CN104861962B - A kind of Cu4I4 class cubane bunch core complex luminescent material based on Phosphine ligands - Google Patents
A kind of Cu4I4 class cubane bunch core complex luminescent material based on Phosphine ligands Download PDFInfo
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- CN104861962B CN104861962B CN201510277880.1A CN201510277880A CN104861962B CN 104861962 B CN104861962 B CN 104861962B CN 201510277880 A CN201510277880 A CN 201510277880A CN 104861962 B CN104861962 B CN 104861962B
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Abstract
The invention discloses a kind of Cu4I4 class cubane bunch core complex luminescent material based on Phosphine ligands and preparation method thereof.The phosphorescent complexes of the present invention, is obtained with the ligand complex containing P by Hydro-Giene (Water Science)., and its molecular structural formula is Cu4I4(p‑anisyl3P)4, p anisyl in formula3P is that electric neutrality contains P part three (p-methoxyphenyl) phosphine.Described coordination compound had both possessed little molecule and had been easily purified the advantage high with luminous efficiency, and had the advantage that easy-to-use organic solvent dissolves.This material is to be obtained with the direct hybrid reaction of solution containing P part by Hydro-Giene (Water Science)., has that simple process, equipment is simple, raw material is easy to get and low cost and other advantages.This material can be as embedded photoluminescent material, it is possible to as the luminescent layer phosphor material in the electroluminescent device of multilamellar organic material composition.
Description
Technical field
The present invention relates to luminescent material technical field, relate to embedded photoluminescent material field and electroluminescent material field, special
Do not relate to field of organic electroluminescent materials.
Background technology
One of material three big pillars being acknowledged as modern social development.And luminescent material is important as one of which
Functional material, all has application widely in the field such as industry, agricultural, medical science, national defence especially.For concrete example, it
Be used as fluorescent whitening agent, fluorescent pigment, fluorescent dye, fluorometric reagent, laser dye, lamp phosphor etc..Especially
Society demand that various information are shown, and under energy crisis background to energy-saving illumination in the urgent need to, greatly
Promote developing rapidly of luminescent material.
Distinguishing from principle of luminosity, luminescent material includes luminescence generated by light and the big class application of electroluminescent two.Luminescence generated by light
Refer to that object is irradiated by external light source, thus obtain energy and produce the phenomenon exciting and being finally directed at luminescence.Ultraviolet radiation,
Visible ray and infra-red radiation etc. all can cause luminescence generated by light.Embedded photoluminescent material can be used for fluorescence analysis, traffic signs, tracking prison
The aspects such as the scintillator in survey, agricultural light conversion film, nuclear detection technology, the fluorescence optical collector in solar energy switch technology.Electroluminescent
Luminous (electroluminescent is called for short EL), refer to that luminescent material, under electric field action, is excited by electric current and electric field
And the phenomenon of luminescence, it is a kind of luminescence process that electric energy is converted directly into luminous energy.There is the material of this performance, can be fabricated to
Automatically controlled luminescent device, such as light emitting diode (LED) and Organic Light Emitting Diode (Organic Light-Emitting
Diode, is called for short OLED).And the big series products of LED and OLED two, all have in advanced flat pannel display and solid-state energy-saving illumination field
There is the most tempting application prospect, and had shown that its good industrialized development impetus at present.
Electroluminescent solid material can be produced and have a variety of, mainly include inorganic semiconductor material, organic molecule
Material, macromolecular material and coordination compound small molecule material.Owing to OLED has energy-conservation, frivolous, free from glare, without ultraviolet, nothing
Infrared ray, driving voltage are low, response time is short, low-temperature characteristics is good, luminous efficiency is high, manufacturing process is simple, all solid state shock resistance
Good, almost without visible angle problem, can manufacture on the substrate of unlike material, can to make the product that can bend etc. numerous
Advantage, enjoys attracting attention of scientific and technological circle and industrial circle in recent years.And along with the development of society, OLED technology is color in (or will)
The fields such as the display terminal of electricity, mobile phone, various display, various illumination use or the military equipment such as decorative lamp, aircraft obtain
Use the most widely.The electroluminescent material that can be used for OLED has fluorescent material and phosphor material two kinds.Due to electroluminescent
Photoreduction process produces singlet excitons and the feature of 75% triplet exciton of 25%, and fluorescent material swashs only with singlet state
Son, phosphor material then can utilize singlet excitons and triplet exciton and luminous simultaneously, and 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 rather than organic
Little molecule, reason is that pure organic molecule at room temperature phosphorescence is the most weak, can not detect phosphorescent emissions the most at all.And coordination compound
Small molecule material can conveniently realize phosphorescent emissions, and can realize high efficiency luminescence, is also easy to prepare and purify, easily
In being fabricated to thin film, it therefore it is the currently the only class phosphor material that is actually used in OLED product luminescent layer.OLED product at present
The phosphor used is the coordination compound containing the noble metal such as iridium, rhenium, and they have shown that preferable serviceability and market table
Existing.But there is cost intensive in such precious metals complex, the especially problem of environmental risk.Therefore, currently for base metal
The research and development of Cu (I) complex phosphorescence material receive much concern, and Cu (I) coordination compound is very cheap, without environmental risk, therefore research and develop
Cu (I) complex luminescent material of novel function admirable is significant and good market application foreground.
More specifically being analyzed, OLED green phosphorescent material the most on sale is all the cooperation of precious metal iridium and platinum etc.
Thing, although they are existing preferably performance in performance, but the price of its costliness also has influence on the popularization of OLED final products
Application and market manifestation.With Cu (I) coordination compound as green phosphorescent material the most 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 be prepared easily by Cu (I) salt and suitable organic ligand, simply in OLED operating temperature range
Its luminous intensity does not still reach application demand.Therefore develop novel cheap Cu (I) coordination compound green phosphorescent material and have great
Actual application value.
Summary of the invention
It is an object of the invention to provide a kind of new green phosphorescent Cu4I4 class cubane bunch core complex luminescent material and
Preparation method.By Hydro-Giene (Water Science). and organic solution complexation reaction containing P part, facilitate and prepared photism at a low price
Cu (I) complex luminescent material that energy is good, its green (partially yellow) phosphorescence luminous intensity is very big, and its decay of luminescence feature is non-
Often meet the OLED requirement to material phosphorescence luminescent lifetime, be applied to OLED emitting layer material and be conducive to product cost
Reduction.
One of technical scheme, is to provide a kind of new green phosphorescent Cu4I4 class cubane bunch core coordination compound and sends out
Luminescent material, by Hydro-Giene (Water Science). with organic carry out solution complexation reaction containing P part and obtain, its molecular structural formula is Cu4I4(p-
anisyl3P)4, p-anisyl in formula3P is that electric neutrality contains P part three (p-methoxyphenyl) phosphine.
Described luminescent material is anorthic system, P-1 space group, cell parameter α=88.232 (14) °, β=75.788 (11) °, γ=88.627 (11) °,Z=
2, Dc=1.579g/cm3, crystal color is colourless；This luminescent material shows as Cu4I4 class cubane bunch core coordination compound, in molecule
Four Cu (I) all use CuI3P tetrahedral coordination pattern, P therein both is from monodentate ligand p-anisyl3P, and four I
It is then the iodide ion of three bridgings, is exactly based on this four I-The bridging of ion, four CuI3P tetrahedron constitutes the most common
Four core class cubane bunch cored structures of limit connection；Its molecular structure such as formula (I):
Described luminescent material is applied to green glow phosphor material, and this material is by the purple of the widest wave-length coverage (200-380nm)
Exciting of outer light, can send the strongest yellow-green light, and its maximum emission wavelength is 540nm, chromaticity coordinates value be (0.3577,
0.5256), luminescent lifetime is 3 microseconds.
Described green phosphorescent luminescent material is used as the luminescent layer phosphorescence in the electroluminescent device of multilamellar organic material composition
Material.
The two of technical scheme, are to provide a kind of green phosphorescent Cu4I4 class cubane bunch core coordination compound luminescence material
Material Cu4I4(p-anisyl3P)4Preparation method.This preparation method is to be occurred by after Hydro-Giene (Water Science). and the mixing of the solution containing P part
Complexation reaction, then removes solvent thus separates 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 completely in acetonitrile；
(2) by part p-anisyl under room temperature3The powder of P is dissolved completely in dichloromethane；
(3) above two solution is mixed, and stirring is allowed to fully occur complexation reaction；
(4) by reacting liquid filtering, and gained filtrate is steamed at vacuumized conditions backspin, remove solvent and i.e. obtain colourless thin
Small crystals product.
In the preparation method of the present invention, mol ratio CuI:p-anisyl of the two reactant3P is 1: 1.
First beneficial effects of the present invention is provided green phosphorescent Cu4I4 class cubane bunch core complex luminescent material
Cu4I4(p-anisyl3P)4, the phosphor material of this neutrality obviously has higher antiallergic perception, can make device more oxygen molecule
Stable, in hgher efficiency；p-anisyl3In P part, P atom has stronger to characteristic electron, also the halogen in structure bear from
Son also has to characteristic electron so that the electron transfer mode of whole coordination compound changes, and effectively inhibits excited state molecule
Structural aberration, make energy transfer efficiency get a promotion, thus improve the luminous efficiency of material；Meanwhile, the p-of big steric hindrance
anisyl3P part is also beneficial to the non-radiative decay suppressing excited state distortion to cause；Therefore this material under ultraviolet excitation in
The strongest green light emission characteristic.This complex material had both possessed advantage that is cheap and that be prone to purification, and had well
Dissolubility, the application further for luminescent material provides technical support.
Beneficial effects of the present invention, next to that preparation green phosphorescent Cu4I4 class cubane bunch core complex luminescent material
Cu4I4(p-anisyl3P)4Method, there is simple process, device therefor is simple, and raw material is simple and easy to get, and production cost is low, can
To obtain the advantages such as the product with very high yield in a short period of time.
Accompanying drawing explanation
Fig. 1. phosphorescent complexes Cu4I4(p-anisyl3P)4The mono-crystalline structures figure of molecule.
Fig. 2. phosphorescent complexes Cu4I4(p-anisyl3P)4Molecule is in unit cell and peripheral space accumulation graph.
Fig. 3. phosphorescent complexes Cu4I4(p-anisyl3P)4X-ray powder diffraction spectrum: (a) is according to embodiment 2
Middle single crystal structural data calculates the spectrogram obtained；B () is the collection of illustrative plates of gained powder in the embodiment of the present invention 1.
Fig. 4. phosphorescent complexes Cu4I4(p-anisyl3P)4Fourier transform infrared (FTIR) spectrogram.
Fig. 5. phosphorescent complexes Cu4I4(p-anisyl3P)4Ultraviolet-ray visible absorbing (UV-Vis) spectrogram.
Fig. 6. phosphorescent complexes Cu4I4(p-anisyl3P)4What crystallite sample measured under 540 nanometer supervisory wavelength excites
Spectrum.
Fig. 7. phosphorescent complexes Cu4I4(p-anisyl3P)4Crystallite sample light emission under 346 nano wave length light excite
Spectrum.
Detailed description of the invention
The process that realizes of the present invention and the performance of material are illustrated by embodiment:
Embodiment 1
The preparation of substantial amounts of crystallite sample: the Hydro-Giene (Water Science). weighing 0.3mmol is dissolved in 10mL acetonitrile to obtain solution A, claims
Take the p-anisyl of 0.3mmol3P part is dissolved in 10mL dichloromethane to obtain solution B, solution A and solution B is mixed, and stirs
Mix and be allowed to fully occur complexation reaction, finally gained colourless solution is filtered, and rotation is evaporated off all solvents, vacuum drying,
It is product, productivity 97% (in terms of Cu) to clear crystal powder.
Embodiment 2
Synthesis Cu (I) coordination compound Cu4I4(p-anisyl3P)4Monocrystalline: the Hydro-Giene (Water Science). of 0.1mmol is dissolved in 4mL acetonitrile
In solution A, weigh the p-anisyl of 0.1mmol3P part is dissolved in 6mL dichloromethane to obtain solution B, by solution A and solution
B mixes, and stirring is allowed to fully occur complexation reaction, is finally filtered by gained colourless solution, covers normal hexane and promote on filtrate
Make product crystallize, after standing a couple of days, separate out a large amount of colourless bulk crystals.Select a 0.32mm × 0.26mm × 0.23mm size
Clear crystal for x-ray crystal structure test.The molecular structure of this compound is shown graphically in the attached figures 1, its structure cell packed structures
It is illustrated in accompanying drawing 2.
To coordination compound Cu4I4(p-anisyl3P)4Pure phase crystal prototype carried out a series of performance test.To the present invention
Material crystals has carried out steady-state fluorescence test, and result shows that this material, under different excitation wavelength effects, can be launched strong
Strong green glow, chromaticity coordinates value is (0.3577,0.5256), concrete excitation spectrum and emission spectrum such as accompanying drawing 6 and accompanying drawing 7 institute
Show.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
It is applied to the green phosphorescent material that multi-wavelength excites, is also very suitable for the green phosphorescent material for OLED luminescent layer.
Claims (5)
1. green phosphorescent Cu4I4Class cubane bunch core complex luminescent material, it is characterised in that: the structural formula of luminescent material
For Cu4I4(p-anisyl3P)4, p-anisyl in formula3P is that electric neutrality contains P part three (p-methoxyphenyl) phosphine；This luminescent material
For anorthic system, P-1 space group, cell parameterα=88.232
° (14), β=75.788 (11) °, γ=88.627 (11) °,Z=2, Dc=1.579g/cm3, crystal face
Color is colourless；This luminescent material shows as Cu4I4Class cubane bunch core coordination compound, four Cu (I) in molecule all use CuI3P
Tetrahedral coordination pattern, P therein both is from monodentate ligand p-anisyl3P, four I are then the iodide ion of three bridgings, just
It is by these four I-The bridging of ion, four CuI3P tetrahedron constitutes the four core class cubanes bunch being the most mutually total to limit connection
Cored structure；Its molecular structure such as formula (I):
Green phosphorescent Cu the most according to claim 14I4The preparation method of class cubane bunch core complex luminescent material, the party
Method comprises the following steps:
(1) under room temperature, the powder of CuI is dissolved completely in acetonitrile；
(2) by part p-anisyl under room temperature3The powder of P is dissolved completely in dichloromethane；
(3) above two solution is mixed, and stirring is allowed to fully occur complexation reaction；
(4) by reacting liquid filtering, and gained filtrate is steamed at vacuumized conditions backspin, remove solvent and i.e. obtain colourless tiny crystalline substance
Body product.
Green phosphorescent Cu the most according to claim 24I4The preparation method of class cubane bunch core complex luminescent material, it is special
Levy and be: mol ratio CuI of the two reactant: p-anisyl3P is 1: 1.
Green phosphorescent Cu the most according to claim 14I4The application of class cubane bunch core complex luminescent material, its feature exists
It is applied to green glow embedded photoluminescent material in described luminescent material.
Green phosphorescent Cu the most according to claim 14I4The application of class cubane bunch core complex luminescent material, its feature exists
Luminescent layer phosphor material in described luminescent material is used as the electroluminescent device of multilamellar organic material composition.
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| 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 |
| 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 |
| 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 |
| CN113025316B (en) * | 2021-03-15 | 2021-12-28 | 山东大学 | High-quantum-yield copper nanocluster fluorescent nanoflower, preparation method thereof and application thereof in LED |
| CN115093436B (en) * | 2022-06-22 | 2024-09-06 | 南京邮电大学 | Preparation and application of X-ray scintillator based on rare earth oxygen cluster and cuprous iodide cluster |
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| EP2543672A1 (en) * | 2011-07-08 | 2013-01-09 | cynora GmbH | Copper(I) complexes, in particular for optoelectronic components |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101016292A (en) * | 2007-02-14 | 2007-08-15 | 南开大学 | 9-(1-Benzimidazolyl)acridine CuI complex, preparing method and application thereof |
| CN101402645A (en) * | 2008-11-17 | 2009-04-08 | 南开大学 | Benzimidazolyl-acridine ligand CuI complex and method of preparing the same |
| EP2543672A1 (en) * | 2011-07-08 | 2013-01-09 | cynora GmbH | Copper(I) complexes, in particular for optoelectronic components |
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