CN104830321B - A kind of three-fold coordination type double-core Hydro-Giene (Water Science). complex luminescent material - Google Patents
A kind of three-fold coordination type double-core Hydro-Giene (Water Science). complex luminescent material Download PDFInfo
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- CN104830321B CN104830321B CN201510277818.2A CN201510277818A CN104830321B CN 104830321 B CN104830321 B CN 104830321B CN 201510277818 A CN201510277818 A CN 201510277818A CN 104830321 B CN104830321 B CN 104830321B
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Abstract
The invention discloses a kind of white red phosphorescent three-fold coordination double-core Hydro-Giene (Water Science). bunch base complex luminescent material and preparation method thereof partially.The phosphorescent complexes of the present invention, is carried out complexation reaction by Hydro-Giene (Water Science). and part and obtains, and its molecular structure is [CuI (o anisyl3P)]2·(CH3CN), o anisyl in formula3P is electric neutrality part three (o-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 by the direct hybrid reaction of solution of Hydro-Giene (Water Science). and three (o-methoxyphenyl) Phosphine ligands, has that simple process, equipment is simple, raw material is easy to get and low cost and other advantages.This material can be as luminescence generated by light white light emitting 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
Luminescent material includes luminescence generated by light and the big class application of electroluminescent two.Luminescence generated by light refers to that object is subject to the external world
The irradiation of light source, thus obtain energy and produce the phenomenon exciting and being finally directed at luminescence.Ultraviolet radiation, visible ray and infra-red radiation
Deng all causing luminescence generated by light.Embedded photoluminescent material can be used for fluorescence analysis, traffic signs, tracking and monitoring, agricultural light conversion film,
The aspects such as the scintillator in nuclear detection technology, the fluorescence optical collector in solar energy switch technology.Electroluminescent
(electroluminescent is called for short EL), refer to that luminescent material, under electric field action, is excited by electric current and electric field and sends out
The phenomenon of light, 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, letter
Claim 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 and lure very much
The application prospect of people, 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 operation principle of OLED is under the effect of extra electric field, and hole and electronics are respectively from positive and negative electrode infusion appliance
Part, is compounded to form exciton at luminescent layer, luminous by the attenuation of exciton.And according to spin statistics principle, singlet excitons and
Triplet exciton respectively accounts for 25% and 75%, so utilizing merely the luminescent layer that fluorescent material makes, and will be at most only with 25%
Input energy, other major part energy then can bring serious heating effect, not only the waste energy and also be unfavorable for device
Long-time stable works.Different from the fluorescent material only with singlet excitons energy, transient metal complex phosphor material
Owing to having the strongest SO coupling effect, all input energy including triplet and triplet can be made full use of,
25% energy existed in fundamentally breaching a very long time limits, and the efficiency of OLED is greatly improved, also
That is, utilize transient metal complex phosphor material that the internal quantum of OLED can be made to reach 100%.Therefore exist
In luminescent material based on OLED research, the research and development of phosphor material are particularly important.
More specifically being analyzed, OLED phosphor material the most on sale is all the coordination compound of precious metal iridium and platinum etc.,
Although they are existing preferably performance in performance, but the price of its costliness also has influence on the popularization and application of OLED final products
And market manifestation.With Cu (I) coordination compound as phosphor material the most long-standing (N.Armaroli, G.Accorsi,
F.Cardinali, A.Listorti, Top.Curr.Chem.2007,280,69-115.), this cheap Cu (I) coordination compound
Luminescent material can be prepared easily by Cu (I) ion and suitable organic ligand, simply in its luminescence of OLED operating temperature range
Intensity does not still reach application demand.Therefore develop novel cheap Cu (I) complex phosphorescence material and there is great actual application
It is worth.Realizing white light emission by a kind of material is then a more attractive problem.
Summary of the invention
It is an object of the invention to provide a kind of new white red phosphorescent three-fold coordination double-core Hydro-Giene (Water Science). bunch basigamy compound partially to send out
Luminescent material and preparation method thereof.By the solution complexation reaction of Hydro-Giene (Water Science). and organic ligand, conveniently and prepare at a low price
The three-fold coordination double-core Hydro-Giene (Water Science). bunch base complex luminescent material that luminescent properties is good, its white red phosphorescent luminous intensity partially is very
Greatly, and its decay of luminescence feature meets the OLED requirement to material phosphorescence luminescent lifetime very much, is applied to OLED
Emitting layer material is conducive to the reduction of product cost.
One of technical scheme, is to provide a kind of new white red phosphorescent three-fold coordination double-core Hydro-Giene (Water Science). bunch base partially
Complex luminescent material, is carried out complexation reaction by Hydro-Giene (Water Science). and part and obtains, and its molecular structure is [CuI (o-anisyl3P)
]2·(CH3CN), o-anisyl in formula3P is electric neutrality part three (o-methoxyphenyl) phosphine.
Described luminescent material is rhombic system, Pnma (No.62) space group, cell parameter α=90 °, β=90 °, γ=90 °,Z=4, Dc=
1.636g/cm3, crystal color is yellow, and profile is block；Coordination compound shows as three-fold coordination double-core Hydro-Giene (Water Science). bunch basigamy and closes
Thing, in double-core bunch, each Cu (I) uses CuI2P Atria coordination mode, one of them P comes from an end group o-
anisyl3P part, two other I is respectively two Cu (I) and shares, and presents the architectural feature of two trianglees limit connection altogether；
Material crystals is additionally gone back one CH of cocrystallization3CN；The molecular structure of luminescent material such as formula (I):
Described luminescent material is applied to white-light phosphor luminescent material, and this material is by the purple of the widest wave-length coverage (300-500nm)
Exciting of outer light or visible ray, can send the strongest white red light partially, and its maximum emission wavelength is 490nm, and chromaticity coordinates value is
(0.3602,0.3533), luminescent lifetime is 2 microseconds.
Described white red phosphorescent luminescent material partially is as the luminescent layer in the electroluminescent device of multilamellar organic material composition
Phosphor material.
The two of technical scheme, are to provide a kind of white red phosphorescent three-fold coordination double-core Hydro-Giene (Water Science). bunch basigamy partially and close
Thing luminescent material [CuI (o-anisyl3P)]2·(CH3CN) preparation method.This preparation method is by Hydro-Giene (Water Science). and part
There is complexation reaction after solution mixing, then solvent is removed thus separate out the crystal of product and realize.Its specific embodiments
It is divided into four steps:
(1) under room temperature, the powder of Hydro-Giene (Water Science). is completely dissolved in acetonitrile；
(2) under room temperature, the powder of part three (o-methoxyphenyl) phosphine is dissolved completely in acetonitrile；
(3) the two solution is mixed, and stirring is allowed to fully occur complexation reaction；
(4) reactant liquor is steamed at vacuumized conditions backspin, remove solvent and i.e. obtain the fine crystals product of yellow.
In the preparation method of the present invention, mol ratio CuI of the two reactant: o-anisyl3P is 1: 1.
First beneficial effects of the present invention is that the white red phosphorescent three-fold coordination double-core Hydro-Giene (Water Science). bunch basigamy partially provided closes
Thing luminescent material [CuI (o-anisyl3P)]2·(CH3CN), wherein halogen iodine serves not only as Bridged-ligends and constructs the double of molecule
Core bunch rigid structure, and the existence of iodine can change the excited state composition of molecule so that the charge transtion of Ni metal to part
(MLCT) excited state adds the biggest halogen charge transtion composition to part, and new (X+M) CT excited state can not only have
Effect promotes intersystem crossing and can effectively suppress the non-radiative decay of excited state；And the phosphine that on the other hand methoxyl group is contained at ortho position is joined
It is bigger sterically hindered that body three (o-methoxyphenyl) phosphine causes Cu (I) around to exist, can stable complex molecule well
Three-fold coordination configuration, thus the non-radiative decay of Inhibitory molecules excited state, thus the phosphorescent emissions that this molecular material has had
Energy.This complex material had both possessed advantage that is cheap and that be prone to purification, and had good dissolubility, entering for luminescent material
One step application provides technical support.
Beneficial effects of the present invention, next to that the white red phosphorescent three-fold coordination double-core Hydro-Giene (Water Science). bunch basigamy compound partially of preparation is sent out
Luminescent material [CuI (o-anisyl3P)]2·(CH3CN) method, has simple process, and device therefor is simple, and raw material is the easiest
, production cost is low, can obtain having the advantage such as product of very high yield in a short period of time.
Accompanying drawing explanation
Fig. 1. phosphorescent complexes [CuI (o-anisyl3P)]2·(CH3CN) mono-crystalline structures figure.
Fig. 2. phosphorescent complexes [CuI (o-anisyl3P)]2·(CH3CN) in unit cell and peripheral space accumulation graph.
Fig. 3. phosphorescent complexes [CuI (o-anisyl3P)]2·(CH3CN) X-ray powder diffraction spectrum: (a) is root
The spectrogram obtained is calculated according to single crystal structural data in embodiment 2；B () is the collection of illustrative plates of gained powder in the embodiment of the present invention 1.
Fig. 4. phosphorescent complexes [CuI (o-anisyl3P)]2·(CH3CN) ultraviolet-ray visible absorbing (UV-Vis) spectrum
Figure.
Fig. 5. coordination compound [CuI (o-anisyl3P)]2·(CH3CN) crystallite sample measures under 490 nanometer supervisory wavelength
Excite spectrogram.
Fig. 6. coordination compound [CuI (o-anisyl3P)]2·(CH3CN) crystallite sample light under 340 nano wave length light excite
Launch spectrogram.
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: weigh 60mg CuI and be dissolved in 20mL acetonitrile, weigh the o-of 110mg
anisyl3P part is dissolved in 20mL acetonitrile (mol ratio of described three kinds of reactants is 1: 1), is mixed by both solution, and
Stirring is allowed to fully occur complexation reaction, finally the rotation of gained yellow reaction liquid is evaporated off all solvents, and vacuum drying obtains Huang
Color crystal powder is product, productivity 99% (in terms of Cu).
Embodiment 2
Synthesis double-core Hydro-Giene (Water Science). bunch basigamy compound [CuI (o-anisyl3P)]2·(CH3CN) monocrystalline: weigh 19mg
After CuI is dissolved in 50mL acetonitrile, then by the o-anisyl of 36mg3P part once adds in above-mentioned solution, and stirring is allowed to complete
Filter after dissolving, filtrate covers isopropanol and promotes product to crystallize, after standing a couple of days, separate out a large amount of yellow bulk crystals.Select
The yellow bulk transparent crystal of one 0.26mm × 0.23mm × 0.18mm size is used for X-ray single crystal diffraction structured testing.Should
The molecular structure of compound is shown graphically in the attached figures 1, and its structure cell packed structures is illustrated in accompanying drawing 2.
To double-core Hydro-Giene (Water Science). bunch basigamy compound [CuI (o-anisyl3P)]2·(CH3CN) pure phase crystal prototype is carried out
A series of performance tests.Material crystals of the present invention has been carried out steady-state fluorescence test, and result shows that this material swashs different
Sending out under wavelength effect, can launch strong white red light partially, chromaticity coordinates value is (0.3602,0.3533), and concrete excites
Spectrum and emission spectrum are as shown in accompanying drawing 5 and accompanying drawing 6.And the transient state fluorometric investigation of this material is shown, its luminescent lifetime is 2 micro-
Second, belong to phosphorescent emissions.Visible, this material can be applicable to the white red phosphorescence material partially that multi-wavelength excites, and is also very suitable for
White light phosphor material for OLED luminescent layer.
Claims (5)
1. a white red phosphorescent three-fold coordination double-core Hydro-Giene (Water Science). bunch base complex luminescent material partially, it is characterised in that: luminous material
The structural formula of material is [CuI (o-anisyl3P)]2·(CH3CN), o-anisyl in formula3P is electric neutrality part three (O-methoxy
Phenyl) phosphine；Described luminescent material is rhombic system, Pnma (No.62) space group, cell parameterα=90 °, β=90 °, γ=90 °,Z=
4, Dc=1.636g/cm3, crystal color is yellow, and profile is block；Coordination compound shows as three-fold coordination double-core Hydro-Giene (Water Science). bunch base
Coordination compound, in double-core bunch, each Cu (I) uses CuI2P Atria coordination mode, one of them P comes from an end group o-
anisyl3P part, two other I is respectively two Cu (I) and shares, and presents the architectural feature of two trianglees limit connection altogether；
Described luminescent material crystal is additionally gone back one CH of cocrystallization3CN；The molecular structure of described luminescent material such as formula (I):
The preparation of white red phosphorescent three-fold coordination double-core Hydro-Giene (Water Science). bunch base complex luminescent material partially the most according to claim 1
Method, the method comprises the following steps:
(1) under room temperature, the powder of Hydro-Giene (Water Science). is completely dissolved in acetonitrile；
(2) under room temperature, the powder of part three (o-methoxyphenyl) phosphine is dissolved completely in acetonitrile；
(3) the two solution is mixed, and stirring is allowed to fully occur complexation reaction；
(4) reactant liquor is steamed at vacuumized conditions backspin, remove solvent and i.e. obtain the fine crystals product of yellow.
The preparation of white red phosphorescent three-fold coordination double-core Hydro-Giene (Water Science). bunch base complex luminescent material partially the most according to claim 2
Method, it is characterised in that: mol ratio CuI of the two reactant: o-anisyl3P is 1: 1.
The whitest red phosphorescent three-fold coordination double-core Hydro-Giene (Water Science). bunch base complex luminescent material partially should
With, it is characterised in that described luminescent material is used as white light embedded photoluminescent material.
The whitest red phosphorescent three-fold coordination double-core Hydro-Giene (Water Science). bunch base complex luminescent material partially should
With, it is characterised in that described luminescent material is used as the luminescent layer phosphorescence material in the electroluminescent device of multilamellar organic material composition
Material.
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| CN102851024A (en) * | 2012-09-28 | 2013-01-02 | 太原理工大学 | Organic electroluminescent material based on bis(2-diphenylphosphinophenyl)ether serving as ligand |
| CN102899029A (en) * | 2012-09-04 | 2013-01-30 | 中国计量学院 | Luminescent material of cuprous iodide complex and preparation method thereof |
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| CN102899029A (en) * | 2012-09-04 | 2013-01-30 | 中国计量学院 | Luminescent material of cuprous iodide complex and preparation method thereof |
| CN102851024A (en) * | 2012-09-28 | 2013-01-02 | 太原理工大学 | Organic electroluminescent material based on bis(2-diphenylphosphinophenyl)ether serving as ligand |
Non-Patent Citations (2)
| Title |
|---|
| COMPLEXES OF COPPER(I) WITH TRIPHENYLPHOSPHINE;G. COSTA et al.;《J. Inorg. Nucl. Chem.》;19651231;第27卷;2581-2584 * |
| Luminescent dinuclear copper(I) halide complexes double bridged by diphosphine ligands: Synthesis, structure characterization, properties and TD-DFT calculations;Xiayi Zhang et al.;《Polyhedron》;20140801;第81卷;687-694 * |
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