CN104961770B - A kind of cuprous complex green phosphorescent material based on pyridine radicals phosphine part - Google Patents
A kind of cuprous complex green phosphorescent material based on pyridine radicals phosphine part Download PDFInfo
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- 0 CC(C)O*1(P(c2ccccc2)(c2ccccc2)c2ncccc2)P(c2ccccc2)(c2ccccc2)c(cccc2)c2Oc(cccc2)c2P1(c1ccccc1)c1ccccc1 Chemical compound CC(C)O*1(P(c2ccccc2)(c2ccccc2)c2ncccc2)P(c2ccccc2)(c2ccccc2)c(cccc2)c2Oc(cccc2)c2P1(c1ccccc1)c1ccccc1 0.000 description 1
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Abstract
The invention discloses a kind of cuprous complex green phosphorescent material based on pyridine radicals phosphine part and preparation method thereof.Phosphorescent complexes of the invention, are obtained by cuprous salt with ligand complex, and its molecular structure is [Cu (POP) (DPPY)] [Cu (POP) (DPPY) (i PrOH)] (PF6)2·(CH2Cl2), POP and DPPY are respectively double (the 2 diphenylphosphine phenyl) ethers of electroneutral Phosphine ligands and the pyridine radicals phosphine of diphenyl 2 in formula.The complex had both possessed small molecule and had been easily purified the advantage high with luminous efficiency, and with heat endurance high.The material is by Cu (CH3CN)4PF6Dichloromethane solution substep hybrid reaction with part POP, DPPY is obtained, with technique it is easy, equipment is simple, raw material is easy to get and low cost and other advantages.The material can be used as luminescence generated by light green light material, it is also possible to make the luminescent layer phosphor material in the electroluminescent device of multilayer organic material composition.
Description
Technical field
The present invention relates to luminescent material technical field, it is related to embedded photoluminescent material field and electroluminescent material field, it is special
It is not to be related to field of organic electroluminescent materials.
Background technology
Luminescent material includes luminescence generated by light and the major class application field of electroluminescent two.Luminescence generated by light refers to that object is subject to the external world
The irradiation of light source, so as to obtain energy production and excite and finally be directed at luminous phenomenon.Ultraviolet radioactive, visible ray and infra-red radiation
Deng can cause luminescence generated by light.Embedded photoluminescent material can be used for fluorescence analysis, traffic sign, tracking and monitoring, agricultural light conversion film,
The aspects such as the fluorescence optical collector in scintillator, solar energy switch technology in nuclear detection technology.Electroluminescent
(electroluminescent, abbreviation EL), refer to luminescent material under electric field action, excited by electric current and electric field and sent out
The phenomenon of light, is a kind of luminescence process that electric energy is converted directly into luminous energy.Material with this performance, can be fabricated to automatically controlled
Luminescent device, such as light emitting diode (LED), Organic Light Emitting Diode (Organic Light-Emitting Diode, abbreviation
) and luminescent electrochemical cell LEC (Light-emitting Electrochemical Cell) OLED.And LED and the major classes of OLED two
Product, all has very tempting application prospect in advanced FPD and solid-state energy-saving illumination field, and at present
Show its good industrialized development impetus.LEC also has very tempting application prospect in solid-state energy-saving illumination field.
Electroluminescent solid material can be produced many kinds, mainly including inorganic semiconductor material, organic molecule
Material, macromolecular material and complex small molecule material.There is energy-conservation, frivolous, free from glare due to OLED, without ultraviolet, nothing
Infrared ray, driving voltage are low, the response time is short, low-temperature characteristics is good, luminous efficiency is high, manufacturing process is simple, all solid state shock resistance
It is good, almost the problem without visible angle, can be manufactured on the substrate of unlike material, can to make the product that can bend etc. numerous
Advantage, enjoys attracting attention for scientific and technological circle and industrial circle in recent years.And with the development of society, OLED technology is color (or will)
The fields such as the display terminal of military equipment such as electricity, mobile phone, various displays, various illumination use or decorative lamp, aircraft obtain
More and more widely use.The electroluminescent material of OLED can be used for two kinds of fluorescent material and phosphor material.Due to electroluminescent hair
Photoreduction process produces 25% singlet excitons and the feature of 75% triplet exciton, and fluorescent material can only be swashed using singlet state
Son, phosphor material can then be lighted using singlet excitons and triplet exciton simultaneously, therefore the research and development of phosphor material seem outstanding
For important.
The research and development object of phosphor material, typically all Metal-organic complex small molecule material is rather than organic
Small molecule, reason is that phosphorescence is very weak at room temperature for pure organic molecule, or even can not detect phosphorescent emissions at all.And complex
Small molecule material can conveniently realize phosphorescent emissions, and can realize efficient luminous, be also easy to prepare and purify, easily
In being fabricated to film, therefore it is the phosphor material that a currently the only class is actually used in OLED product luminescent layers.Current OLED products
The phosphor for being used is the complex containing noble metals such as iridium, rheniums, and they have shown that preferable performance and market table
It is existing.Using these phosphor materials, the performance of LEC devices has also had preferable performance.But such precious metals complex is deposited
Costly, the especially problem of environmental risk.Therefore, currently for the research and development of base metal Cu (I) complex phosphorescence material
Receive much concern, Cu (I) complex very inexpensively, without environmental risk, therefore the Cu (I) of the new function admirable of research and development coordinates
Thing luminescent material is significant and good market application foreground.
More specifically it is analyzed, OLED green phosphorescent materials on sale at present are all the cooperations of precious metal iridium and platinum etc.
Thing, although their existing preferably performances in performance, but its expensive price also has influence on the popularization of OLED final products
Using and market manifestation.And with Cu (I) complexs as green phosphorescent material it is then long-standing (N.Armaroli,
G.Accorsi, F.Cardinali, A.Listorti, Top.Curr.Chem.2007,280,69-115.), this cheap Cu
(I) complex luminescent material can easily be prepared by Cu (I) ions and suitable organic ligand, simply in OLED operating temperature models
Enclose its luminous intensity and do not reach application demand still.Therefore developing new cheap Cu (I) complexs green phosphorescent material has weight
Big actual application value.
The content of the invention
It is an object of the invention to provide a kind of new cuprous complex green phosphorescent material based on pyridine radicals phosphine part and
Its preparation method.By the solution complexation reaction of Cu (I) salt and organic ligand, luminescent properties have been prepared conveniently and inexpensively
With Cu (I) complex luminescent material of good thermal stability, its green phosphorescent luminous intensity is very big, and its decay of luminescence feature
Meet very much the requirement of OLED or LEC devices to material phosphorescence luminescent lifetime, be applied to OLED or LEC devices and light
Layer material is conducive to the reduction of product cost.
One of technical scheme, is to provide a kind of new green phosphorus of the cuprous complex based on pyridine radicals phosphine part
Luminescent material, by Cu (I) salt Cu (CH3CN)4PF6Substep complexation reaction is carried out with organic ligand to obtain, its molecular structure is [Cu
(POP)(DPPY)][Cu(POP)(DPPY)(i-PrOH)](PF6)2·(CH2Cl2), POP is the double (2- of electroneutral Phosphine ligands in formula
Diphenylphosphine phenyl) ether, DPPY is pyridine radicals phosphine part diphenyl -2- pyridine radicals phosphines.
The luminescent material is rhombic system, Pca21Space group, cell parameter is α=90 °, β=90 °, γ=90 °,Z=4, DC=1.405g/cm3, crystal
Color is colourless；The luminescent material structure shows as ionic complex, and wherein hexafluoro-phosphate radical is counter anion, and is coordinated
Cation then has two kinds, and the room between complex is filled in addition with dichloromethane；In coordination cation, one kind is by cuprous
Ion and part POP, DPPY are complexed the coordination cation to be formed, and cuprous ion uses CuNP in the cation3Distortion tetrahedron
Type coordination mode, one of P and N is respectively from P and pyridine groups in a bidentate bridging ligand DPPY, and another
Two P then come from a bidentate bridging ligand POP；Another coordination cation, be by cuprous ion and part POP, DPPY,
I-PrOH is complexed the coordination cation to be formed, and cuprous ion uses CuOP in the cation3Tetrahedral coordination mode, wherein one
Individual P and O is respectively from the i-PrOH of an end group part DPPY and a coordination, and another two P then comes from one
Bidentate bridging ligand POP；Its molecular structure such as formula (I)：
The luminescent material is applied to green glow phosphor material, and the material is subject to the purple of wave-length coverage (300-450nm) very wide
Exciting for outer light or visible ray, can send very strong green light, and its maximum emission wavelength is 510nm, and chromaticity coordinates value is
(0.2794,0.4117), luminescent lifetime is 5 microseconds.
The green phosphorescent luminescent material is used as the luminescent layer phosphorescence in the electroluminescent device of multilayer organic material composition
Material.
The two of technical scheme, are to provide a kind of cuprous complex green phosphorescent material based on pyridine radicals phosphine part
Material [Cu (POP) (DPPY)] [Cu (POP) (DPPY) (i-PrOH)] (PF6)2·(CH2Cl2) preparation method.The preparation method
It is by Cu (CH3CN)4PF6With the dichloromethane solution substep hybrid reaction of part POP, DPPY, the crystalline substance of finally revolving generation product
Body powder and realize.Its specific embodiment is divided into five steps：
(1) at room temperature by Cu (CH3CN)4PF6Powder is completely dissolved in acetonitrile, obtains settled solution A；
(2) POP powder is completely dissolved in dichloromethane at room temperature, obtains settled solution B；
(3) by solution B add solution A in, and stirring be allowed to react completely, obtain settled solution C；
(4) it is allowed to react completely toward dichloromethane solution D of the addition containing DPPY in solution C, and stirring；
(5) finally reaction gained pale yellow solution is rotated to dry, vacuum drying under normal temperature decompression, obtains crystalline white
Color powdered product.
In preparation method of the invention, the mol ratio Cu (CH of three kinds of reactants3CN)4PF6: POP: DPPY is 1: 1:
1。
Beneficial effects of the present invention are the cuprous complex green phosphorescent materials based on pyridine radicals phosphine part for being provided first
Material [Cu (POP) (DPPY)] [Cu (POP) (DPPY) (i-PrOH)] (PF6)2·(CH2Cl2), wherein introducing rigid pyridine radicals
Phosphine ligands are conducive to molecular-excited state to light, and charge transtion (MLCT) feature of Ni metal to part can be effectively facilitated between being and altered
More, the numerous phenyl ring and on DPPY parts and POP parts, very big steric hindrance is formd around coordination ball, can be effective
Suppress the structural aberration correlation Nonradiative Decay Process of molecular-excited state, thus the phosphorescent emissions that the complex material has had
Energy.The complex material had both possessed advantage that is cheap and being easy to purifying, and was hair with good dissolubility and heat endurance
The further application of luminescent material provides technical support.
Beneficial effects of the present invention, next to that preparing the cuprous complex green phosphorescent material based on pyridine radicals phosphine part
[Cu(POP)(DPPY)][Cu(POP)(DPPY)(i-PrOH)](PF6)2·(CH2Cl2) method, it is easy with technique, it is used
Equipment is simple, and raw material is simple and easy to get, low production cost, can in a short period of time obtain having very product of high yield etc. excellent
Point.
Brief description of the drawings
Fig. 1 phosphorescent complexes material [Cu (POP) (DPPY)] [Cu (POP) (DPPY) (i-PrOH)] (PF6)2·
(CH2Cl2) molecule mono-crystalline structures figure.
Fig. 2 phosphorescent complexes material [Cu (POP) (DPPY)] [Cu (POP) (DPPY) (i-PrOH)] (PF6)2·
(CH2Cl2) molecule in unit cell and its peripheral space accumulation graph.
Fig. 3 phosphorescent complexes material [Cu (POP) (DPPY)] [Cu (POP) (DPPY) (i-PrOH)] (PF6)2·
(CH2Cl2) X-ray powder diffraction collection：A () is that the spectrogram for obtaining is calculated according to single crystal structural data in embodiment 2；(b)
It 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)] (PF6)2·
(CH2Cl2) thermal gravimetric analysis curve, abscissa represents temperature, and ordinate represents percetage by weight.
Fig. 5 phosphorescent complexes material [Cu (POP) (DPPY)] [Cu (POP) (DPPY) (i-PrOH)] (PF6)2·
(CH2Cl2) ultraviolet-ray visible absorbing (UV-Vis) spectrogram.
Fig. 6 phosphorescent complexes material [Cu (POP) (DPPY)] [Cu (POP) (DPPY) (i-PrOH)] (PF6)2·
(CH2Cl2) crystallite sample determined under 510 nanometers of supervisory wavelengths excite spectrogram.
Fig. 7 phosphorescent complexes material [Cu (POP) (DPPY)] [Cu (POP) (DPPY) (i-PrOH)] (PF6)2·
(CH2Cl2) crystallite sample excites the light emission spectrum figure of lower measure in 370 nano wave length light.
Specific embodiment
The performance of implementation process of the invention and material is illustrated by embodiment：
Embodiment 1
Substantial amounts of phosphorescent complexes material [Cu (POP) (DPPY)] [Cu (POP) (DPPY) (i-PrOH)] (PF6)2·
(CH2Cl2) crystallite sample preparation：Weigh 0.1mmol (37.3mg) [Cu (CH3CN)4]PF6It is dissolved in 5mL dichloromethane, obtains
Settled solution A；0.1mmol (53.9mg) POP is weighed again to be dissolved in 5mL dichloromethane, obtains colorless cleared solution B；By solution B
It is added in solution A, stirring turns into settled solution C after reacting completely；Then weigh 0.1mmol (26.3mg) DPPY and be dissolved in 5mL
In dichloromethane, colourless transparent solution D is obtained；D is slowly added into above-mentioned mixed solution C again, is stirred for making at room temperature
Abundant reaction；Finally gained pale yellow solution is filtered, and rotates all solvents of removing, vacuum drying obtains white crystal
Powder is product, yield 94% (in terms of Cu).
Embodiment 2
Synthesis phosphorescent complexes material [Cu (POP) (DPPY)] [Cu (POP) (DPPY) (i-PrOH)] (PF6)2·
(CH2Cl2) monocrystalline：The gained White crystalline product powder 50mg of embodiment 1 is weighed, is completely dissolved with 10mL dichloromethane again
After filter, isopropanol is covered on filtrate and promotes product to crystallize, separate out a large amount of colourless bulk crystals after standing a couple of days.Select one
The colourless bulk crystals of 0.48mm × 0.40mm × 0.39mm sizes are tested for x-ray crystal structure.The molecule of the compound
Structure chart is shown graphically in the attached figures 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)] (PF6)2·(CH2Cl2)
Pure phase crystal prototype carried out a series of performance tests.Steady-state fluorescence test is carried out to material crystals of the present invention, as a result table
The bright material can launch strong green light under different excitation wavelength effects, chromaticity coordinates value for (0.2794,
0.4117), specific excitation spectrum and emission spectrum are as shown in accompanying drawing 6 and accompanying drawing 7.And to the transient state fluorometric investigation table of the material
Bright, its luminescent lifetime is 5 microseconds, belongs to phosphorescent emissions.It can be seen that, the material can be applied to the green phosphorescent material that multi-wavelength excites
Material, is also very suitable for the green phosphorescent material for OLED or LEC device luminescent layers.
Claims (2)
1. a kind of cuprous complex green phosphorescent material based on pyridine radicals phosphine part, it is characterised in that：Green phosphorescent material
Structural formula is [Cu (POP) (DPPY)] [Cu (POP) (DPPY) (i-PrOH)] (PF6)2·(CH2Cl2), POP is electroneutral in formula
Double (the 2- diphenylphosphines phenyl) ethers of Phosphine ligands；DPPY is pyridine radicals phosphine part diphenyl -2- pyridine radicals phosphines in formula；This is green at room temperature
Color phosphor material is rhombic system, Pca21Space group, cell parameter isα
=90 °, β=90 °, γ=90 °,Z=4, DC=1.405g/cm3, crystal color is colourless；The green phosphorus
Luminescent material structure shows as ionic complex, and wherein hexafluoro-phosphate radical is counter anion, and coordination cation then has two kinds,
The room between complex is filled in addition with dichloromethane；In coordination cation, one kind be by cuprous ion and part POP,
DPPY is complexed the coordination cation to be formed, and cuprous ion uses CuNP in the cation3Distortion tetrahedral coordination mode, wherein
One P and N is respectively from P and pyridine groups in a bidentate bridging ligand DPPY, and another two P then comes from one
Individual bidentate bridging ligand POP；Another coordination cation, is complexed and is formed by cuprous ion and part POP, DPPY, i-PrOH
Coordination cation, cuprous ion uses CuOP in the cation3Tetrahedral coordination mode, one of P and O difference
Come from the i-PrOH of an end group part DPPY and a coordination, and another two P then comes from a bidentate bridging ligand
POP；Its molecular structure such as formula (I)：
2. the application of cuprous complex green phosphorescent material according to claim 1, it is characterised in that the green phosphorescent material
Material has maximum emission peak at 510nm, as embedded photoluminescent material, or can be sent out as the luminescent layer in multilayer electroluminescent device
Luminescent material.
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| 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 |
| 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 |
| 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 |
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| EP2594571A1 (en) * | 2011-11-16 | 2013-05-22 | Cynora GmbH | Copper complexes for optoelectronic applications |
| CN104140808B (en) * | 2014-06-10 | 2016-02-10 | 中国计量学院 | A kind of cuprous complex luminescent material of tetrahedral of Han oxazolyl pyridine ligand |
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