CN104861962A - Cu4I4 cubane-like cluster core complex luminous material based on phosphine ligand - Google Patents
Cu4I4 cubane-like cluster core complex luminous material based on phosphine ligand Download PDFInfo
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- CN104861962A CN104861962A CN201510277880.1A CN201510277880A CN104861962A CN 104861962 A CN104861962 A CN 104861962A CN 201510277880 A CN201510277880 A CN 201510277880A CN 104861962 A CN104861962 A CN 104861962A
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- cubane
- cu4i4
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- anisyl
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Abstract
The invention discloses a Cu4I4 cubane-like cluster core complex luminous material based on a phosphine ligand and a preparation method of the Cu4I4 cubane-like cluster core complex luminous material. A phosphorescent complex of the luminous material is obtained by cuprous iodide and a P-containing ligand through complexing, and has a molecular structural formula of Cu4I4(p-anisyl3P)4, in which p-anisyl3P is electrically neutral P-containing ligand tri(p-methoxyphenyl)phosphine. The complex has the advantages that micromolecules are easy to extract, the luminous efficiency is high and the complex is easily dissolved by using an organic solvent. The material is obtained by directly mixing and reacting the cuprous iodide and a solution of the P-containing ligand, and has the advantages of being simple and convenient in technology, simple in related equipment, high in raw material availability, low in cost and the like. The material can serve as a photoluminescence material, and can also serve as a luminous layer phosphor material in an electroluminescent device formed by multiple layers of an 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
One of material three large pillars being acknowledged as modern social development.And luminescent material is as wherein a kind of important functional materials, all has application widely especially in the field such as industry, agricultural, medical science, national defence.Concrete example, they can be used as white dyes, high-visibility pigment, fluorescence dye, fluorescent reagent, laser dyes, lamp phosphor etc.Particularly society is to the demand of various information displaying, and under energy dilemma background to energy-saving illumination in the urgent need to, facilitate developing rapidly of luminescent material widely.
Distinguish from principle of luminosity, 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) and Organic Light Emitting Diode (OrganicLight-Emitting Diode is called for short OLED).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.
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.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) salt 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 new green phosphorescent Cu4I4 class cubane bunch core complex luminescent material and preparation method thereof.By cuprous iodide and organic solution coordination reaction containing P part, facilitate and prepared the good Cu of luminescent properties (I) complex luminescent material at an easy rate, its green (partially yellow) phosphorescence luminous intensity is very large, and its decay of luminescence feature meets the requirement of OLED to material phosphorescence luminescent lifetime very much, is applied to the reduction that OLED emitting layer material is conducive to product cost.
One of technical scheme of the present invention, is to provide a kind of new green phosphorescent Cu4I4 class cubane bunch core complex luminescent material, and by cuprous iodide with organicly carry out solution coordination reaction obtain containing P part, its molecular structural formula is Cu
4i
4(p-anisyl
3p)
4, p-anisyl in formula
3p is that electric neutrality contains P part three (p-methoxyphenyl) phosphine.
Described luminescent material is triclinic(crystalline)system, P-1 spacer, unit cell parameters
α=88.232 (14) °, β=75.788 (11) °, γ=88.627 (11) °,
z=2, D
c=1.579g/cm
3, crystal color is colourless; This luminescent material shows as Cu4I4 class cubane bunch core title complex, and four Cu (I) in molecule all adopt CuI
3p tetrahedral coordination pattern, P wherein comes from unidentate ligand p-anisyl
3p, four I are then the iodide ion of three bridgings, just by these four I
-the bridging of ion, four CuI
3p tetrahedron constitutes four core class cubane bunch cored structures of limit connection altogether mutually between two; Its molecular structure is such as formula (I):
Described luminescent material is applied to green glow phosphor material, this material is subject to exciting of the UV-light of very wide wavelength region (200-380nm), very strong yellow-green light can be sent, its maximum emission wavelength is 540nm, chromaticity coordinates value is (0.3577,0.5256), luminescent lifetime is 3 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 green phosphorescent Cu4I4 class cubane bunch core complex luminescent material Cu
4i
4(p-anisyl
3p)
4preparation method.There is coordination reaction by cuprous iodide with after mixing containing the solution of P part in this preparation method, is then removed by solvent thus separate out the crystal of product and realize.Its specific embodiments is divided into four steps:
(1) under room temperature, the powder of CuI is dissolved in acetonitrile completely;
(2) under room temperature by part p-anisyl
3the powder of P is dissolved in methylene dichloride completely;
(3) by above-mentioned two kinds of solution mixing, and stirring makes it fully coordination reaction to occur;
(4) by reacting liquid filtering, and gained filtrate is steamed, except namely desolventizing obtains colourless fine crystals product at vacuumized conditions backspin.
In preparation method of the present invention, the mol ratio CuI:p-anisyl of described two kinds of reactants
3p is 1: 1.
First beneficial effect of the present invention is provided green phosphorescent Cu4I4 class cubane bunch core complex luminescent material Cu
4i
4(p-anisyl
3p)
4, the phosphor material of this neutrality obviously has higher against sensitive to oxygen molecule, and device can be made more stable, and efficiency is higher; P-anisyl
3in P part, P atom has stronger to characteristic electron, the halogen anion in structure is also had also to have to characteristic electron, the transfer transport mode of whole title complex is changed, effectively inhibit the structural aberration of excited state molecule, energy transfer efficiency is got a promotion, thus improves the luminous efficiency of material; Meanwhile, the p-anisyl of large steric hindrance
3p part is also conducive to suppressing excited state to distort the non-radiative decay caused; Therefore this material presents strong green light emission characteristic under ultraviolet excitation.This complex material had both possessed the cheap advantage with being easy to purifying, and had good solvability, for the further application of luminescent material provides technical support.
Secondly beneficial effect of the present invention is preparation green phosphorescent Cu4I4 class cubane bunch core complex luminescent material Cu
4i
4(p-anisyl
3p)
4method, 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 Cu
4i
4(p-anisyl
3p)
4the single crystal structure figure of molecule.
Fig. 2. phosphorescent complexes Cu
4i
4(p-anisyl
3p)
4molecule is in unit cell and peripheral space accumulation graph.
Fig. 3. phosphorescent complexes Cu
4i
4(p-anisyl
3p)
4x-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 Cu
4i
4(p-anisyl
3p)
4fourier transform infrared (FTIR) spectrogram.
Fig. 5. phosphorescent complexes Cu
4i
4(p-anisyl
3p)
4ultraviolet-ray visible absorbing (UV-Vis) spectrogram.
Fig. 6. phosphorescent complexes Cu
4i
4(p-anisyl
3p)
4the excitation spectrum that crystallite sample measures under 540 nanometer supervisory wavelength.
Fig. 7. phosphorescent complexes Cu
4i
4(p-anisyl
3p)
4the light emission spectrum of crystallite sample under 346 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: the cuprous iodide taking 0.3mmol is dissolved in 10mL acetonitrile and obtains solution A, takes the p-anisyl of 0.3mmol
3p part is dissolved in 10mL methylene dichloride and obtains solution B, by solution A and solution B mixing, and stirring makes it fully coordination reaction to occur, finally gained colourless solution is filtered, and revolve all solvents of steaming removing, vacuum-drying, obtains clear crystal powder and is product, productive rate 97% (in Cu).
Embodiment 2
Synthesis Cu (I) title complex Cu
4i
4(p-anisyl
3p)
4monocrystalline: the cuprous iodide of 0.1mmol to be dissolved in 4mL acetonitrile to obtain solution A, takes the p-anisyl of 0.1mmol
3p part is dissolved in 6mL methylene dichloride and obtains solution B, by solution A and solution B mixing, and stirring makes it fully coordination reaction to occur, and is finally filtered by gained colourless solution, filtrate covers normal hexane and impels product crystallization, after leaving standstill a couple of days, separate out a large amount of colourless bulk crystals.The clear crystal selecting a 0.32mm × 0.26mm × 0.23mm 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 title complex Cu
4i
4(p-anisyl
3p)
4pure 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 glow, and chromaticity coordinates value is (0.3577,0.5256), 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 3 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 luminescent layer.
Claims (5)
1. a green phosphorescent Cu4I4 class cubane bunch core complex luminescent material, is characterized in that: the structural formula of luminescent material is Cu
4i
4(p-anisyl
3p)
4, p-anisyl in formula
3p is that electric neutrality contains P part three (p-methoxyphenyl) phosphine; This luminescent material is triclinic(crystalline)system, P-1 spacer, unit cell parameters
α=88.232 (14) °, β=75.788 (11) °, γ=88.627 (11) °,
z=2, D
c=1.579g/cm
3, crystal color is colourless; This luminescent material shows as Cu4I4 class cubane bunch core title complex, and four Cu (I) in molecule all adopt CuI
3p tetrahedral coordination pattern, P wherein comes from unidentate ligand p-anisyl
3p, four I are then the iodide ion of three bridgings, just by these four I
-the bridging of ion, four CuI
3p tetrahedron constitutes four core class cubane bunch cored structures of limit connection altogether mutually between two; Its molecular structure is such as formula (I):
2. the preparation method of green phosphorescent Cu4I4 class cubane bunch core complex luminescent material according to claim 1, the method comprises the following steps:
(1) under room temperature, the powder of CuI is dissolved in acetonitrile completely;
(2) under room temperature by part p-anisyl
3the powder of P is dissolved in methylene dichloride completely;
(3) by above-mentioned two kinds of solution mixing, and stirring makes it fully coordination reaction to occur;
(4) by reacting liquid filtering, and gained filtrate is steamed, except namely desolventizing obtains colourless fine crystals product at vacuumized conditions backspin.
3. the preparation method of green phosphorescent Cu4I4 class cubane bunch core complex luminescent material according to claim 2, is characterized in that: mol ratio CuI: the p-anisyl of described two kinds of reactants
3p is 1: 1.
4. the application of green phosphorescent Cu4I4 class cubane bunch core complex luminescent material according to claim 1, is characterized in that described luminescent material is applied to green glow embedded photoluminescent material.
5. the application of green phosphorescent Cu4I4 class cubane bunch core complex luminescent material according to claim 1, is characterized in that described luminescent material is used as the luminescent layer phosphor material in the electroluminescent device of multilayer organic materials composition.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106867503A (en) * | 2017-03-18 | 2017-06-20 | 福州大学 | Reversible force/heat/solvent multiple stimulation responsive materials that cuprous iodide/tri- (4 chlorphenyl) phosphine is constructed and preparation method thereof |
| CN112920222A (en) * | 2021-02-08 | 2021-06-08 | 浙江理工大学 | Cuprous complex luminescent material, preparation method thereof and application of cuprous complex luminescent material in 2-methylpyrazine and pyrimidine VOCs (volatile organic compounds) sensing |
| CN113025316A (en) * | 2021-03-15 | 2021-06-25 | 山东大学 | High-quantum-yield copper nanocluster fluorescent nanoflower, preparation method thereof and application thereof in LED |
| CN113122229A (en) * | 2019-12-31 | 2021-07-16 | Tcl集团股份有限公司 | Quantum dot material, preparation method thereof, thin film and quantum dot light-emitting diode |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106867503A (en) * | 2017-03-18 | 2017-06-20 | 福州大学 | Reversible force/heat/solvent multiple stimulation responsive materials that cuprous iodide/tri- (4 chlorphenyl) phosphine is constructed and preparation method thereof |
| CN106867503B (en) * | 2017-03-18 | 2019-02-22 | 福州大学 | Reversible force/heat/solvent multiple stimulation responsive materials and preparation method thereof that cuprous iodide/tri- (4- chlorphenyl) phosphine is constructed |
| CN113122229A (en) * | 2019-12-31 | 2021-07-16 | Tcl集团股份有限公司 | Quantum dot material, preparation method thereof, thin film and quantum dot light-emitting diode |
| CN113122229B (en) * | 2019-12-31 | 2023-04-18 | Tcl科技集团股份有限公司 | Quantum dot material, preparation method thereof, thin film and quantum dot light-emitting diode |
| CN112920222A (en) * | 2021-02-08 | 2021-06-08 | 浙江理工大学 | Cuprous complex luminescent material, preparation method thereof and application of cuprous complex luminescent material in 2-methylpyrazine and pyrimidine VOCs (volatile organic compounds) sensing |
| CN112920222B (en) * | 2021-02-08 | 2023-10-03 | 浙江理工大学 | Cuprous complex luminescent material, preparation method thereof and application thereof in sensing of 2-methylpyrazine and pyrimidine VOCs |
| CN113025316A (en) * | 2021-03-15 | 2021-06-25 | 山东大学 | High-quantum-yield copper nanocluster fluorescent nanoflower, preparation method thereof and application thereof in LED |
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