CN104893715B - Copper iodide phosphorescent complex light-emitting material containing Cu4I4 cluster core - Google Patents
Copper iodide phosphorescent complex light-emitting material containing Cu4I4 cluster core Download PDFInfo
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Abstract
The invention discloses a yellow green phosphorescent complex light-emitting material containing a Cu4I4 cubane cluster core and a preparation method of the yellow green phosphorescent complex light-emitting material. The phosphorescent complex is prepared by complexing copper iodide and a P-containing ligand and has a molecular structure as follows: Cu4I4(m-anisyl3P)4, wherein m-anisyl3P in the formula is a P-containing ligand electric-neutral tri(m-methoxyphenyl)phosphorus. The complex is not only easily purified because of being micromolecular and high in light-emitting efficiency, but also is easily dissolved by using an organic solvent. The material is obtained by directly mixing copper iodide and a P-containing ligand solution and reacting and has the advantages that the process is simple and convenient, the equipment is simple, raw materials are available, the cost is low and the like. The material can be used as a photoluminescent material and can also be used as a phosphorescent material for a light-emitting layer in an electroluminescent device made of multilayer organic materials.
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 yellow/green phosphor material the most on sale is all precious metal iridium and platinum etc.
Coordination compound, although they are existing preferably performance in performance, but the price of its costliness also has influence on OLED final products
Popularization and application and market manifestation.The most long-standing as yellow/green phosphor material with Cu (I) coordination compound
(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 at OLED
Its luminous intensity of operating temperature range does not still reach application demand.Therefore novel cheap Cu (I) coordination compound yellow/green is developed
Phosphor material has great actual application value.
Summary of the invention
It is an object of the invention to provide a kind of new yellow green phosphorescence Cu4I4 class cubane bunch core complex luminescent material and
Its preparation method.By Hydro-Giene (Water Science). and organic solution complexation reaction containing P part, facilitate and prepared luminescence at a low price
Cu of good performance (I) complex luminescent material, phosphorescence luminous intensity is very big for its yellow green (partially yellow), and its decay of luminescence is special
Levy the requirement meeting very much OLED to material phosphorescence luminescent lifetime, be applied to OLED emitting layer material and be conducive to product
The reduction of cost.
One of technical scheme, is to provide a kind of new yellow green phosphorescence Cu4I4 class cubane bunch core coordination compound
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(m-
anisyl3P)4, m-anisyl in formula3P is that electric neutrality contains P part three (m-methoxyphenyl) phosphine.
Described luminescent material is monoclinic system, C2/c space group, cell parameter A=90 °, β=118.656 (10) °, γ=90 °,Z=4, Dc=1.653g/
cm3, crystal color is colourless；This luminescent material shows as Cu4I4 class cubane bunch core coordination compound, four Cu (I) in molecule
All use CuI3P tetrahedral coordination pattern, P therein both is from monodentate ligand m-anisyl3P, four I are then three bridgings
Iodide ion, be exactly based on this four I-The bridging of ion, four CuI3P tetrahedron constitutes and is the most mutually total to the four of limit connection
Core class cubane bunch cored structure；Its molecular structure such as formula (I):
Described luminescent material is applied to green-yellow light phosphor material, and this material is by the widest wave-length coverage (200-370nm)
Exciting of ultraviolet light, can send the strongest yellow-green light, and its maximum emission wavelength is 550nm, chromaticity coordinates value be (0.3766,
0.5296), luminescent lifetime is 4 microseconds.
Described yellow green phosphorescent light-emitting materials is used as the luminescent layer phosphorus in the electroluminescent device of multilamellar organic material composition
Luminescent material.
The two of technical scheme, are to provide a kind of yellow green phosphorescence Cu4I4 class cubane bunch core coordination compound luminous
Material C u4I4(m-anisyl3P)4Preparation method.This preparation method is to be sent out by after Hydro-Giene (Water Science). and the mixing of the solution containing P part
Raw 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 m-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:m-anisyl of the two reactant3P is 1: 1.
First beneficial effects of the present invention is provided yellow green phosphorescence Cu4I4 class cubane bunch core coordination compound luminescence material
Material Cu4I4(m-anisyl3P)4, the phosphor material of this neutrality obviously has higher antiallergic perception, can make device oxygen molecule
More stable, in hgher efficiency；m-anisyl3In P part, P atom has stronger to characteristic electron, and also the halogen in structure is born
Ion also has to characteristic electron so that the electron transfer mode of whole coordination compound changes, and effectively inhibits excited state to divide
The structural aberration of son, makes energy transfer efficiency get a promotion, thus improves the luminous efficiency of material；Meanwhile, the m-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 yellow-green light emission characteristic.This complex material had both possessed advantage that is cheap and that be prone to purification, and had very well
Dissolubility, the further application for luminescent material provides technical support.
Beneficial effects of the present invention, next to that preparation yellow green phosphorescence Cu4I4 class cubane bunch core complex luminescent material
Cu4I4(m-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(m-anisyl3P)4The mono-crystalline structures figure of molecule.
Fig. 2. phosphorescent complexes Cu4I4(m-anisyl3P)4Molecule is in unit cell and peripheral space accumulation graph.
Fig. 3. phosphorescent complexes Cu4I4(m-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(m-anisyl3P)4Fourier transform infrared (FTIR) spectrogram.
Fig. 5. phosphorescent complexes Cu4I4(m-anisyl3P)4Ultraviolet-ray visible absorbing (UV-Vis) spectrogram.
Fig. 6. phosphorescent complexes Cu4I4(m-anisyl3P)4What crystallite sample measured under 550 nanometer supervisory wavelength excites
Spectrum.
Fig. 7. phosphorescent complexes Cu4I4(m-anisyl3P)4Crystallite sample light emission under 340 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 m-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 96% (in terms of Cu) to clear crystal powder.
Embodiment 2
Synthesis Cu (I) coordination compound Cu4I4(m-anisyl3P)4Monocrystalline: the Hydro-Giene (Water Science). of 0.1mmol is dissolved in 4mL acetonitrile
In solution A, weigh the m-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 0.49mm × 0.48mm × 0.43mm 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(m-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-yellow light, chromaticity coordinates value is (0.3766,0.5296), 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 4 microseconds, belongs to phosphorescent emissions.Visible, this material can
It is applied to the yellow green phosphor material that multi-wavelength excites, is also very suitable for the yellow green phosphor material for OLED luminescent layer.
Claims (5)
1. a yellow green phosphorescence Cu4I4 class cubane bunch core complex luminescent material, it is characterised in that: the structure of luminescent material
Formula is Cu4I4(m-anisyl3P)4, m-anisyl in formula3P is that electric neutrality contains P part three (m-methoxyphenyl) phosphine；This luminescence material
Material is monoclinic system, C2/c space group, cell parameterα=
90 °, β=118.656 (10) °, γ=90 °,Z=4, Dc=1.653g/cm3, crystal color is colourless；
This luminescent material shows as Cu4I4 class cubane bunch core coordination compound, and four Cu (I) in molecule all use CuI3P tetrahedron is joined
Bit pattern, P therein both is from monodentate ligand m-anisyl3P, four I are then the iodide ion of three bridgings, are exactly based on this
Four I-The bridging of ion, four CuI3P tetrahedron constitutes the four core class cubane bunch cored structures being the most mutually total to limit connection；
Its molecular structure such as formula (I):
The most according to claim 1, the preparation method of yellow green phosphorescence Cu4I4 class cubane bunch core complex luminescent material, should
Method comprises the following steps:
(1) under room temperature, the powder of CuI is dissolved completely in acetonitrile；
(2) by part m-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.
The preparation method of yellow green phosphorescence Cu4I4 class cubane bunch core complex luminescent material the most according to claim 2, its
It is characterised by: mol ratio CuI of the two reactant: m-anisyl3P is 1: 1.
The application of yellow green phosphorescence Cu4I4 class cubane bunch core complex luminescent material, its feature the most according to claim 1
It is that described luminescent material is applied to green-yellow light embedded photoluminescent material.
The application of yellow green phosphorescence Cu4I4 class cubane bunch core complex luminescent material, its feature the most according to claim 1
It is the luminescent layer phosphor material that described luminescent material is used as in the electroluminescent device of multilamellar organic material composition.
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| CN108586536B (en) * | 2018-06-29 | 2020-04-28 | 湖北大学 | 2- [ (2-dimethylamino phenyl) (phenyl) phosphine ] -N, N-dimethylaniline cuprous iodide complex and synthetic method thereof |
| CN113896738B (en) * | 2020-06-22 | 2023-10-20 | 福建江夏学院 | Non-rare earth copper-iodine cluster-based yellow fluorescent powder and synthetic method and application thereof |
| 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 |
| CN113025107B (en) * | 2021-05-10 | 2021-12-21 | 中山大学 | Preparation method and application of cuprous iodide-based hybrid fluorescent coating |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626789A (en) * | 2013-11-22 | 2014-03-12 | 中国计量学院 | Binuclear cuprous complex luminescent material and preparation method thereof |
| CN103865523A (en) * | 2014-03-03 | 2014-06-18 | 中国计量学院 | Double-core cuprous iodide complex luminescent material |
| CN103880867A (en) * | 2014-03-03 | 2014-06-25 | 中国计量学院 | Di-nuclear cuprous complex green luminescent material and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626789A (en) * | 2013-11-22 | 2014-03-12 | 中国计量学院 | Binuclear cuprous complex luminescent material and preparation method thereof |
| CN103865523A (en) * | 2014-03-03 | 2014-06-18 | 中国计量学院 | Double-core cuprous iodide complex luminescent material |
| CN103880867A (en) * | 2014-03-03 | 2014-06-25 | 中国计量学院 | Di-nuclear cuprous complex green luminescent material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Using cuprophilicity as a multi-responsive chromophore switching color in response to temperature, mechanical force and solvent vapors;Xiao-Chen Shan et al.;《Journal of Materials Chemistry C》;20130501;第1卷;4339–4349 * |
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