cuprous complex luminescent material of yellow phosphorescence tetrahedral according to claim 1, is characterized in that described luminescent material is applied to gold-tinted embedded photoluminescent material.
5. the application of the cuprous complex luminescent material of yellow phosphorescence tetrahedral 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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| CN201410270867.9A CN104140808B (en) | 2014-06-10 | 2014-06-10 | A kind of cuprous complex luminescent material of tetrahedral of Han oxazolyl pyridine ligand |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104946245A (en) * | 2015-07-02 | 2015-09-30 | 浙江理工大学 | CuBrN2P type cuprous complex yellow phosphorescent material based on diphenyleneimine |
| CN104961770A (en) * | 2015-06-17 | 2015-10-07 | 中国计量学院 | Pyronyl phosphine ligand based cuprous-complex green phosphorescent material |
| CN105733565A (en) * | 2016-04-18 | 2016-07-06 | 中国计量大学 | Benzoxazolyl isoquinoline cuprous complex luminous material |
| CN105754591A (en) * | 2016-04-18 | 2016-07-13 | 中国计量大学 | Crystal form of benzoxazolyl isoquinoline cuprous complex luminescent material |
| CN105754590A (en) * | 2016-04-18 | 2016-07-13 | 中国计量大学 | Methyl-substituted benzoxazolyl cuprous pyridine complex yellow phosphor material |
| CN107617419A (en) * | 2016-07-16 | 2018-01-23 | 天津师范大学 | Application of thiocyanate radical Cu (II) complexs that 3 (oxadiazole of 5 methyl 1,3,4) pyridines are constructed in dyestuff is adsorbed |
| CN108794513A (en) * | 2017-04-28 | 2018-11-13 | 中国计量大学 | A kind of cuprous complex luminescent material of green phosphorescent of double phosphines and pyridines mixture |
| 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 |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104961770A (en) * | 2015-06-17 | 2015-10-07 | 中国计量学院 | Pyronyl phosphine ligand based cuprous-complex green phosphorescent material |
| CN104946245A (en) * | 2015-07-02 | 2015-09-30 | 浙江理工大学 | CuBrN2P type cuprous complex yellow phosphorescent material based on diphenyleneimine |
| CN105733565A (en) * | 2016-04-18 | 2016-07-06 | 中国计量大学 | Benzoxazolyl isoquinoline cuprous complex luminous material |
| CN105754591A (en) * | 2016-04-18 | 2016-07-13 | 中国计量大学 | Crystal form of benzoxazolyl isoquinoline cuprous complex luminescent material |
| CN105754590A (en) * | 2016-04-18 | 2016-07-13 | 中国计量大学 | Methyl-substituted benzoxazolyl cuprous pyridine complex yellow phosphor material |
| CN105733565B (en) * | 2016-04-18 | 2017-05-24 | 中国计量大学 | Benzoxazolyl isoquinoline cuprous complex luminous material |
| CN107617419A (en) * | 2016-07-16 | 2018-01-23 | 天津师范大学 | Application of thiocyanate radical Cu (II) complexs that 3 (oxadiazole of 5 methyl 1,3,4) pyridines are constructed in dyestuff is adsorbed |
| CN108794513A (en) * | 2017-04-28 | 2018-11-13 | 中国计量大学 | A kind of cuprous complex luminescent material of green phosphorescent of double phosphines and pyridines mixture |
| 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 |
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