CN104961770A - Pyronyl phosphine ligand based cuprous-complex green phosphorescent material - Google Patents
Pyronyl phosphine ligand based cuprous-complex green phosphorescent material Download PDFInfo
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Abstract
The invention discloses a pyronyl phosphine ligand based cuprous-complex green phosphorescent material and a preparation method thereof. The phosphorescent complex of the pyronyl phosphine ligand based cuprous-complex green phosphorescent material is obtained through cuprous salt and ligand complexation, a molecular structure of the phosphorescent complex is [Cu(POP)(DPPY)][Cu(POP)(DPPY)(i-PrOH)(PF6)2.(CH2C12), the POP and the DPPY in the formula are respectively electrically neutral phosphine ligand bis(2-diphenylphosphinophenyl) ether and diphenyl-2-pyridylphosphine. The complex has the advantages that micro-molecules are easy to purify and luminous efficiency is high and has high heat stability. The pyronyl phosphine ligand based cuprous-complex green phosphorescent material is obtained through step-by-step mixing and reaction of Cu(CH3CN)4PF6 and dichloromethane solutions of the ligands POP and DPPY, has the advantages that a process is simple and convenient, a device is simple, raw materials are easy to obtain, cost is low and the like, can serve as a green photo-luminescent material and can also serve as a luminous-layer phosphorescent material consisting of multiple layers of organic materials and used in 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, thus the generation of acquisition energy excites and is 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 aspects such as the scintillator in fluorometric analysis, traffic sign, tracking monitor, agricultural light conversion film, nuclear detection technology, the 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, and being subject to the phenomenon of electric current and exciting of electric field and luminescence, is a kind of luminescence process electric energy being directly converted to luminous energy.There is the material of this performance, automatically controlled luminescent device can be made into, such as photodiode (LED), Organic Light Emitting Diode (Organic Light-EmittingDiode is called for short OLED) and luminescent electrochemical cell LEC (Light-emitting Electrochemical Cell).And the large series products of LED and OLED two, in the flat pannel display of advanced person and solid-state energy-saving illumination field, all there is very tempting application prospect, and shown its good industrialized development impetus at present.LEC also has very tempting application prospect in solid-state energy-saving illumination field.
Can produce electroluminescent solid material has a variety of, 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, 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 the problem of visible angle, can manufacture on the substrate of unlike material, can make the many merits such as the product that can bend, and enjoys attracting attention of scientific and technological circle and industrial community in recent years.And along with the development of society, OLED technology (or by) colour TV, mobile phone, various indicating meter, various illumination with or the field such as display terminal of the military equipment such as decorative lamp, aircraft obtain using more and more widely.The electroluminescent material that can be used for OLED has fluorescent material and phosphor material two kinds.Because electroluminescent process produces the singlet excitons of 25% and the feature of 75% triplet exciton, and fluorescent material can only utilize singlet excitons, phosphor material then can utilize singlet excitons and triplet exciton and luminous simultaneously, and therefore the research and development of phosphor material seem particularly important.
The research and development object of phosphor material is all generally Metal-organic complex small molecule material instead of organic molecule, and reason is pure organic molecule, and at room temperature phosphorescence is very weak, can not detect phosphorescent emissions even at all.And title complex small molecule material can realize phosphorescent emissions easily, and can realize high efficiency luminescence, being also easy to preparation and purifying, being easy to be made into film, is therefore that a unique class is actually used in the phosphor material of OLED product luminescent layer at present.The phosphorescent substance that current OLED product adopts is the title complex containing the precious metal such as iridium, rhenium, and they have shown good use properties and market manifestation.Utilize these phosphor materials, the performance of LEC device has also had good performance.But there is cost intensive in such precious metals complex, the especially problem of environmental risk.Therefore, research and development at present for base metal Cu (I) complex phosphorescence material 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 green phosphorescent material on sale is at present all the title complex of precious metal iridium and platinum etc., although they are existing performance preferably in performance, the price of its costliness also has influence on applying of OLED the finished product and market manifestation.With Cu (I) title complex as green phosphorescent material then long-standing (N.Armaroli, G.Accorsi, F.Cardinali, A.Listorti, Top.Curr.Chem.2007,280,69-115.), Cu (I) complex luminescent material of this cheapness can be prepared easily by Cu (I) ion and suitable organic ligand, does not just still reach application demand in its luminous intensity of OLED operating temperature range.Therefore Cu (I) the title complex green phosphorescent 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 cuprous title complex green phosphorescent material based on pyridyl Phosphine ligands newly and preparation method thereof.By the solution coordination reaction of Cu (I) salt and organic ligand, facilitate and prepared the Cu of luminescent properties and good thermal stability (I) complex luminescent material at an easy rate, its green phosphorescent luminous intensity is very large, and its decay of luminescence feature meets OLED or LEC device to the requirement of material phosphorescence luminescent lifetime very much, is applied to the reduction that OLED or LEC device emitting layer material is conducive to product cost.
One of technical scheme of the present invention, is to provide a kind of cuprous title complex green phosphorescent material based on pyridyl Phosphine ligands newly, by Cu (I) salt Cu (CH
3cN)
4pF
6carry out substep coordination reaction with organic ligand to obtain, its molecular structure is [Cu (POP) (DPPY)] [Cu (POP) (DPPY) (i-PrOH)] (PF
6)
2(CH
2cl
2), in formula, POP is two (the 2-diphenylphosphine phenyl) ether of electric neutrality Phosphine ligands, and DPPY is pyridyl Phosphine ligands phenylbenzene-2-pyridyl phosphine.
Described luminescent material is rhombic system, Pca2
1spacer, unit cell parameters is
α=90 °, β=90 °, γ=90 °,
z=4, D
c=1.405g/cm
3, crystal color is colourless; This luminescent material structure shows as ionic complex, and wherein hexafluoro-phosphate radical is counter anion, and coordination cation then has two kinds, and methylene dichloride is filled in the room between title complex in addition in addition; In coordination cation, a kind of is the coordination cation formed by cuprous ion and part POP, DPPY complexing, and in this positively charged ion, cuprous ion adopts CuNP
3distortion tetrahedral coordination mode, one of them a P and N comes from P in a bidentate bridgingligand DPPY and pyridine groups respectively, and another two P then come from a bidentate bridgingligand POP; Another kind of coordination cation is the coordination cation formed by cuprous ion and part POP, DPPY, i-PrOH complexing, and in this positively charged ion, cuprous ion adopts CuOP
3tetrahedral coordination mode, one of them a P and O comes from the i-PrOH of an end group part DPPY and coordination respectively, and another two P then come from a bidentate bridgingligand POP; Its molecular structure is such as formula (I):
Described luminescent material is applied to green glow phosphor material, this material is subject to the UV-light of very wide wavelength region (300-450nm) or exciting of visible ray, very strong green light can be sent, its maximum emission wavelength is 510nm, chromaticity coordinates value is (0.2794,0.4117), luminescent lifetime is 5 microseconds.
Described green phosphorescent luminescent material is used as the luminescent layer phosphor material in the electroluminescent device of multilayer organic materials composition.
Technical scheme two of the present invention, is to provide a kind of cuprous title complex green phosphorescent material based on pyridyl Phosphine ligands [Cu (POP) (DPPY)] [Cu (POP) (DPPY) (i-PrOH)] (PF
6)
2(CH
2cl
2) preparation method.This preparation method is by Cu (CH
3cN)
4pF
6with the dichloromethane solution substep hybrid reaction of part POP, DPPY, finally revolve steaming and produce the crystal powder of product and realize.Its specific embodiments is divided into five steps:
(1) under room temperature by Cu (CH
3cN)
4pF
6powder is dissolved in acetonitrile completely, obtains settled solution A;
(2) under room temperature, POP powder is dissolved in methylene dichloride completely, obtains settled solution B;
(3) solution B is added in solution A, and stirring makes it complete reaction, obtains settled solution C;
(4) in solution C, add the dichloromethane solution D containing DPPY, and stirring makes it complete reaction;
(5) finally will react gained pale yellow solution to steam to dry at normal temperature decompression backspin, vacuum-drying, obtains crystalline white powder product.
In preparation method of the present invention, the mol ratio Cu (CH of described three kinds of reactants
3cN)
4pF
6: POP: DPPY is 1: 1: 1.
First beneficial effect of the present invention is the provided cuprous title complex green phosphorescent material based on pyridyl Phosphine ligands [Cu (POP) (DPPY)] [Cu (POP) (DPPY) (i-PrOH)] (PF
6)
2(CH
2cl
2), the pyridyl Phosphine ligands wherein introducing rigidity is conducive to molecular-excited state luminescence, Ni metal effectively can promote intersystem crossing to charge transtion (MLCT) feature of part, and the numerous phenyl ring on DPPY part and POP part, define very large sterically hindered around coordination ball, can the structural aberration of effective Inhibitory molecules excited state to be correlated with Nonradiative Decay Process, thus the phosphorescent emissions performance that had of this complex material.This complex material had both possessed the cheap advantage with being easy to purifying, and had good solvability and thermostability, for the further application of luminescent material provides technical support.
Secondly beneficial effect of the present invention is preparation cuprous title complex green phosphorescent material [Cu (POP) (DPPY)] [Cu (POP) (DPPY) (i-PrOH)] (PF based on pyridyl Phosphine ligands
6)
2(CH
2cl
2) method, have simple process, equipment used is simple, and raw material is simple and easy to get, and production cost is low, can obtain having the advantages such as the product of very high yield in a short period of time.
Accompanying drawing explanation
Fig. 1. phosphorescent complexes material [Cu (POP) (DPPY)] [Cu (POP) (DPPY) (i-PrOH)] (PF
6)
2(CH
2cl
2) the single crystal structure figure of molecule.
Fig. 2. phosphorescent complexes material [Cu (POP) (DPPY)] [Cu (POP) (DPPY) (i-PrOH)] (PF
6)
2(CH
2cl
2) molecule is in unit cell and the accumulation graph of peripheral space.
Fig. 3. phosphorescent complexes material [Cu (POP) (DPPY)] [Cu (POP) (DPPY) (i-PrOH)] (PF
6)
2(CH
2cl
2) X-ray powder diffraction: (a) be according in embodiment 2 single crystal structural data calculate obtain spectrogram; B () is the collection of illustrative plates of gained powder in the embodiment of the present invention 1.
Fig. 4. phosphorescent complexes material [Cu (POP) (DPPY)] [Cu (POP) (DPPY) (i-PrOH)] (PF
6)
2(CH
2cl
2) thermal gravimetric analysis curve, X-coordinate represents temperature, and ordinate zou represents weight percentage.
Fig. 5. phosphorescent complexes material [Cu (POP) (DPPY)] [Cu (POP) (DPPY) (i-PrOH)] (PF
6)
2(CH
2cl
2) ultraviolet-ray visible absorbing (UV-Vis) spectrogram.
Fig. 6. phosphorescent complexes material [Cu (POP) (DPPY)] [Cu (POP) (DPPY) (i-PrOH)] (PF
6)
2(CH
2cl
2) crystallite sample measure under 510 nanometer supervisory wavelength excite spectrogram.
Fig. 7. phosphorescent complexes material [Cu (POP) (DPPY)] [Cu (POP) (DPPY) (i-PrOH)] (PF
6)
2(CH
2cl
2) the light emission spectrogram that measures under 370 nano wave length optical excitation of crystallite sample.
Embodiment
The performance of implementation procedure of the present invention and material is illustrated by embodiment:
Embodiment 1
A large amount of phosphorescent complexes material [Cu (POP) (DPPY)] [Cu (POP) (DPPY) (i-PrOH)] (PF
6)
2(CH
2cl
2) preparation of crystallite sample: take 0.1mmol (37.3mg) [Cu (CH
3cN)
4] PF
6be dissolved in 5mL methylene dichloride, obtain settled solution A; Take 0.1mmol (53.9mg) POP to be again dissolved in 5mL methylene dichloride, obtain colorless cleared solution B; Solution B is joined in solution A, after stirring complete reaction, become settled solution C; Then take 0.1mmol (26.3mg) DPPY to be dissolved in 5mL methylene dichloride, obtain colourless transparent solution D; Joined lentamente by D in above-mentioned mixed solution C, stirred at rt for another makes it abundant reaction again; Finally filtered by gained pale yellow solution, and revolve all solvents of steaming removing, vacuum-drying, obtains white crystalline powder and is product, productive rate 94% (in Cu).
Embodiment 2
Synthesis phosphorescent complexes material [Cu (POP) (DPPY)] [Cu (POP) (DPPY) (i-PrOH)] (PF
6)
2(CH
2cl
2) monocrystalline: take embodiment 1 gained White crystalline product powder 50mg, again dissolve rear filtration completely with 10mL methylene dichloride, filtrate covers Virahol and impels product crystallization, leave standstill after a couple of days and separate out a large amount of colourless bulk crystals.The colourless bulk crystals selecting a 0.48mm × 0.40mm × 0.39mm size is used 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 phosphorescent complexes material [Cu (POP) (DPPY)] [Cu (POP) (DPPY) (i-PrOH)] (PF
6)
2(CH
2cl
2) pure phase crystal prototype carried out a series of performance test.Steady-state fluorescence test has been carried out to material crystals of the present invention, result shows that this material is under different excitation wavelength effects, can launch strong green light, and chromaticity coordinates value is (0.2794,0.4117), 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 5 microseconds, belongs to phosphorescent emissions.Visible, this material can be applicable to the green phosphorescent material that multi-wavelength excites, and is also suitable for very much the green phosphorescent material of OLED or LEC device luminescent layer.
Claims (4)
1. based on a cuprous title complex green phosphorescent material for pyridyl Phosphine ligands, it is characterized in that: the structural formula of luminescent material is [Cu (POP) (DPPY)] [Cu (POP) (DPPY) (i-PrOH)] (PF
6)
2(CH
2cl
2), in formula, POP is two (the 2-diphenylphosphine phenyl) ether of electric neutrality Phosphine ligands; In formula, DPPY is pyridyl Phosphine ligands phenylbenzene-2-pyridyl phosphine; Under room temperature, this complex luminescent material is rhombic system, Pca2
1spacer, unit cell parameters is
α=90 °, β=90 °, γ=90 °,
z=4, D
c=1.405g/cm
3, crystal color is colourless; This luminescent material structure shows as ionic complex, and wherein hexafluoro-phosphate radical is counter anion, and coordination cation then has two kinds, and methylene dichloride is filled in the room between title complex in addition in addition; In coordination cation, a kind of is the coordination cation formed by cuprous ion and part POP, DPPY complexing, and in this positively charged ion, cuprous ion adopts CuNP
3distortion tetrahedral coordination mode, one of them a P and N comes from P in a bidentate bridgingligand DPPY and pyridine groups respectively, and another two P then come from a bidentate bridgingligand POP; Another kind of coordination cation is the coordination cation formed by cuprous ion and part POP, DPPY, i-PrOH complexing, and in this positively charged ion, cuprous ion adopts CuOP
3tetrahedral coordination mode, one of them a P and O comes from the i-PrOH of an end group part DPPY and coordination respectively, and another two P then come from a bidentate bridgingligand POP; Its molecular structure is such as formula (I):
2. the preparation method of cuprous title complex green phosphorescent material according to claim 1, the method comprises the following steps:
(1) under room temperature by Cu (CH
3cN)
4pF
6powder is dissolved in acetonitrile completely, obtains settled solution A;
(2) under room temperature, POP powder is dissolved in methylene dichloride completely, obtains settled solution B;
(3) solution B is added in solution A, and stirring makes it complete reaction, obtains settled solution C;
(4) in solution C, add the dichloromethane solution D containing DPPY, and stirring makes it complete reaction;
(5) finally will react gained pale yellow solution to steam to dry at normal temperature decompression backspin, vacuum-drying, obtains crystalline white powder product.
3. the preparation method of cuprous title complex green phosphorescent material according to claim 2, is characterized in that: the mol ratio Cu (CH of described three kinds of reactants
3cN)
4pF
6: POP: DPPY is 1: 1: 1.
4. the application of cuprous title complex green phosphorescent material according to claim 1, is characterized in that described luminescent material has maximum emission peak at 510nm place, can be used as embedded photoluminescent material, or is used as the light emitting layer luminesces material in multilayer electroluminescent device.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN108794512A (en) * | 2017-04-28 | 2018-11-13 | 中国计量大学 | A kind of cuprous complex yellow phosphorescence material of double phosphines and triazole mixture |
| CN108794514A (en) * | 2017-04-28 | 2018-11-13 | 中国计量大学 | A kind of cuprous complex orange phosphor material of Xantphos and PBO mixed matchings |
| WO2021047132A1 (en) * | 2019-09-09 | 2021-03-18 | 苏州大学 | Fluorescent color-changing material, preparation method and application thereof |
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| JP2008303152A (en) * | 2007-06-05 | 2008-12-18 | Idemitsu Kosan Co Ltd | New copper complex and organic electroluminescent device using the same |
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2015
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| JP2008303152A (en) * | 2007-06-05 | 2008-12-18 | Idemitsu Kosan Co Ltd | New copper complex and organic electroluminescent device using the same |
| WO2013072508A1 (en) * | 2011-11-16 | 2013-05-23 | Cynora Gmbh | Heteroleptic copper complexes for optoelectronic uses |
| CN104140808A (en) * | 2014-06-10 | 2014-11-12 | 中国计量学院 | Tetrahedral cuprous complex luminescent material containing oxazolyl pyridine ligands |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| CN108794512A (en) * | 2017-04-28 | 2018-11-13 | 中国计量大学 | A kind of cuprous complex yellow phosphorescence material of double phosphines and triazole mixture |
| CN108794514A (en) * | 2017-04-28 | 2018-11-13 | 中国计量大学 | A kind of cuprous complex orange phosphor material of Xantphos and PBO mixed matchings |
| WO2021047132A1 (en) * | 2019-09-09 | 2021-03-18 | 苏州大学 | Fluorescent color-changing material, preparation method and application thereof |
| US11873449B2 (en) | 2019-09-09 | 2024-01-16 | Soochow University | Fluorescent chromic material, preparation method and use thereof |
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